UNCLASSIFIED A.E.R.E. I@.

2673
NPcc/mm/211

I N URA"[ALLOYS WITH HIGH SOIUTE

!I!RA.NSI?O~UTIONS
SOUBILITY I N THE B.C.C. y PKASE

PART I

P r e l i m h a y Observations On The "Banded Structures" Produced By Non

Equilibrium Transf'ormat ions I n U r a n i u m Alloys.

by
A, G. HaRDING
M, B. WALIlRON

ABSTRACT

The high temperature body centred cubic y phase i n uranium a l l o y s with

approximately I O at 7; titanium, niobium, zirconium, o r molybdenum can be
rendered metastable under c r i t i c a l cooling conditions; it may transform
thence by a shear mechanism t o form a characteristic banded structure or
by a nucleation and growth process t o equiaxed grains. These decomposition
structures w i t h d i f f e r i n g m t a l l o g r a p h i c appearances give similar X-ray
patterns. The structures are designated " d i s t o r t e d a" since the p a t t e r n s
correspond t o a contraction i n t h e b-direction of the no- orthorhombic
a c e l l . The formation of these metastable structures i s apparently
dependent upon composition, cooling r a t e and the effect of the solute
element on the incubation period and decomposition rate of the metastable
y phase.

U.K. A.E.A.Research Group,

Atomic Energy Research Establishment,
HAR:am.

September, 1958.
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 Page
I. Introduction I

2. R e ~ a r a t i o nof SIXcimens 2
hiaterials 2
Alloy preparation 2

3. Le tallography 2
4- Experimental methods 3
(I) Control of cooling r a t e 3
(2) Q u a l i t a t i v e deformation experiments 3
5. ILe tslllographic observations on the occurrance of
" b b d e d s t r u c t u r e s " i n uranium-titanium a l l o y s 3
(I ) E f f e c t of cooling rate on microstructure of
uranium-ti t anium a l l o y s 4
( 2 ) Effect of uranium p u r i t y on microstructure af
quenched uranium 11.5 a t d) titanium a l l o y s 4
( 3 ) E f f e c t of end quenching on microstructure of
uranium- 11.5 at sb titanium alloys 5
6. Influence of d i f f u s i o n r a t e on microstmctures of alloys w i t h
niobium, molybdenum, titanium and sirconium 6
(I) Xffect of end quenching from y phase i n t o mercury 6
( 2 ) Effect of annealing a l l o y s end quenched i n t o mercury 6
( 3 ) Effect of end quenching from y phase i n t o backing
pump oil 7
7. Annealing of' "banded s t r u c t u r e s " i n uranium-titanium a l l o y s 8
8. The e f f e c t of d e f o m t i o n of r e t a i n e d y phase i n a l l o y s of
uranium 12 at 7~ titanium and 12 at $ molybdenum 8

9. Annealing of r e t a i n e d y phase i n uranium I 2 at 70 titanium a l l o y s 9

IO. X-ray exarninat ion 9
11. D i 3 cussion 9
hc1:novil edf';ernents 12

lieference s 43
11. 5"ab:lc 01' rnicrostruc:tures o f uranium- 4..9 at.?;, 9.2 at.70
and -13.5 at.;^ Litaniuin d . l o y s on quenching and air
cooling,. 4-
111. The ei'f'ect of uranium purity on t h e microstructure af'
quenched uranitun 1 1 .T tits.niun alloys 5
IV. Table of phases i d e r i t i f i e t i by X - r a y and metallography 15
 A c l i a r a c t e r i s t i c banded microstructure w a s observed a t A.E.R.E. during
investiktation of t h e s t a b i l i t y of a grain s i z e a f t e r annealing uranium
a l l o y s ctmta.ining 9.2 a t ;;J t i t a n i u m , quenched from the y phase. (Fig. 1
and 7 ) ; other b i n r y s t r u c t u r e has been noted are
uranium-t it aniuni ? 3 9 4 9 51, uran+um-T@ybdenum (496)P
uranium-vanadium k j thorium-zirconnun , and i n the
ternary uranium- zirconium-t it a n i urn

Various explanations have bEen advanced t o account for t h i s structure.

I n e a r l y w r Lon the uranium-titanium equilibriuii diagram Buzzard, L i s s ,
and Ficl- e PA a t t r i b u t e d i t t o a dispersion of two phases y a d 6 , whilst
I h a p t o n ~ 2 ) ,considered it a m r n a l y associated w i t h an unidentified
iiipurity. hnerican reportsY4,5) describe the banded structure as
" d i s t o r t e d u t ' , i d e n t i f i e d i n a uranium 11.5 at. 5; moJ,yl)rl$num a l l o y )(': as

w.
a body ce t r e d orthorhombic c e l l of dimensions a = 7.00 A b = 6-84 A
c=3.42

A review of' the uranium a l l o y systems i n which t h i s structure has been

found shows t'nat i n each case thc body centred cubic (U.C.C.) y phase,
s t a b l e a t high temperature and W:L th ccmsidei-able solute s o l u b i l i t y ,
decornposes t o an orthorhombic a at l o w temperature i n equilibrium with a
second phase, e.g. the compound IJ2Ti i n the uranium-titanium system or t h e
s o l i d s o l u t i o n y ' i n the uranium.-molybdenum system.

A bancied st t u r e of s i m i l a r metallographic appearance i n indium-

thallium a l l o y s ?"), has been a t t r i b u t e d t o the thermal transf'ormation of
the high temperature f ace-centred cubic t o ' low temperature f ace-centred
tetragono1 (3'. C. T ) s o l i d solution and t e ystallographic r e l a t i o n s h i p s
of' transformation have been determined tq2T
system, a similar structure i s developed when a B. C.C. phase t r a n f o
I n t h e vanadium-oqgen

to form a lovr teinperature ordered body-centred tetragonol l a t t i c e 91 3 y

Comparable bands are produced on, P. C. T.
copper-manganese and :'pqg~11 I ( ' 4 d )
- B. C. C. trarsformati 011 i n
has a t t r i b u t e d t h e i r f orination t o
tviirming. 1:iiodownick has reviewed the literature oil inetastable
transfornations i n copper-zinc, copper-tin and copper-alununium, 111 thesc
systems, over a lirnited co~iipositj.onrange, both a c i c l a r m d banded t y p
s t r u c t u r e s a r e produced by + shear transformation of metastable

Baniec s t r u c t u r e uranium d l o y s are technologically iinpor h n t

since i t i s reported t h a t r e t a i n e d y i n uranium molybdenum a d
strained a in ura_niyn-niobium shcvr enhanced corrosion resistance t o h.igh
te;nperatwe water ( ~OGQC).

