Effect of Alloying Additions on the Weldability of 70 Cu-30 Ni

The effects of four elementsP, Sb, Fe and Mnon hot-cracking sensitivity are analyzed statistically, and Sb and the combination of Sb-Mn are found to be beneficial

BY W. F. SAVAGE, E. F. NIPPES, A N D J. E. CASTERAS

ABSTRACT. The effects of minor alloying additions on the hot-cracking sensitivity of 70 Cu-30 Ni alloy were evaluated in a full-factorial experiment. Composition modification of the as-received base material was accomplished by means of a novel remelt operation, and the weldability of the alloy was evaluated by the employment of the Tigamajig test. By applying the method of Yates, the resulting treatment effects of four elementsP, Sb, Fe, and Mnwere tabulated for the statistically significant, as-welded cracking parameters. It was proposed that the most harmful combinatorial treatments were those which most severely lowered the effective solidus temperature of the alloy and, thus, most drastically impaired, the hot ductility of the material. By means of a Gleeble-simulation technique, considerable improvement in the hot ductility of a P-modified lot of material was observed f o l l o w i n g a cold reduction between welding and testing events. It is suggested that improved hot-cracking resistance could be expected in subsequent passes in multipass welding if an interpass cold reduction of the weldment were employed. Because hot cracks were backfilled, the effective distribution coefficients for the elements Fe, M n , and Ni could be calculated from electron beam microprobe data. Introduction Hot cracking in a single-phase alloy generally occurs above the solidus temperature of the lowest-melting composition present. 1 The degree and extent of solute microsegregation in the weld microstructure determines

the magnitude of the lowest effective solidus temperature present. Thus, factors which modify the prevailing growth mode in the solidified weld will greatly influence hot-cracking sensitivity. A certain degree of control over both the temperature gradient existing in the liquid and the growth rate of the solid is possible by selection of the welding parameters. 2 " 1 Control of the shape of the weld pool by careful selection of welding conditions can drastically modify the pattern of microsegregation existing in the solidified weld. Certain minor alloying elements are believed to exert considerable influence on weldability. The impact of the composition factor is compounded by the heat-to-heat variations in compositions of both the major and minor alloying elements permitted for a given commercial material. 3 " 11 As a result of input from industry (via INCRA), four elements and appropriate levels for each were selected for study, based on control difficulties in scrap processing and/or alloying content required for physical properties, e.g., corrosion resistance. The pertinent reported effects of P, Sb, Fe, and Mn on the mechanical properties and weldability of Cu, Ni, and Cu-Ni alloys""1" may be summarized as follows: 1. Small additions of Fe, M n , P,

and Sb solid-solution strengthen Cu, Ni, and Cu-Ni alloys at the levels of concentration employed in this investigation. Sb is a much more effective hardener of Cu than is M n or P. 2. P is universally identified as an embrittling element in Cu-Ni and Ni alloys subjected to hot work. It has been reported, furthermore, that P is also injurious to the weldability of the cupronickels. When present in oxygen-free Cu, P also results in a loss of high-temperature ductility. 3. Sb appears to have no detrimental effect on either the hot workability of Cu or Ni, or on the weldability of Cu-Ni alloys. Sb in oxygen-free Cu appears to increase the room-temperature toughness slightly. 4. Fe and M n are generally considered innocuous alloying additions. Neither element seems to have a great effect on either the mechanical properties or weldability at low concentrations in Cu, Ni, or Cu-Ni alloys.

Object
The objectives of this experiment were to: 1. Investigate the effect of four minor alloying elements, P, Sb, Fe, and M n , often present in commercial cupronickel, either as intentional additions or as " t r a m p " elements, on the hot-cracking propensity. 2. Determine whether an improvement in hot-cracking resistance could be effected by a thermo-mechanical treatment involving cold work and recrystallization.

W. F. SAVAGE is Professor of Metallurgical Engineering and Director of Welding Research, and E. F. NIPPES is Professor of Metallurgical Engineering, Rensselaer PolyMaterials and Procedure technic Institute, Troy, New York; j. E. CASTERAS, former Graduate Student at RPI, Hot-Cracking Evaluation is now Research Engineer, ASARCO Inc., South Plainfield, New jersey. Material. The 70 Cu-30

Ni

base

W E L D I N G RESEARCH SUPPLEME NT j 375-s

Table 1 - C h e m i c a l Analyses of As-Received Material and GTA-Remelted Samples Unmodified (as-rec'd material) 69.96 29.99 0.0008 <0.002 0.03 0.0013 0.0001 0.0017 Modified (GTAremelted)

