Research in the

in Proc. of the Int. Conf. on Welding Research

198O1slOsaka University,
University, Osaka, Japan, 113,
113, 1980.
1980.
1980's,
Oxygen arid Nitrogen Contamination During
Submerged Arc Welding of Titanium
T. W. Eaqar*
The oxygen content of titanium submerged a r c weld metal i s primarily
dependent upon the p u r i t y and composition of the s t a r t i n g flux while nitrogen
contamination of t h e deposit i s shown t o r e s u l t from adsorption of atmospheric
gases on the hot electrode and baseplate p r i o r t o me1 tinq of the flux. As
reported previously by other i n v e s t i g a t o r s , chloride additions improve the
operating c h a r a c t e r i s t i c s of the f l u o r i d e fluxes, b u t i t i s shown here t h a t
the oxygen content of the weld metal may be affected adversely. The
reprocessing and reuse of the fused slaq was a l s o investigated as a means of
reducing the costs of submerged a r c welding of titanium. In general i t i s
found t h a t the c o s t of titanium submerged a r c welding does not compare
favorably with the c o s t of a l t e r n a t e processes such as qas metal arc welding
of titanium. The advantages and disadvantages of flux shielded weldinq of
t i tanium a r e out1 ined.

I.

Introduction

Welding of heavy section titanium s t r u c t u ~ e sin the open atmosphere i s

c u r r e n t l y performed by e i t h e r the'gas tungsten arc o r the gas metal a r c
processes; however, these processes present numerous d i f f i c u l t i e s , primary of
which i s prevention of oxygen and nitrogen contamination of the weld metal.
In order t o prevent such contamination, copious amounts of argon or helium
gas, combined with elaborate s h i e l d s , a r e used. These arrangements a r e
capable of reducing the t o t a l contamination level t o an increase of l e s s than
100 ppm oxygen and 20 ppm nitrogen; however, the s h i e l d s a r e cumbersome and
the i n i t i a l j o i n t preparation must be closely control led t o provide adequate
cleanliness. If any e r r o r s a r e made during the process, the system i s
unforgiving; and the contaminated weld, i f found, can only be corrected by
removal and rewelding. All of the above requirements lead t o increased
f a b r i c a t i o n costs f o r titanium s t r u c t u r e s .
Although f i r s t developed twenty-five years ago by Gurevich ( I ) , the
process of submerged a r c welding (SAW) of titanium has not been used widely
outside of the Soviet Union. This i s due primarily t o the poor operating
c h a r a c t e r i s t i c s and bead q u a l i t y of welds produced by o t h e r investigators
(2-5). In p a r t i c u l a r , two s t u d i e s ( 4 , 5 ) indicate t h a t both the oxygen and
the nitrogen content of the weld deposit might be too high t o produce j o i n t s
of adequate f r a c t u r e toughness f o r many applications. Nonetheless, i t has
been found t h a t welding of titanium i n the presence of a metal halide flux
e . g . , CaF2) has the advantage of providing chemical control of the oxygen
content of the weld metal ( 1 ~ 7 Such control would make the welding
process more forgiving of operator e r r o r and hence might be expected t o
simplify and reduce the costs of titanium s t r u c t u r a l f a b r i c a t i o n . The present
study was undertaken t o determine the source of oxygen and nitrogen contamation of the titanium SAW weld pool and t o develop techniques f o r control of
the process,

Associate Professor, Department of Materials Science and Engineering,

Massachusetts I n s t i t u t e of Technology, Cambridge, Massachusetts, 02139,
U.S.A.

I I.

