STUDY OF ALPHA CASE
FORMATION ON
HEAT TREATED TI-6-4 ALLOY
Solar Atmospheres
processes critical
aerospace titanium parts
for the aerospace industry.
As is typical with the heat
treatment of important
titanium parts, alpha case
is a quality issue that
requires attention.
Don Jordan*
Solar Atmospheres Inc.
Souderton, Pa.
*Member of ASM International and member,
ASM Heat Treating Society
Fig. 1 All-metal (molybdenum) hot zone.
HEAT TREATING PROGRESS MAY/JUNE 2008
S
olar Atmospheres processes
critical titanium parts for the
aerospace industry, and the
formation of alpha case is a
heat treatment quality issue
that requires careful attention. Based
on its experience in titanium heat
treating, it is unusual to have alpha
case on parts that have a bright sur-
face after heat treatment. However,
the presence of alpha case on Ti-6Al-
4V has been noted in laboratory re-
ports. For example, it was reported
that subjecting parts to a vacuum
level of 5 10-5 torr prior to heating
to 1300F, and maintaining a good
vacuum level throughout the cycle
produces bright parts, yet the mate-
rial exhibited alpha case to a depth
of 0.0004 in. Because this contradic-
tion is perplexing, Solar Atmospheres
Technology Center conducted a pro-
gram both to better understand this
discrepancy and the overall propen-
sity of alpha case formation on
Ti-6Al-4V during vacuum stress
relieving at 1300F.
Test Conditions
Test specimens (4 in. long 0.75 in.
wide 0.094 in. thick) were taken
from Ti-6Al-4V sheet and run in lab-
oratory vacuum furnaces using dif-
ferent atmosphere parameters. The
heat treatment used in production
was used as the baseline cycle: pump
Fig. 2 Graphite-insulated hot zone.
down to 10-4 torr or lower; ramp up
at 300F/h to 1300F; hold 30 min-
utes; vacuum cool at 50 to 75F/h to
below 600F work thermocouple;
and argon cool.
The base cycle was run in Solars
all-metal (molybdenum) hot zone
(Fig. 1) with heat up started at 7
10-5 torr. The test sample was placed
on the moly rails. After the cycle, the
sample surface spanning the rails
was slightly discolored (light grey/
gold/brown), but areas shielded by
contact with the support rails re-
mained bright. Both the bright and
discolored areas were examined met-
allographically to check for the pres-
ence of alpha case. Metallographic
specimens were etched using Krolls
reagent (~8 s), followed by swab
etching with 2% ammonium bifluo-
ride (~5 s). No alpha case was re-
vealed.
Test cycle 2 was run in the metal
hot zone, but with the specimen
spanning a 6 in. 3.5 in. container of
1-in. deep titanium sponge powder
placed in the bottom of the furnace
to act as a getter (scavenging reagent
for residual gases). After the cycle,
the entire surface of the sample was
bright, but the sample suffered a
slight weight loss of 0.0003 g. It was
assumed, based on the sample con-
dition after the base cycle, that no
alpha case was present. The weight
45

Fig. 3 Coloration of test sample from cycle 4
(graphite-insulation; damp conditions).
Fig. 4 Cycle 4 sample at blue region shows
alpha case. 1,000
Fig. 5 Cycle 4 sample at purple region shows
alpha case. 1,000
Fig. 6 Coloration of test sample from cycle 5
(graphite insulation; less humid conditions).
Fig. 7 Cycle 5 sample at purple/blue region
shows alpha case. 1,000
Fig. 8 Cycle 5 sample at bronze region shows
alpha case. 1,000
Fig. 9 Coloration of test sample from cycle 6
(run in air).
46
loss was attributed to the sample
being a thoroughly cleaned in the
high vacuum at high temperature.
Test cycle 3 was the same as the
base cycle, but run in a graphite-in-
sulated hot zone (Fig. 2) with heat up
started at 3 10-5 torr. The test sample
was slightly discolored except in the
areas shielded by the moly support
rails, and the sample experienced a
slight weight gain of 0.0004 g. No
alpha case was observed at the clean
or discolored regions.
Test cycle 4 was run in the
graphite-insulated hot zone after
leaving the furnace open to the shop
atmosphere for three hours on a
damp morning. Heat up was started
at 3 10-4 torr, and ramped at
1200F/h. Out-gassing commenced
at about 200F, increasing the pres-
sure by 2 10-4 torr. After the cycle,
the specimen surface was blue
except at the contact locations with
the rails where it was purple, and the
sample experienced a weight gain of
0.0012 g. Metallographic examina-
tion (Fig. 3) revealed alpha case at the
blue region to an average depth of
about 0.0004 in. (Fig. 4) and at the
purple region to a depth of about
0.0003 in. (Fig. 5).
Test cycle 5 was the same as cycle
4, except it was run on a less humid
(dry) morning, which produced less
outgassing. The specimen surface
was purple/blue, except at the loca-
tions in contact with the rails, where
it was bronze (Fig. 6), and the sample
experienced a slight weight gain of
0.0014 g. Metallographic examina-
tion revealed alpha case at the
purple/blue region to an average
depth of about 0.0003 in. (Fig. 7), and
at the bronze region to a depth of
about 0.0002 in. (Fig. 8).
Test cycle 6 was run in air at 1300F
for one hour. The color of the spec-
imen after treatment was dull
grey/brown (Fig. 9). Metallographic
examination revealed alpha case to
a depth of about 0.00015 in. (Fig. 10).
This alpha case was different than
anything else observed from vacuum
Fig. 10 Cycle 6 sample shows alpha case.