Element Cu Ni P Sb

_ 0.006 0.0025 0.18 0.23

Fe
Mn

Pb
S

m a t e r i a l u s e d i n this i n v e s t i g a t i o n w a s arc-cast at I n c o ' s S t e r l i n g Forest f a c i l i t y a n d w a s h o t r o l l e d t o V* i n . (3.2 m m ) p l a t e b y t h e Revere C o p p e r a n d Brass Company. Table 1 summarizes the c h e m i c a l c o m p o s i t i o n of t h e u n m o d i f i e d a s - r e c e i v e d , basic b i n a r y a l l o y . Experimental Design. The effect of f o u r m i n o r a l l o y i n g e l e m e n t s P , Sb, Fe, a n d M n o n t h e h o t - c r a c k i n g s e n s i tivity was investigated by Tigamajig tests 1 0 p e r f o r m e d o n 16 lots o f m o d i f i e d c o m p o s i t i o n p r o d u c e d in asreceived plate by means of the remelt o p e r a t i o n d e s c r i b e d b e l o w . T h e effects of these elements w e r e investig a t e d at t w o levels o f c o n c e n t r a t i o n : 1. T h e n o m i n a l l e v e l o f t h e h i g h purity, as-received material. 2. A l l o f t h e p o s s i b l e 16 c o m b i n a t i o n s in t h e f u l l f a c t o r i a l e x p e r i m e n t a l d e s i g n of 0.01 w / o P, 0 . 0 0 3 w / o Sb, 0 . 2 5 w / o Fe, a n d 0 . 3 w / o M n . CTA-Remelt Operation. The remelt o p e r a t i o n used to m o d i f y t h e c o m p o sitions of a relatively small v o l u m e of t h e plates is s h o w n in Fig. 1 a n d is summarized below: 1. A n a l l o y insert, p r e p a r e d by c o l d c o m p a c t i n g an a p p r o p r i a t e m i x t u r e of h i g h - p u r i t y metal p o w d e r s for each

combinatorial treatment, was inserted i n t o a p r e - m a c h i n e d "/^ i n . (8.7 m m ) w i d e g r o o v e a l o n g t h e 5 i n . (127 m m ) c e n t e r l i n e o f each of t h e s i x t e e n Vis X 5 X 6 i n . (3.2 X 127 X 152 m m ) specimen plates. 2. A series o f t h r e e G T A passes w e r e made using a sinusoidal w e a v e pattern t o r e m e l t a n d m i x t h e insert w i t h a v o l u m e o f t h e basic b i n a r y p l a t e . T h e plates w e r e m e c h a n i c a l l y r e s t r a i n e d d u r i n g this o p e r a t i o n o n an A l h e a t sink t o m a i n t a i n c o n s t a n t h e a t - f l o w c h a r a c t e r i s t i c s f r o m p l a t e t o p l a t e . By s t a n d a r d i z a t i o n of t h e r e m e l t - w e l d i n g p r o c e d u r e , the extent, shape, and prevailing g r o w t h m o d e of the c o m p o s i t i o n - m o d i f i e d remelted region were k e p t as s i m i l a r as p o s s i b l e . T h e w e l d i n g c o n d i t i o n s s u m m a r i z e d in T a b l e 2 were chosen to maintain a full-penetration weave bead. 3. A t m o s p h e r i c c o n t a m i n a t i o n w a s m i n i m i z e d by p e r f o r m i n g the GTAr e m e l t o p e r a t i o n in h i g h - p u r i t y Ar w i t h i n a dry box. Starting and run-off tabs w e r e a p p l i e d t o t h e plates t o m i n i m i z e e n d effects. The compacts were made from h i g h - p u r i t y C u , N i , Sb, Fe, M n , a n d Cu 3 P p o w d e r s . F o l l o w i n g b l e n d i n g , the powders were cold-compacted u n d e r 30 t o n s / i n . 2 (4220 k g / c m 2 ) u s i n g a minimal film of zinc stearatea c e t o n e l u b r i c a n t a p p l i e d t o t h e sides of the die plunger. The dimensions of each c o m p a c t w e r e Via x 'Vis x 3 i n . (1.6 X 8.7 X 7 6 m m ) ; t w o w e r e req u i r e d for each plate. Following the GTA-remelt operat i o n , reinforcements o n the b o t t o m of t h e plates w e r e m i l l e d flat, and t h e plates w e r e c u t , d r i l l e d , a n d d e g r e a s e d t o p r o v i d e test s p e c i m e n s , as i l l u s t r a t e d in Fig. 2. M i c r o s c o p i c o b s e r v a -