The puq>ose of $ h i s i n v e s t i l p t i o n therefore was a s c e r t a i n the

q u a l i t a t i v e conditions necessary t o develop t h i s structure in uranium
- ~ I l o y s ,studyirq p r i n c i p a l l y the system uraniurn-titaniwi1.
 Three types of uranium of d i f f e r e n t e x t r a c t i o n h i s t o r y were used.

1. Early B r i t i s h calcium reduced uranium.

2. American calcium reduced uranium.

3. S p r i n g i e l d s magnesium reduced uranium.

Analyses of these metals a r e presented i n Table I.

The alloying additions came from a number of sources. V a n Arkel t i t a n i u m

w a s supplied by I. C. I. Metals Division Research Department, molybdenum f r o m
normal Biurex 0.020'' sheet, niobium with a n annealed hardness of 80-90 VPN
from Springfields; and graphite melted -011 zirconium from Murex.

Analyses of these metals a r e cpoted in Table I.

2.2 Alloy preparation

A l l alloys were prepared by arc c a s t i n g on a water-cooled copper hearth

using a tungsten electrode i n a n atmosphere of g e t t e r e d argon under reduced
pressure. Alloy specimens o r 60 gms. w e r e c a s t i n t o a sausage shaped mould,
homogeneity being achieved by repeated turning and remelting.

Ingots for end quenching experiments w e r e loosely canned i n a mild s t e e l

tube, swaged a t 6WoC from -0.4-0" t o -0.26" dianaeter and f i n a l l y machined
t o 0.250" f .001". To prevent oxidation during'annealing, specimens were
sealed i n a vacuum of -0.05 nun Hg. i n silica capsules; when annealing a t
1000°C specimens were loosely wrapped i n 0.010" tantalum f o i l t o prevent
r e a c t i o n with t h e silica.

IJe tallography

Samples were mounted e i t h e r i n b a k e l i t e or i n cold s e t t i n g LIarco r e s i n

S.B. 28c. a t room temperature without applied stress. For i n i t i a l preparation,
t o reduce t o a minimum surface deformation induced by polishing, only
320-600 grade Tri-M-ite papers were used, with p a r a f f i n as a lubricant.
Subsequent polishing with 5-15r-I diamond paste on blanket c l o t h w a s followed
by 5-10 minutes a t t a c k polish on a m a t t terylene c l o t h impregnated with a
suspension of l5cc y A120 i n 25cc concentrated HN03, 25cc Cr20 and 50cc
a
H20. Most s t r u c t u r e s i n ?hese a l l o y s were revealed by p o l a r i s e l i p l i t a f t e r
a t t a c k polish. I n the uranium-titanium system, the banded s t r u c t u r e responded

cathode and current density of -

t o electro-etchirqy i n t h e attack p o l i s h y l u t i o n a t 300C using a u r a n i ~ u n
4 anip/cm . The compound i n t h i s s-ytem
U z T i , c o u l i L be made t o contract markedly w i t h an a matrix by room teinperature
o x i u a t i o n f'm 413 hours. A l l o y s of uranium- niobium were cxmnined riiore
oatisf'actorily a f t e r a n a t t a c k polish i n 5Occ concentrated lPj0 l0cc
vmcentrat,ed HiJOj, locc concenkatcil F I ~ S O ~6, droi>s 40,~HF and J C C Cr203. 4'

- 2 -
 Following t h i s polish the struct;ure could be viewed by normal illumination.
Alloys of uranium-molybdenum res8ponded to a t t a c k polishing i n chromic- n i t r i c
i n t h e quenched condition. I n the annealed s t a t e , y and a could be
contrasted by a 20 secondp e t c h i n a mixture of 5Occ concentrated n i t r i c
acid and 50cc g l a c i a l ace t i c acid.

4. Experimeiltd methods

bo1 Control of cooling r a t e

I n the i n i t i a l experiments, specimens were cooled e i t h e r by breaking

t h e capsule under water, by immersion of the encapsulated specimen i n
water, o r by allowing t o c o o l i n air. Since f i n e r control proved ne e s m y ,
use was made of an end penching apparatus at Battersea Polytechnic p177,
modified i n both specimen holder and quenching f l u i d : the holder w a s made
i n eircaloy, since the e x i s t i n g one i n s t a i n l e s s s t e e l would have alloyed
with the uranium specimen at 10o(l°C, and a s i l i c o n e vacuum o i l w a s used
i n l i e u of the mercury quench, s:ince surface alloying could be detrimental
i n subsequent annedings. Mercury w a s used a t a l a t e r s t a g e t o obtain a
higher quenching rate (Section 6,,I ) when it w a s found t h a t traces of
owgen i n the vacuum quenching furnace formed an adherent protective film
on the specimen.

4. 2 Qualitative def armation experiments

The e f f e c t of deformation on polished surfaces i s reported i n Section 80

For these experiments a polished face w a s prepared on the mounted specimen
and the s t r u c t u r e examined p r i o r t o &formation. The specimen w a s removed
f’rm the mount and subjected t o two successive deformations with intermediate
examinat ion.

(a) A m a l l l o c a l s t r a i n induced by the use of an a u t o m t i c centre

punch.
(b) A g r e a t e r deformation by squeezing across the diameter of the
specimen i n a vice. Since t h e specimens were t h i n c i r c u l a r
discs, t h e r e s u l t a n t s t r a i n e d area w a s concave i n shape
r a d i a t i n g from the point of‘ applied stress.