400
HEAT TREATING PROGRESS MAY/JUNE 2008
processing in that it had a 0.000015
to 0.00002 in. thick continuous grey
oxide at the surface (Fig. 11).
A summary of test cycle conditions
and results is given in Table 1.
Comparative Data
At the same time as the alpha-case
study, Solar also was conducting de-
velopment work on hydriding scrap
Ti-6Al-4V fasteners. One cycle in the
graphite insulated furnace had
oxygen contamination in the furnace
during the cycle (ramp to 1200F at
600F/h, hold for 30 min, cool at
50F/h). Fasteners were processed in
a 4 in. diameter 10 in. high stainless
steel container with an open top and
sealed bottom. The top first 2 in. of
material was discolored ranging
from light gold to dark gold/bronze,
purple, blue, and green (Fig. 12). The
part surface below the first 2-in. layer
was light gold.
No alpha case was observed on the
light gold colored fastener, but was
observed on the multicolored fas-
teners to an average depth of about
0.0003 in. The surface etched white,
and there was no distinct mor-
phology change compared with the
structure below it, as with other test
samples processed in vacuum (Fig.
13). Alpha case on a dark blue-col-
ored fastener had a different appear-
ance with white etching alpha
grains more prominent at the sur-
face, which is more characteristic of
typical text-book alpha case where a
morphology change consisting of
concentrated stabilized alpha is
present at the surface compared with
the base metal. The depth of this case
extended to 0.0004 in. (Fig. 14).
Test results indicate that only
deeply colored surfaces of heat
treated titanium have alpha case. To
evaluate further, Solar examined a
test specimen (bright surface) from a
wrought titanium alloy sheet that the
laboratory reported contained a
0.0004 in. alpha case. One side had
no alpha case (Fig. 15a) and the other
showed a nebulous zone (Fig. 15b);
Fig. 11 Cycle 6 sample alpha case contains a
thin oxide layer at the surface. 1,000
Table 1 Test cycle conditions and test results
Test Furnace conditions
1 All metal Mo hot zone
2 All metal Mo hot zone +
Ti sponge getter
3 Same as #1, but graphite insulation.
4 Same as #3, but furnace open 3 h
in damp conditions
5 Same as #3, but furnace open 3 h
in dry conditions
6 Anneal carried out in air
a nonuniform zone dispersed among
areas having no alpha case. The struc-
ture of saw-cut sample ends was
masked due to disturbed metal.
In addition, a non-heat treated ti-
tanium weldment section (Fig. 16)
was evaluated. The back side of the
weldment (opposite the weld be-
tween the titanium sheet and extru-
sion) had some light brown discol-
oration. No alpha case was observed
at the discolored region in the weld-
ment cross section, nor at other areas
along the sheet, or areas of the extru-
sion, or weld metal (Fig. 17).
Summary
Bright heat treated Ti-6Al-4V, and
lightly discolored (light yellow/
gold/brown) material show no evi-
dence of alpha case. Alpha case was
only observed on darkly discolored
material. Running samples in an all-
graphite hot zone produced compa-
rable alpha case results to samples
run in an all-metal hot zone when
processing at comparable vacuum
levels.
There was a morphology differ-
ence associated with the sample that
was heat treated in air at 1300F for
one hour, amounting to a continuous
surface grey oxide that accounted for
about 10% of the alpha case depth. It
is surmised that the scale served as a
barrier film limiting oxygen reaction,
accounting for a white etching alpha
case depth of only 0.00015 in.
Fig. 12 Coloration of Ti-6Al-4V fastener run
in graphite-insulated furnace that had oxygen
contamination.
HEAT TREATING PROGRESS MAY/JUNE 2008
Pump down, Ramp up, Alpha
torr F/h Surface condition case
710-5 300 Slight discolor (lt. gray/gold/brown) No
310-4 300 Bright No
310-5 300 Same as #1 No
310-4 1200 Blue (out-gas at 200F) 0.0004
in. deep
310-4 1200 Purple/blue (out-gas less than #4) 0.0003
in. deep
1300 Gray/brown with 0.00002 in. outer 0.00015
oxide layer in. deep
Fig. 14 Dark blue-colored fastener shows
classic text-book type alpha case. 1,000
Recommendations
It is recommended that furnaces
be pumped down to 5 10-5 torr min-
imum and held for at least one hour
before starting heat up to degas sol-
vents, air, and water from the furnace
hot zone and workload. A ramp rate
of 600F/h maximum is recom-
mended. If considerable out-gassing
occurs during heat up, hold the tem-
perature at which out-gassing com-
mences until the vacuum level drops
(a)
below 2 x 10-4 torr.
The more titanium surface area
present in a given load, the better for
minimizing alpha case. Since tita-
nium powder has an extremely high
surface area or gettering capacity, it
is an excellent choice for a getter.
(b)
It is necessary to establish a clear
definition of define alpha case be- Fig. 15 One side of bright heat treated
tween customer and heat treater. titanium sample shows alpha case (a); the
opposite side shows a nonuniform zone of alpha
Standards that reference acceptable/
case dispersed among alpha case-free areas (b).
unacceptable photomicrographs 1,000
should be established as the basis
for inspection acceptance. The stan-
dards need to include detailed
polishing and etching procedures to
ensure consistency in the analyt-
ical technique. HTP
For more information: Don Jordan, Solar
Atmospheres Inc.; e-mail: dfj@solaratm. Fig. 16 Cross section of titanium to extrusion
com; Web site: www.solaratm.com. weldment (non-heat treated). 50
Fig. 13 Multicolored fastener shows alpha
case with no distinct change in morphology Fig. 17 Back surface of sheet from weldment
compared to the structure below. 1,000 shown in Fig. 16 does not contain alpha case. 400
47