Experimental

Bead on p l a t e welds were made on 19 mm thick Ti-6A1-4V extra low i n t e r s t i t i a l grade material. Electrodes of s i m i l a r composition of diameters
1.6 mm, 2.4 mm and 3.2 mm were used; however, i t was found t h a t the l a r g e s t
diameter electrode produced the most consistent r e s u l t s . The oxygen and
nitrogen contents of the base p l a t e were 0.12% and 0.012% respectively. In
the e l e c t r o d e s , t h e values were 0.08% oxygen and 0.008% nitrogen.
Although a number of d i f f e r e n t welding conditions were t e s t e d , the
majority of the welds were produced with DC electrode p o s i t i v e , 36 v o l t s ,
300 amperes, 15 mm electrode extension a t 30 cm/min travel speed. Several
welds were made with external argon shieldinq in order t o reduce atmospheric
contamination and hence t o measure the contamination produced by the f l u x
alone; however, most welds were made without external shielding.
Reagent grade chemicals were used t o produce the f l u x e s , most of which
were melted under vacuum o r i n e r t gas. llonetheless, several fused fluxes
were found t o be contaminated with several percent oxygen due t o adsorption
of water vapor on the s t a r t i n g material. I t was found t h a t high purity flux
could only be obtained from optical q u a l i t y c r y s t a l s which had been fused in
an atmosphere of HF o r HC1. The oxygen content of such flux i s believed t o
be l e s s than 50 ppm.
After melting, a l l fluxes were crushed and screened t o 60 t o 160pm
powder. Care was taken t o avoid contamination of the crushed powder with the
moisture in the atmosphere.
After welding, cores were machined from the center of the weld bead.
These samples were analyzed by i n e r t qas fusion f o r oxygen and by the Kjeldahl
method f o r nitrogen. The oxygen content of the fused fluxes was determined
from x-ray powder d i f f r a c t i o n i n t e n s i t i e s .
III., Results and Discussion
Over one hundred weld beads were produced f o r t h i s study; only a few of
which a r e presented in the following tables. Inspection of Table I reveals
much useful information concerning t h e chemical properties of several titanium
fluxes. Weld 1 , produced with optical q u a l i t y c r y s t a l s has an oxygen content
of 1000 ppm which does not d i f f e r from the base metal/electrode analysis;
however, t h i s weld i s contaminated with 500 ppm nitrogen. I t i s i n t e r e s t i n g
t o note t h a t although-atmospheric contamination i s present, as evidenced by
the elevated nitrogen in the weld deposit, the oxygen content of the weld bead
i s not increased. This r e s u l t has been reproduced with optical qua1 i t y CaF2
fluxes more than a dozen times. If the oxygen content of the flux i s raised
t o 1.2% CaO as in Weld 2 , the oxygen content of the weld metal i s increased
t o approximately 2800 ppm even i n t h e presence of atmospheric shielding, cf.
Weld 3. I t has been found in a l l welds t h a t the oxygen content of the deposit
made with CaF2-CaO fluxes i s d i r e c t l y proportional t o the amount of CaO
impurity in the flux. For example, x-ray analysis of the slag from Weld 6
revealed t h a t 1.6% CaO was present. Use of argon shieldinu reduces the oxidation of the f r e e calcium i n the f l u x , as seen by comparing Helds 7 and 8 ;
thereby reducing the oxygen content of the metal deposit. The oxygen level
of the deposits made with pure CaF2 appears t o be independent of the amount of
atmospheric contamination. The atmospheric contamination may be estimated
from the nitrogen content of the weld deposits.