5. Metallographic observations‘on t h e occurence of banded s t r u c t u r e s i n

uranium-titanium a l l o y s ..
P f e i l (I8) has shown a r e l a t i o n s h i p between g r a i n s i z e and annealing
time i n alloys of uranium 11.5 at titanium and has explained the limited
growth rate by the r e s t r a i n i n g a c t i o n of the dispersion of the hexagonal
compound U2Ti which exists i n equilibrium with a uranium. If such a l l o y s
were u s e f u l as reactor f u e l s , on grounds of r e l a t i v e absorption c r o s s
sections, the p a r t i a l s u b s t i t u t i o n of niobium o r zirconium for titanium
would be desirable. To study t h e effectiveness of this s u b s t i t u t i o n , a n
attempt was f i r s t made t o reproduce Pfeil’s r e s u l t s .

- 3 -
5.1 E f f e c t of cooling r a t e and a l l o y content on microstructure i n uranium
titanium alloys

Three groups of a l l o y s were prepared with titanium contents of 4.. 9, 9.2

and 13.5 a t ;/J. The ingots w e r e sectioned i n t o ten pieces, which were
subsequently annealed f o r 24 hours and cooled t o room temperatme a t various
rates. The r e s u l t s are tabulated.

TAEGE I1
Table of microstructures of uranium -
4.9 a t TO, 9.2 at Y6 and 43.5 a t titaniun
a l l o y s on quenching and a i r coolin<

Atomic $l loOO°C w a t e r quench 1000°C w a t e r quench 10oO°C a i r cool

Titanium direct i n capsule i n capsule

4.9 'didmanstat ten a Equiaxed a grains EquiaxRd a g r a i n s

Average 120 p Average 26 p

9.2 Widmanstatten a Equiaxed a g r a i n s Equiaxed a grains

Average 7 p Average 15 p
I
I 4
Banded s t r u c t u r e a Equiaxed a grains Equiaxed a grains
at o r i g i n a l y grain Average 13 p Average 10 p
boundaries
I I c

The Widmanstatten form of a i n the 4.9 and 9.2 at p a l l o y s on quenching

is i l l u s t r a t e d Fig. 2. The s t r u c t u r e s did not correspond with those reported
by P f e i l and t h i s l e d t o an i n v e s t i g a t i o n of the effect of uranium p u r i t y
on the metallographic s t r u c t u r e at a constant titanium content.

5 2 The effect of uranium p u r i t y on microstructure i n quenched 11.5 a t 510

titanium a l l o y
-
A group of uranium 11.5 a t 6! titanium a l l o y s w e r e prepared using a base
m d a l the three t y p e s of uranium of d i f f e r i n g impwrity content. (Table I)
Specimens were annealed a t 1000°C f o r 24 hours and quenched i n water a t
room temperature.

- 4 -
 The e f f e c t o f uranium p u r i t y on the microstructure of quenched u r a n i u m
11.5 a t YO titanium alloys

Cooling Calcium reduced

-
lylagne sium reduced American calcium
Rate. uranium uranium reduced uranium

Water quenched "Banded s t r u c t u r e " Structure of Banded structure

out of capsule with r e t a i n e d 7' r e t a i n e d Y with only. SO- bands
Some grains of a local areas are broad and
a t y boundarie 21. showing lenticular i n
some a almost transformation t o shape resembling
Widmanstatten i n banded structure. a c i c u l a r a.
appearance.

Water quenched Fine grained a Pine g r a i n e d a Some f i n e grai&

i n capsule which has grown Some areas of a. Considerable
from o r i g i n a l y' r e t a i n e d y are percentage of
boundaries l a r g e r detectable. r e t a i n e d y,a i s
than that f o r m d present at y
within y grains. boundaries and
Average k.2 p Average 3.8 p within grains.
1vlax.e 20. p Max. 1 4 v Average 4.0 p
hhx. 6.5 p
J

Variations i n s t r u c t u r e across the specimens suggested t h a t cooling rate

w a s c r i t i c a l . Alloys of two uranium p u r i t i e s were therefore prepared and
examined after end quenching i n s i l i c o n e o i l .

5.3 E f f e c t of end quenching on microstructure i n 11.5 a t YU titanium alloys

A number of samples were prepared f o r end quenching (Section 2.2) using

magnesium and calcium reduced uran:Lum with 11.5 at 70 titanium. The
f a b r i c a t e d specimens weke f i st hornogenised 'at 1oooOC f 24 hours followed
treatrnent it w a s hoped that any U2Ti
t 600°C would be taken i n t o solution and

0
rid quenched i n t o s i l i c o n e o i l f r o m 1000 C
a f t e r 30 minutes at temperature, !l!he specimens were examined f o r s t r u c t u r e ,
g r a i n s i z e and hardness. The reprciduciljility of s t r u c t u r e s i n the specimens
examined w a s poor, banded structunbs being obtained at the quenched t i p
in som cases uf' both calcium and magnesium reduced alloys. Fig. 3 shows
the s t r u c t u r e and hardness curves f o r a l l o y s f o r which repeats were obtained.

The ranges of s t r u c t u r e and hardness produced by t h i s t e c h n i q e were then

mmpared i n uranium a l l o y s of 9.2 e.t )L molybdenum, niobium and titanium.

- 5 -
 Influence of diffusion r a t e on microstructure in alloys with niobium molybdenum,
titanium and zirconium

6.1 Effect of end quenching from the y phase i n t o mercuqy

Alloys of uranium 9.2 a t 70 niobium, molybdenum and titanium w e r e prepared

and hoinogenised as described i n Section 5.3.

Retained y with a a t grain boundaries

Retained y with a a t grain boundaries and with t h e
grains.

6.2 E f f e c t of annealing a l l o y s end quenched i n t o mercury'

The three specimens end quenched i n mercury (Section 6. I)were annealed

f o r 24 hours at 60@C t o examine the decomposition from t h e metastable
banded microstructures t o equilibrium phases. P a r t i c u l a r note w a s taken
of t h e form and amount of high s o l u t e phases, Le., U2Ti i n uranium-titanium,
y2- i n uranium-niobium and y e i n uranium-molybdernun.