Table 2Welding Conditions Used During Remelt Operation W e l d i n g current W e l d i n g voltage Arc gap Electrode Travel speed Oscillation 144 A dcsp

9-10 V
%s in. (2.4 mm) measured cold V a in. (3.2 mm) EWTh2 90 deg incl. angle 0.9 ipm (22.9 m m / m i n ) A m p l i t u d e 0.5 in. (12.7 mm) peak-to-peak frequency 26 oscillat i o n s / m i n ; sinusoidal pattern 3, back and forth, consecutive Water-cooled Al 2 h o l d - d o w n bars parallel to w e l d centerline 40 cfh (19 liters/min) argon Positive-pressure argon 3-phase rectifier

Number of passes Backing plate Restraint

Torch gas Purge gas Power supply

t i o n at X 4 0 f a i l e d t o i n d i c a t e a n y c r a c k i n g in e i t h e r t h e r e m e l t e d r e g i o n or in t h e base m a t e r i a l in a n y of t h e GTA-remelted specimens. Tigamajig Testing. W i t h t h e w e l d i n g c o n d i t i o n s s h o w n i n T a b l e 3, a s t a t i o n ary G T A arc w a s s t r u c k at m i d s p a n o f each sample and m a i n t a i n e d for 9 s e c o n d s (s). A t t h e e n d o f t h a t t i m e , a n o m i n a l a u g m e n t e d strain o f 0.785% was s u d d e n l y a p p l i e d to t h e s p e c i m e n t h r o u g h the action of the die block, w i t h arc c u t - o f f o c c u r r i n g s i m u l t a n e o u s l y . T h e arc t i m e w a s s e l e c t e d t o provide a weld pool showing incomplete penetration prior to the establishment of steady-state heat-flow conditions. As a result of these events, hot

Powder metal compact

Fig. 1Schematic illustration of remelt operation: (A) machined plate; (B) melting and mixing of powder metal compact (plate is mechanically restrained along AB and CD); (C) preparation of Tigamajig specimens

376-si DECEMBER

1978

Table 3Welding Conditions Used During Tigamajig Testing Arc Arc Arc Arc current voltage time length 115 A dcsp 9-10 V 9s Vie in. (1.6 mm) measured cold %. in. (2.4 mm) EWTh2 90 deg incl. angle 35 cfh (16.5 liters/min) argon None 3-phase rectifier 0.785% [8.5 in. (216 mm) die block]

13/ D /32

-Composition modified region

/ T \

Electrode Shielding gas

4U
ALL DIMENSIONS IN INCHES specimens

Fig. 2Dimensions

of Tigamajig

Post arc time delay Power supply Nominal augrr strain

GTA SPOT

- APPARENT FUSION LINE -EXTENT OF PARTIALLY MEITED REGION

tm
Fig. 3Details of hot-cracked region. Marble's reagent etch, section parallel plate surface. X 6 5 (reduced 35% on reproduction) to cracks w e r e p r o d u c e d w i t h i n the m o d i f i e d region adjacent to the GTA s p o t w e l d in all s p e c i m e n s . T h i s s i t u a t i o n , therefore, resembles hot cracking t h a t o c c u r s in a p r e v i o u s pass d u r i n g a m u l t i p l e - p a s s w e l d m a d e u n d e r restraint. T h e a p p e a r a n c e of t h e h o t cracks produced is i l l u s t r a t e d in Fig. 3. Cracking Data. After testing, the t o t a l crack l e n g t h , t h e m a x i m u m crack l e n g t h , a n d t h e average c r a c k l e n g t h w e r e m e a s u r e d at X 40 in each s p e c i m e n in t h e a s - w e l d e d c o n d i t i o n . S i m i lar d a t a w e r e a c c u m u l a t e d f o r each specimen following metallographic polishing to a horizontal plane located (A) PHOSPHORUS (Unmodified) a p p r o x i m a t e l y 0.010 i n . (0.254 m m ) b e l o w the original surface. Chemical Analyses. Chemical analyses of t h e r e m e l t e d r e g i o n s w e r e m a d e f o r e a c h of t h e e x p e r i m e n t a l specimens. From the original specimens, groups w e r e selected on the basis of t h e i r c h e m i c a l c o m p o s i t i o n . The distributions of c o m p o s i t i o n s and important statistical quantities of t h e s e g r o u p s are i l l u s t r a t e d i n Figs. 4 - 7 . O n l y the c r a c k i n g data f r o m these s p e c i m e n s w e r e c o n s i d e r e d in this investigation. T h e average c o m p o s i t i o n s o f t h e a l l o y m o d i f i c a t i o n s , s h o w n i n Figs. 4 - 7 , are also p r e s e n t e d in T a b l e 1 f o r (A) ANTIMONY (Unmodified)
H