The above finding t h a t the oxygen content of titanium submerged a r c weld

deposits i s controlled s o l e l y by the purity of the s t a r t i n g f l u x i s consistent
with the report of Gurevich t h a t the CaO content of CaF2 fluxes must be maintained below 0.5% ( 8 ) . For many applications, even t h i s level may be too high
t o maintain s u f f i c i e n t l y low oxygen in the weld metal.
The r e s u l t s of Welds 2 through 5 indicate t h a t nitrogen contamination of
t h e weld deposit r e s u l t s from adsorption of atmospheric gases on regions of
the hot electrode and base p l a t e which are not protected by t h e flux. I t will
be noted t h a t argon shielding, which d i l u t e s the nitrogen in the surrounding
atmosphere, always reduces nitrogen con tami nat ion. Longer electrode extensions always increase the ni troqen content. Anodizing the t i tanium electrode
and baseplate have been found t o reduce the level of nitrogen contamination by
50 t o 100 ppm, while not measurably increasing the oxygen content. Vaporization of v o l a t i l e halides such as KC1, NaF, or NaCl provide some shielding from
atmospheric gases, thereby reducing the amount of nitrogen contamination, c f .
Welds 9 through 15. The most e f f e c t i v e method f o r controlling nitrogen contamination i s external argon shielding.
In many of the e a r l i e s t r e p o r t s , Gurevich noted t h a t chlorides must be
added t o titanium SAW fluxes in order t o improve the operating characterist i c s . A number of such fluoride-chloride fluxes have been studied and have
been found t o provide g r e a t e r weld penetration than pure CaF2 fluxes. Nonet h e l e s s , Welds 9 through 17 i n d i c a t e t h a t the addition of chlorides and in
one case, the addition of NaF, tends t o increase the oxygen content of the
weld deposit. Weld 16 suggests t h a t the increase in oxygen may be related
more t o reduced a c t i v i t y of the calcium cation in the other blended fluxes
than t o the addition of the chloride anion. Based upon a Temkin regular s o l ution model, the addition of 20 mole percent NaCl or KC1 t o CaF2 would reduce
the a c t i v i t y of CaF2 by 40 t o 50% ( 9 ) . This reduced CaF2 a c t i v i t y could explain the increased oxygen content of welds 9-15 and 17. Gurevich a l s o found
t h a t the addition of a cation with a very high oxyqen a f f i n i t y such as lanthanum may reduce the oxygen content of the weld deposit t o 700 ppm (10).
One obvious d i f f i c u l t y with the use of optical p u r i t y CaF2 as a welding
flux i s the expense; however, since t h i s flux i s e s s e n t i a l l y n e u t r a l , i t may
be possible t o reuse the fused slag thereby reducing the cost of the flux.
The r e s u l t s of an experiment examining the reuse of the titanium slag i s shown
in Table 11. I t i s readily noted t h a t both the oxygen and nitrogen content of
the fluxes increase with increasing use. In one case, the flux was dried in
an HCI-Clz furnace a t 500 in order t o remove the CaO which remained a f t e r
the fourth reuse. I t i s seen t h a t the drying did reduce the amount of oxygen
by a f a c t o r of two If the flux i s dried a f t e r each use, i t i s possible t h a t
i t would maintain i t s low oxygen potential f o r many uses.
One advantage of reusing f l u x , in addition t o improved economy, i s t h a t
the contamination of the f l u x by small amounts of titanium, as measured by
x-ray fluorescence, improves the operating c h a r a c t e r i s t i c s of the flux without
the addition of hygroscopic chloride s a l t s . The reused f l u o r i d e flux produced
a more s t a b l e a r c , a b e t t e r weld bead contact angle and a smoother surface
than did the unused CaF2.

An economic comparison of SAW versus GMAW of titanium has been performed.

A t the measured flux consumption r a t e of 4.5 kg of f l u x per kg of electrode
deposited, and the present c o s t of optical q u a l i t y CaF2 of $18 per k g , SAW i s
approximately s i x t y percent more expensive than GMAW. I f multiple reuse of
of the f l u x could reduce the c o s t t o $2.25 per kg of f l u x , the two processes

would be roughly equal i n c o s t (11).

I t should be a l s o be noted t h a t the submerged a r c weld deposits produced
i n t h i s study a r e generally i n f e r i o r in shape and surface appearance t o those
c u r r e n t l y produced by GMAW. A parametric study of t h e welding process para-