A p l o t of hardness (Fig. 4) shows t h a t the hardnesses developed a f t e r

annealing are reasonably uniform along t h e length of the specimens.

Uranium-molybdenum alloy. The hardness r i s e on a n p a l i n g would appear

t o be associated w i t h t h e p r e c i p i t a t i o n of y' and the f o r m t i o n of s t r a i n
free a from the s t r a i n e d a produced on quenching. Fig. I O i l l u s t r a t e s the

- 6 -
fonn i n which y ' i s precipitated.

Uranium-niobium alloy. The tlanded structure on quenching has a lower

hardness than t h e equilibrium phases produced by short t h annealing.

The disycrsion of y2, d i f f i c u l t to see a t x570 (Fig. 11) may s t i f f e n

the f i n e equiaxed a fonned. The a grain s i z e and y2 dispersion and s i z e
w i l l therefore control the hardness.

Uraniurn-titanium alloys. The hardness change i n this specimen is i n

two d i s t i n c t parts.

(a) An increase i n hardness ,Df t h e banded s t r u c t u r e and some r e t a i n e d y.

(b) A decrease i n hardness i n the regions of o r i g i n a l slaw cooling,

where the a and y + a s t r u c t u r e s w e r e v i s i b l e with a presumed
submicroscopic U 2 T i displ%sion. (Fig. 12)

To o b t a i n f u r t h e r irformation on t h e transformation c h a r a c t e r i s t i c s
of these alloys, specimens were end quenched i n t o backing pump o i l
r e s u l t i n g i n a slower graduated cooling rate.

6.3 Effect of end quenching from the y phase i n t o backing pump o i l .

Alloys of 10 a t 70 niobium, moltybdenum and zirconium were homogenised as

described i n Section 5.3., and end quenched into backing pump o i l .

It w a s considered that t h i s seriesof samples w u l d give information on the

transformation products at slower cooling rates than mercury quenching.
The hardness curves are given i n Fig. 13.

Uranium-molybdenum alloys. I'he banded s t r u c t u r e i s again found with t h e

slaver cooling rates on o i l quenching. No evidence of a second phase can be
found metallographically. X-ray evidence (Section 9) shows the structure
t o be a f o r m cf d i s t o r t e d a-

Uranium-zirconium alloys- Since the d i f f u s i o n rate i n uranium-zirconium

appears t o be intermediate between t i n uranium-molybdenum and
uranium-titanium a l l o y s , t h i s s p e d enables the influence of d i f f u s i o n
rate t o be examined. The s t r u c t u r e developed varied along the length only
s l i g h t l y , and that a t the quenched t i p is i l l u s t r a t e d i n Fig. 14, A t the
slaw cooled end of t h e specimen, t h e structuxe on transfonnation of metastable
y w a s tending towards intermediate1 products of, a nucleation and growth type.

Uranium-niobium alloy. b1erc:ury quenching of t h i s a l l o y produced a

banded s t r u c t u r e throughout t h e length, A t the slower cooling rates on o i l
quenching a s e r i e s of t r a n s f o m t i o n products a r e formed which could
account f o r the marked hardness changes. These products are i l l u s t r a t e d
i n Pigs. 15-16.

- 7 -
1

7. Annealin!: of t113andedStructures" i n uranium-titanium alloys,

Alloy specimens of American calcium reduced uranium-11.5 at $ titanium

mre water quenched from 1000°C t o give a banded structure and subsequently
annealed at 6 0 0 O C . The change of hardness w a s noted (Fig. 17) and the
c h a r a c t e r i s t i c s of t h e transf ormation ob served metallographically.

Decomposition of the supersaturated s o l i d s o l u t i o n i n t o equilibrium phases

occurred i n two s t a g e s t o be seen i n F i g s 18 and 19. I n i t i a l precipitation
of U 2 T i has taken place along the r i b s uf' t h e bands, followed by secondary
p r e c i p i t a t i o n of U2Ti, simultaneously with nucleation and growth a€' "new" a
g r a i n s f r m previous y boundaries and from s i t e s within t h e banded structure.

The growth of the presuniably strain-free a i s apparently associated w i t h

s o l u t i o n and r e p r e c i p i t a t i o n of t h e U 2 T i i n a lamellar form at r i g h t angles
t o the interf'ace between s t r a i n f r e e and the banded structure. (Fig. 18 )
Re-solution of U2Ti i s indicated by the change i n form and d i r e c t i o n uf' the
two stages of precipitation.

8. The effect of deformation of retained y i n uranium 12 a t YO t i t a n i u m and

12 a t > O molybuenum a l l o y s ,

The common high temperature phase of these two alloys, B.C.C. y, can be
r e t a i n e d (according t o metallographic evidence) at room temperature
depending upon the following conditions being favourable.

(a) AUOY content.

(b) Rate of cooling from the y phase f i e l d .

(c) Impurity content of t h e base metal uranium.

(d) Annealing t i m e i n t h e y phase f i e l d ( 6 )

With a magnesium reduced uranium a l l o y of 12 a t 7; titanium, metallographically

the y phase a:,pears to be r e t a i n e d by w a t e r quenching. The y grain s i z e i n t h e
alloy examined i s 2O-3Q.t and t h e hardness as cpenched 600 V.P.N.

The y phase has a l s o been r e t a i n e d i n uranium molybdenum a l l o y s of this

composition range by similar quenching, r e s u l t i n g i n a hardness of 350 V.P.N.
at a grain size of 3511.
The e f f e c t of deformation (Section 4.2) on t h e structure of these two
a l l o y s w a s compared. The surface of the uranium-molybdenum alloy showed
s l i p l i n e s and on metallographic examination, af'ter removal of t h e surface
l a y e r by normal polishing techniques, only y grains were identified.

I n t h e t i t a n i u m a l l o y the e f f e c t on t h e polished surface is severe

(Fig. 20). Bands a r e r a i s e d which remain i n evidence af'ter polishing
(Figs 21,22). Since both grains and bands a r e now rendered r e s p n s i v e un&r
polarised l i g h t (Fig. 23) it i s evident t h a t the simple cubic structure has
been disturbed, and a more complex farm developed. These bands tend t o be
l e n t i c u l a r i n shape, sirnilar t o a conventional martensite needle, unlike
 brrs the p a r a l l e l bands produckd on quenching. Fig. 1.

9. Annealiw, of Hetained y i n a urar&um - 12 a t 20 titanium a l l o y

Two specimns from the same rod were annealed f o r 24 hours a t 1000°C
then quenched i n o i l and mercury respectively. The metallographic appearance
of t h e two a l l o y s o.n examination suggested retained y although a weak response
t o p o l a r i s e d l i g h t was observed. Hardness on these two a l l o y s however
differed, the o i l quenched sample being 620 V.P.N. and the water quenched
lc15 V.P.N.
0
These specimens were s u b s e q x n t l y annealed at 300 C f o r 24 hours.
Examination w a s made 1113 t a l l o g r a p h i o a l l y and hardness determined after i n t e r v a l s
of 1,3,7 and 24 hours at temperatix*e.

The change i n hardness i s shcw Fig. 24. Metallographically the

specimens responded more strongly t o polarised l i g h t . The X-ray structure
after 24 hcurs showed a p a t t e r n sinular to y with considerable l i n e
broadening; it could not be indexed as cubic and w a s designated yo (Section IO).

10. X-ray examination

A number of small specimens of uranium a l l o y s with molybdenum niob'ium,

t i t a n i u m and zirmnium were cooled a t varying r a t e s from t h e y phase f i e l d
and the s t r u c t u r e examined by a glancing angle technicpe. An attempt w a s
then made t o c o r r e l a t e X-ray with metallographic structures. R e s u l t s are
tabulated Table IV. Some outstanding differences may be noted.
1 I. The banded structure shows a d i s t o r t e d a s t r u c t u r e designated a&
( d i s t o r t e d a formed by shear.) Fig. 25a.

2. The nucleation and growth o f , g r a i n s i n a uranium -11.5 a t p

titanium a l l o y a t fast m o l i n g r a t e s obtained on o i l quenching,
results i n an X-ray s t r u c t u r e similar t o a& The d i s t o r t e d
a l a t t i c e produced by t h t s mechanism has been designated aA.
(Distorted a by nucleation and growth). (Fig. 25b.)

3. Idetallographically no d i s t i n c t i o n can be made between :a and a

uranium.

4. Lbtallographic i d e n t i f i m t i o n of y i s not s u f f i c i e n t . A d i s t o r t e d
form of Y, Y
0
, i s produced, whi& has only been distinguished by
X-ray d i f f r a c t i o n . (Fig. 25c. )

5. Two types of d i s t o r t i o n can occur t o a. A simple contraction of the

b a x i s a s i n (Fig. 25b.) when the 002 moves t o coincide w i t h the
021, and a more complex change r e s u l t i n g i n systematic l i n e
s p l i t t i n g a s observed i n a uranium-molybdenum and a uranium-
niobium allqy. (Fig 25d)

11. Discussion

Ii'rm these expcrimental r e s u l t s a n attempt has been nwle t o account f o r

the l a c k of r e p r o d u c t i b i l i t y on quenchin[), small specinlens of uranium-ti tcmium,

- 9 -
 and f o r the v a r i a t i o n s i n bchaviour between systems.

The experkncnts of Section 5.1. indicate that irrespective of cooling

r a t e , t h e r e e x i s t s a l i m i t i n g cornposition below which metastable y decomposes
by a nucleation and growth mechanism. Below t h i s minimum cornposition, cooling
r a t e inf'luences t h e metallographic fonn of a prothrced, but no X-ray structure
examination has been made t o show whether the a c e l l i s distorted; above, t h i s
J m i n i m u m composition, cooliqq r a t e and p u r i t y a r e variables which mst be
controlled t o induce reproducible transformations. An increase i n t o t a l
impurity i n t h e base uranium results i n a more rapid decomposition from
metastable y phase. Section 5.2. The e f f e c t i v e impurities may e i t h e r
combine with the solute and decrease the a l l o y composition, o r induce more
r a p i d nucleation.

The influence of cooling r a t e a t a f i x e d alloy content on microstructure

i f of g r e a t e s t i n t e r e s t i n uranium-titanium alloys. The i n t e r p r e t a t i o n
of the s t r u c t u r a l changes associated with the hardness variation, was based
on metallographic i d e n t i f i c a t i o n of phases, but subsequent examination of
small quenched specimens has shown t h a t such i d e n t i f i c a t i o n i s not rnnclusive.
The d i s t o r t e d y phase yo and the nucleation and g r m t h form of d i s t o r t e d
a, 4 can only be i d e n t i f i e d as d i s t i n c t from y and a respectively by X-ray
examination (Section IO)

From the metallographic examination of end quenched specimens, and X-ray

examination of the small wenched specimens, it has been possible however
t o d r a w some conclusions as t o t h e mechanism of t r a n s f o r m t i o n i n these alloys.
A high cooling rate developed on mercury quenchhg i s mcessary t o produce
a shear transformation t o t h e banded s t r u c t u r e t (Fig. 4). X-ray evidence
suggests t h a t t h i s s t r u c t u r e i s a modification of the orthorhombic a c e l l .

A t slower cooling r a t e s developed a t the slow cooled end of the end

quenched rods an equiaxed g r a i n s t r u c t u r e is formed by nucleation and
growth which has a similarly d i s t o r t e d a c e l l .

A phase presumed t o be y has been metallographically detected a t oooling

rates intermediate between those necessary t o produce the two types of
distor-ted a. This suggests t h a t the banded s t r u c t u r e i s produced athermally
and some s t a b i l i s i n g mechanism prevents decomposition of metastable y a t
intermediate cooling rates. This s t a b l i s a t ion i s associated with a marked
hardness r i s e 400 -3 600 V.P.N.