meters provided no s i g n i f i c a n t improvement in t h i s a r e a ; however, the improvements in bead shape with a d d i t i o n of chlorides t o t h e f l u x or with f l u x reuse
suggest t h a t f u r t h e r improvements a r e possible. There i s l i t t l e doubt t h a t
Soviet i n v e s t i g a t o r s may be capable of producing t e c h n i c a l l y useful submerged
a r c welds in titanium, but i t i s not c l e a r t h a t t h e process i s economical
compared t o t h e a1 t e r n a t i v e s .
In conclusion, t h e use of h a l i d e f l u x e s when welding titanium shows
promise of providing means of improving the a r c behavior, of c o n t r o l l i n g the
weld bead shape and penetration and of c o n t r o l l i n g t h e oxygen content of the
deposit. On the negative s i d e , t h e f l u x e s a r e required t o be of high p u r i t y ,
which makes them expensive; they are often hygroscopic and in many cases they
produce noxious fumes. The advantages of f l u x shielded welding of titanium
w i l l only be r e a l i z e d i f these disadvantages can be overcome.
Acknowledgements
The author wishes t o express appreciation t o t h e many people who have
contributed t o t h i s work. These include C. S. Chai, J . J s G u l l o t t i , G. Hunter, Dr. G . B. Kenney, M. Ring, B o A. Russell and Professor D. R.
Sadoway. The support of t h e Office of Navel Research i s a l s o appreciated.
REFERENCES
( 1 ) S. M. Gurevich and S. V. Mischenki , A v t , Svarka, No. 5 , 1956, p.1.
( 2 ) B. Cliche, Report No. RAM-00-107, Canadair L t d . Montreal, Canada, 1964.
( 3 ) H a F. Petsch, Final Report, Contract No. N00140-68-C-0148, General
Dynamics Corporation, Groton, CT, 1968.
( 4 ) D. C. Hill and C. L. Choi, Neld J . , 55 No. 6 , 1976, p. 152-s.
( 5 ) S. Marya and F. LeMaitre, 5emes ~ o u r % e s d'Etude d u t i t a n e e t de s e s
A1 l i a g e s , Nantes, France, November, 1978.
( 6 ) S. M, Gurevich e t a l . , A v t . Svarka, No. 4 , 1964, pp..93-94.
( 7 ) C. S. Chai , J . J . G u l l o t t i and T. W. Eagar, Technical Report No. 2 ,
Contract N00014-77-C-0569, Mass. I n s t . of Technology, Cambridge, MA,
30 Sept. 1978.
( 8 ) 5. M. Gurevich and L. K. Bosak, A v t . Svarka, No. 11, 1964, pp. 47-50.
( 9 ) F. D. Richardson, Physo Chem. of Me1 t s in Metal1 urgy, Academic Press,
New York, 1974, ~ o l 1 .
(10) S. M. Gurevich e t a l . , A v t . Svarka, No. 4 , 1964, pp. 93-94.
Technical Report No. 3, Contract N00014-77-C-0569,
(11 ) G. Hunter e t a1
Mass. I n s t . of Technology, Cambridge, MA, 30 Sept. 1979.

.,

Tab1 e I .
Weld
No.

E f f e c t s of titanium f l u x composition and welding process parameters

on t h e oxygen and nitrogen content of t h e weld d e p o s i t .

Flux
Composition

Oxygen
Percent

Nitrogen
Percent

Weld Bead
Appearance

Remarks

Fused Fluxes
1
2
3.
4

Optical CaF2
CaF2-1.2% CaO
CaF2-1.2% CaO
CaF2-1.2% CaO

CaF2-1.2% CaO

CaF2-20% Ca
7 CaF2-2% Ca
8
CaF2-2% Ca
Blended Fluxes*
6

good
poor
fair
poor
fair

Anodized
e l e c t r o d e and
basepl a t e

cracked
poor
poor

9
10
11
12
13
14
15

CaF2-1% NaF

very poor

CaFz-5% NaCl
CaF2-10% NaCl
CaF2-20% NaCI
CaF2-5% KC1
CaF2-10% KC1
CaF2-20% KC1

poor
poor
very poor
poor
poor

16

CaF2-10% CaCl2

17

CaF2-10% SrC12-3% LiCl

Argon shielded
19 mm e l e c t r o d e
extensi on

-Argon shielded

poor
poor
very poor

Suggested by
reference ( 5 )

A1 1 blended f l u x e s were made with optical q u a l i t y CaF2 and KC1 c r y s t a l s .

The CaC12, SrCl2 and LiCl were dried in an HCL-C12 atmosphere a t 500C

Table 11.

Oxygen and nitrogen content of titanium submerged a r c welds made

with reused optical q u a l i t y CaF;? flux.

No. of f l u x

Oxygen
Percent

Nitrogen

Reuses

Percent

Remarks

New

0.10

0.06

--

0.09

Flux dried in liC1-C12

furnace a f t e r fourth reuse.