The simplest explanation of t h e range of hardness observed would be

p r e c i p i t a t i o n hardening by a submicroscopic dispersion of one of the phases
produced on decmposition of the y phase. This dispersed phase may also
prevent the transformation by shear a t the "martensite start" temperabre
t o the banded structure. A t more r a p i d cooling r a t e s p r e c i p i t a t i o n would
be suppressed and metastable y could then transform by shear.

Evidence supporting t h i s mncept of decomposition i s found S r m

examination of the annealing behaviour of quenched alloys.

If t h e banded s t r u c t u r e forins i n t h e absence of p r e c i p i t a t i o n on cooling,

then a harClnes;s r i s e will be e x p c t e d on a n n e a l i y , t h i s structure.

- 10 -
 S i m i l a r l y , i n < r e a s of' p e a k hardne,ss, which supgest the presence of a second
phase d i s p c r s i o n , anncalinjr, could r e s u l t i n the aggloineration of p a r t i c l e s
with a decrease i n i n t e r n a l s t r a i n and hardness. Uoth of these e f f e c t s
were observed. (Section 6.2)

I n t h e uranium a l l o y s e x h i b i t i n g d i s t o r t e d a s t r u c t u r e s , o r r e t a i n e d y
on quenching f r o i n the y pliase f i e l d , t h e cormon phases of the system a r e -
a high temperature I3.C. C. structun: e x h i b i t i n g high s o l u t e s o l u b i l i t y and
a t law tenipcratures an orthorhombic s t r u c t u r e o f low s o l u t e s o l u b i l i t y ,
existing i n equilibrium with a second phase of high a l l o y content.

A t t h i s s t a g e , thererore, t h e phase u; and u l appear t o be metastable

s t r u c t u r e s a s s o c i a t e d with poss iblt? supersaturation.

The l i i i u t e d experiments on def'ormtion show t h a t t h e r e t a i n e d y

s t r u c t u r e i n a 12 a t . ; . u titanium al:Loy can be transformed t o th ui s t r u c t u r e
by t h e a p p l i c a t i o n of e x t e r n a l s t r e s s . S t r a i n a s s o c i a t e d with p r e c i p i t a t i o n ,
preventing shear, can be considered as being overcome by a d d i t i o n a l external
stress.

The annealing experiments a t .300°C on m t a s t a b l e y, support t h e view

t h a t p r e c i p i t a t i o n caused hardening (Fig. 24);X-ray evidence ( S e c t i o n I O )
i n d i c a t e s t h a t y s t r u c t u r e s subjected t o this type of t r e a t m n t cease t o
have cubic symmetry.

E x a i i n a t i o n of t h e systems other t h a n uranium-titanium, i n d i c a t e s t h a t

cooling rate i s not a c r i t i c a l f a c t o r i n t h e d e c m p o s i t i o n of y phase t o
I ' ai.
A s i n g l e s t r u c t u r e i s obtained throughout t h e l e n g t h of t h e uranium-
9.2 at. $ niobium ~ncluranium-9.2 e t . $ molybdenum a l l o y s on mercury
quenching (Section 6.1 ). The hardness associated with these banded s t r u c t u r e s
i s a l s o r e l a t i v e l y constant and considerably lower than t h a t obtained ,on
quenching t h e uranium-9.2 a t . $I t i t a n i u m alloy. If' y decomposes t o a, only
if p r e c i p i t a t i o n of a second phase i s prevented, t h e n decomposition i n t h e s e
alloys i s much slower than i n uranium-titsniirm. Subsequent annealing experi-
ments (Section 6.2) i n d i c a t e t h a t F r e c i p i t a t i o n docs occur a t 6OO0C (as
i n d i c a t e d by a hardness rise) whereas t h i s can occur at 3OO0C i n uranium-
titanium allc,ys. A t t h e slow rates of cooling on q u e n c h i 3 i n t o backing pump
o i l , t h e uranium-molybdenum a l l o y decomposed t o a banded as s t r u c t u r e whilst
t h e uranium-niobium a l l o y showed et hardness v a r i a t i o n a s s o c i a t e d with a
varying microstructure. Metallographically these s t r u c t u r e s a r e not c l e a r ,
but th$y mny be considered as intermediate products between t h e r e a c t i o n s
y+ a s and y-+ a + y2.

Three mechanisms may be postulated f o r t h i s range of microstructures i n

t h e uranium-niobium al.loys:

.- 11 -
 1. They a r e the result of varying tims i n a c r i t i c a l temperature
range i n which decomposition may occur.

2. The coolinE; r a t e may suppress t h e temperature of transformation

of y t o varying temperatures r.esulting in a change of mechanism.

3. The transforniation may involve y-P-a transformation a t t h e slowest

cooling rate.

The a l l o y with eirconium,which has a diffusion r a t e intermediate between

t i t a n i u m and molybdenum, shows that at the slowest r a t e of cooling on
quenching i n backing pump o i l banded s t r u c t u r e s a r e no longer found. The
a b i l i t y f o r a l l o y s of uranium-niobium, uranium-zirconium and uranium-
molybdenum t o decompose at slow r a t e s of cooling t o u i i n d i c a t e s t h a t the
development of' a metastable y i s r e l a t i v e l y easy and p r e c i p i t a t i o n of a
second phase t o i n h i b i t the shear of the metastable y t o f orm a; does not
occur ( L e . =fusion i s slow).

C r i t i c a l v a r i a b l e s upon which t h e transformation y t o u; depends

appear to be:

1. The tendency of t h e s o l u t e atom t o s t a b i l i s e y t o an M, temperature.

2. The d i s t o r t i o n of t h e a and y s t r u c t u r e s by t h i s s o l u t e atom

(dependant upon atomic s i z e , e l e c t r o n i c structure, etc. ,)

3. The diffusion c o e f f i c i e n t s of s o l u t e i n a and y phases.

4. The p u r i t y of the uranium and a l l o y i n g elements.

5. The cooling rate.

This analysis of the fragmentary experimental evidence presented i n

(Part I) suggested a more d e t a i l e d study of t h e transformation processes
i n uranium-titanium alloys. The examination of s u i t a b l y chosen a l l o y s i s
described and discussed i n P a r t 11.

Acknowledgements

The authors wish t o thank the staff a t t h e P u b r Research I n s t i t u t e

f o r t h e i r helpful discussion, p a r t i c u l a r l y Dr. G. I. W i l l i a m s and Miss C.
Knight f o r t h e i r c a r e f u l examination crf the X-ray films.

- 12 -
. brs References

1. Buzzard, R.W., L i s s , R.B., Fickle, D . P . , A.E. C.D. 3418.

2. Knapton, A.G., J.I.IvI. 1954-5 811 p.497,

3. Browne, J.D., P f e i l , P.C.L., Wil:lj.amson, J.K. tLE.R.E. h4/R 2698.
4. W. A. P.Do - 127.
50 W.A.P.D. - MM - 413.
6. Hills, R.F., Hodkin, D. A.&.R.E,, Private communication.

7. H a t t , B.A., Brooks G. 13. Fulmer Research I n s t i t u t e . Private conmunication.

8. hlurrray, J. H. , (Ihiss) A. J!i.R.E. P r i v a t e coi,munication.

9. H m l e t t , B. L E . 1. Aldermaston. Private communication.

io, '8.A.P.D. - P.W.R. - P.M.M. 282,

11. Gut-, Lo AeIoMohLEo Vole 188. p.1472,

12. Bowles, J.S., Barrett, C.S., Gutlhlan, L. A.I.M.M.E. Vole 188. p.1478.

13. Seybolt, A.U., Swnsion, H.T. Journal of Metals. Vol 5. No. 2 Sect, 2. p.292.

14 Vorrell, F.T. Journal of Applied Physics. 1948. Vol. 19. IO, p.929.

15. Miodownick, A.P. University of' London t h e s i s August, l95&

16. 'v7.A.P.D. - MI4 - 271.

17. Miodownick, A.P. A.E.H.E. x/pR 1712.

18. Pf'eil, P.C.L. A.E.R.E.. Mk

/ 1712. ' *-, , I

19. B o s t r o m , W. A. , Holteman, E.K. "The metastable garnma phase i n uranium

base molybdenum alloys. 1957 Nuclear E r g b e r i n g Science Congress.

- 13 -
 TARLX I

Analysis i n p.p.m. of: metal.

Uranium base m t a l Alloying element

Impwits Calcium iagne sium hcricari Titanium Niobium Idolybdenum

reduced reduced Calcium
rednoed

AI 120 61 <IO0
C 450 225 ( 2&&) 30 30
Ca <I00
cr <25 <IO00
cu 2 < 50
Fe 12 900 100-400 < 100
u <I <IO0
Mn 3 Total
i m p m it y
Mo 100 <IO00 less than
Ni 15 <IO0 200 p.p.m.
Si 25 180 100-700
Ti <15 <600
v <I <lo00
w <20
Zr

- 14-
 Specimen fieat Treatment 1,dicrost r u c t u re X-ray structure

0
625 loo0 C liercury Banded s t r u c t u r e A distorted a
American Calcium quenched as E’igs. 1 and 7 pat tern.
reduced Designated ai
U r anitun Fig. 25a
11.5 at.;o
t itaniwn
- I

648 IOOOOC Bier cury Banded decomposed a + U2Ti.

hiagne sium quenched annealec i n t o equiaxed
reduced one day a t 6OOOCI. g r a i n s responsive
Uranium t o polarised
9.2 at.;id t i t a n i m l i g h t and 2nd
phase. U2Ti.

0
614 IO00 C Mercury Large grains Distorted y
h g n e sium quenched slightly film. Designate(
reduced responsive t o YO
Uranium polarised l i g h t Broad l i n e s
11.5 at.jb which cannot be
titanium indexed on
normal y l a t t i c x
Fig. 25c.

400 ~ O O O Cwater VI idmanst at t e n Distorted a

iLa;.,ne sium quenched banded micro- p a t t e r n with
reduced structure line splitting.
Uranium Fig. Z5d
10 at.,o iriolybdem

626 1000°C A i r cooled Small equiaxed Distorted a

Calcium reduced g r a i n s responsiw pattern.
IJranium t o polarised a; + u T.
2
11.5 a t 2 d light
Fig. Z5b.
t i taniurn

- 15 -
A . E . R . E . M/R 2 6 7 3 Fig, 1 X 1850
Banded s t r u c t u r e i n uranium - 9.2 atB%
titanium alloy.

A.E.R.E. M/R 2 6 7 3 Fig. 2 X 570

A c c i c u l a r a l p h a develoried on w a t e r q u e n c h i n g
a uranium 9.2 at.% t i t a n i u m a l l o y .
 oi
t
I

w r 7
-'
D
t I
0 / /
/

/ x'
/
p'
x
-'
@ /
(yyo
/ x- -x MAGNESIUM REDUCED
/ URANIUM I .
/
9'
/
0- -- 0 CALCIUM REDUCED
URANIUM

I I I I I I 1 I 1

--
THREAD I" 2" 3"
DEPTH OF IMMERSION
I"
SPECIMEN LENGTH, INCHES.

I URANIUM I METALLOGRAPHIC STRUCTURE I

CALCIUM REDUCED I EQUIAXED d G R A I N S
RETAINED WITH aL
I AT GRAIN BOUNDARIES
I 6 WITH oc
MAONESlUM REDUCED1 EQUIAXED oC GRAINS. ATORAIN RETAINED k+

A.E.R.E. M/R.2673. F I G . 3. V I C K E R S PYRAMID HARDNESS NUMBER AND MICROSTRUCTURE

ALONG URANIUM 11.5 AT O/O TITANIUM ALLOY RODS END QUENCHED INTO SILICONE OIL.
 500

400

300

200

IO0 I I I I I
iREAD I" 2" QUENCHED TIP
DEPTH OF;; IMMERSION

w
URANIUM

I
9.8 A + %
NOLYBDENUM
A.E.R.E. M/R 2 6 7 3 Fig. 5 X 570
S t r u c t u r e a t t i p . o f end quenched u r a n i u m
9 . 2 a t o % molybdenum allciy.

A.E.R.E. M/R 2 6 7 3 Fig. 6 X 570

S t r u c t u r e a t t i p o f end quenched uranium
9.2 a t o % niobium alloy.
A.E.R.E. H/R 2 6 7 3 Fig, 7 X 570 ' -

Structure at tip o f end quenched uranium

9.2 at,% t i t a n i u m a l l o y ,

A.E,R.E. M/R 2 6 7 3 Fig. 8 X 570

U r a n i u m - 9.2 at.% t i t a n i u m a l l o y e n d
quenched into mercury, Transformation to
alpha grains,
 A.E.R.E. M/R 2 6 7 3 Fig. 9 X 570
Uranium - 9.2 a t o % i:itanium a l l o y end
quenched i n t o mercury, Transformation to
a l p h a a t gamma g r a i n b o u n d a r i e s ,

A . E . R . E . M/R 2 6 7 3 Fig,, 10 X 570

S t r u c t u r e of u r a n i u m - 9.2 a t . % m o l y b d e n u m
a l l o y , end quenched i n t o mercury and
a n n e a l e d a t 6 O O 0 C f o r 211 h o u r s . a + y ' .

A
A.E,R,E. M/R 2 6 7 3 Fig. 1 1 X 570
Structure of uranium -9.2 at.% niobium
a l l o y , end quenched i n t o mercury and a n n e a l e d
a t 6OO0C f o r 2 4 h o u r s . a + y 2 "

A.E.R.E. M/R 257.3 F i g , 12 X 570

Structure of uranium - 9.2 a t o % t i t a n i u m
a l l o y , end quenched i n t o mercury and a n n e a l e d
a t 6OO0C f o r 24 hours. a + U2Ti.
 300

x-x URAN~UM IO AT% NIOBIUM

URANIUM10 AT?, ZIRCONIUM

0 0 URANIUM \O A T 7, b4CU2YBDENUM.

>

200

I I I I , I . , I 1
T H R E A D END I” 2’ QUENCHED TIP

A.E.R.E. MjR.2673. FIG. 13. VICKERS PYRAMID HARDNESS NUMBER ALONG

URANIUM ALLOY RODS END QUENCHED IN BACKING PUMP OIL.
A.E.R.E. itl/R 2 6 7 3 F i g , 14 X 570
Banded s t r u c t u r e i n u r a n i u m - 10 at.% zir-
c o n i u m a l l o y e n d q u e n c l i e d i n t o b a c k i n g pump
o i I.

A.E.R.E. M/R 2 6 7 3 F i g . 15 X 570

Decomposition s t r u c t u r e i n uranium - 10 a t . %
n i o b i u m a l l o y e n d q u e n c l i e d i n t o b a c k i n g pump
oil. l05" from thread.
A.E.R.E. M/R 2 6 7 3 F i g , 16 X 570
Decomposition structure i n uranium - 10 at.%
n i o b i u m a l l o y e n d q u e n c h e d i n t o b a c k i n g pump
oil. 2.811 f r o m t h r e a d .

A.E.R.E. M/R 2 6 7 3 Fig. 18 X 570

D e c o m p o s i t i o n o f baiided s t r u c t u r e i n a
uranium - 11.5 a t n % titanium a l l o y .
D

VICKERS PYRAMIO
H)rl30NEW3 NUMBER,

71
L

c,

0
I
D
z
c,
m

X
i
e
 A.E.R.E. M/R 2 6 7 3 Fig. 19 X 1350
Decomposition o f banded s t r u c t u r e i n u r a n i u m
- 11.5 a t o % t i t a n i u m a l l o y .

A.E.R.E. M/R 2 6 7 3 Fig. 20 X 570

-
R e t a i n e d gamma i n u r a n i u m 12 ato% titanium
alloy. View o f surfiice on deforming i n a
vice.
 A . E . R o E . M/R 2 6 7 3 F i g , , 21
Banded s t r u c t u r e produced by v i c e d e f o r m a t i o n
o f retained y i n a uranium -
12 at.% titanium
alloy.

A.E.R.E. M/R 2 6 7 3 Fig. 22

Banded s t r u c t u r e p r o d u c e d by v i c e d e f o r m a t i o n
o f retained y i n a uranium -
12 a t o % titanium
alloy,
A . E . R . E . M/R 2 6 7 3 F i g . 23 X 570
Polarised l i g h t photomicrograph of retained
gamma i n a u r a n i u m - 12 at.% t i t a n i u m a l l o y
following deformation i n a vice. Polished
face.
 600

I - SO0
x--X QUENCHED INTO MERCURY
e--@QUENCHED INTO O I L .

I 1 I I I I I I I I I I I

4 8 12 20\6 24
ANNEAL1N G TIME, HOURS.

A.E.R,E. M/R.2673. F l G . 2 4 . CHANGE OF VICKERS PYRAMID

HARDNESS NUMBER ON ANINEALING RETAINED 8 STRUCTURES
AT 300°C.
 C

A.E.R.E. M/R 2673 Fig. 25

a) O i s t o r t e d a l p h a p a t t e r n o f as' i n u r a n i u m - 1 1 . 5 a t . % t i t a n i u m a l l o y ,
625.
b) Distorted alpha pattern of ai i n u r a n i u m - 11.5 a t . % t i t a n i u m a l l o y .
626.
c) D i s t o r t e d p a t t e r n o f yo i n u r a n i u m - 11.5 a t . % t i t a n i u m a l l o y . 614.
d) Distorted alpha pattern of a uranium - 10 a t . % molybdenum a l l o y
showing systematic l i n e s p l i t t i n g . 400.
e) Normal alpha uranium p a t t e r n . 642.