c o m p a r i s o n w i t h t h e analysis o f t h e u n m o d i f i e d base m e t a l . Electron-Beam Microprobe Analysis. M o s t of t h e h o t c r a c k s w e r e b a c k f i l l e d , as s h o w n in Fig. 8. T h e l i q u i d in t h e d i f f u s i o n g r a d i e n t at t h e s o l i d - l i q u i d i n t e r f a c e t e n d s t o p e n e t r a t e , or b a c k fill, the n e w l y o p e n e d crack. Thus a g o o d estimate of the d i s t r i b u t i o n coeff i c i e n t s o f t h e v a r i o u s s o l u t e s can be o b t a i n e d b y analysis o f t h e m a t e r i a l in t h e backfilled crack. This segment of t h e investigation w a s c a r r i e d o u t o n an e l e c t r o n p r o b e microanalyzer by the point-count t e c h n i q u e . A t y p i c a l traverse is i n d i c a t e d b y l i n e A B in Fig. 8. T h e g r a p h i c a l results o f t y p i c a l analyses are s h o w n in Figs. 9, 10, a n d 1 1 , f o r N i , Fe, a n d M n , respectively. Weldability Improvement This p o r t i o n of t h e i n v e s t i g a t i o n , concerned w i t h improving the hotcracking sensitivity of a particularly susceptible, P-modified cupronickel, involved hot-ductility measurements carried out o n the Gleeble.2" T w o types of specimens w e r e prepared: 1. Plates i n i t i a l l y 0.125 i n . (3.2 m m ) thick and m o d i f i e d w i t h a P-addition (B) ANTIMONY (Modified)
14

(B)PHOSPHORUS

(Modified)

X< 0.0020 x ; 0.0008 S =00007 X =0.0058 S =0 0 0 3 5 2

CO UJ

s=

CO

12
CL 10

X = 0.0025 S = 0.0002

<
U-

w 8 o m

<
o 6
CD

'
0

h n ..

0.002 0.004 WEIGHT %

0006 0.012 WEIGHT %

Al

2
0

I
2 } 0.002 0 004 WEIGHT % 3 0.002 0.004 WEIGHT %

Fig. 4Distribution of compositions for specimens (A) unmodified; (B) modified. Average composition deviation = S

containing P: = X, standard

Fig. 5Distribution of compositions (A) unmodified; (B) modified

for specimens

containing

Sb:

WELDING

R E S E A R C H S U P P L E M E N T I 377-s

(A) IRON (Unmodified)

(3) IRON (Modified)

(A) MANGANESE (Unmodified)

KL
14 X =0.0013 S = 0.0004
CO

(B) MANGANESE (Modified)

12 .
J

P10.

X =0.0295 S =00055 5

X =0.1819 S =0.0743

12

12

X 0.2304 S = 0.0963

> < co 8
O

y
a 10 3

<
LU 2

"> 8
6

LU 6

14

I 4

I<
2

1
2 0 0,002 WEIGHT 0.004 % 0.006 3 0 1 0.2 0.3 0 . 4 WEIGHT %

0.04 0.08 WEIGHT %

0.1

IIII I i .. 0.2 0.3 0.4 0.5 0.6 WEIGHT%

t
0.6

0.5

Fig. 6Distribution of compositions (A) unmodified, (B) modified

for specimens

containing

Fe:

Fig. 7Distribution of compositions (A) unmodified; (B) modified

for specimens containing

Mn:

GTA SPOT

G l e e b l e s p e c i m e n s , 0.1 i n . (2.5 m m ) t h i c k b y %a i n . (7.9 m m ) w i d e by 314 i n . (82.6 m m ) l o n g , w e r e m a c h i n e d f r o m these plates w i t h the c o m p o s i t i o n modified region centered l o n g i t u d i nally. These specimens w e r e subjected to either of t w o t h e r m o - m e c h a n i c a l c y c l e s ( P r o g r a m A or B) in t h e G l e e b l e , w i t h all t e s t i n g b e i n g d o n e in an a r g o n (Ar) a t o m o s p h e r e c h a m b e r . Program A. S p e c i m e n s w e r e h e a t e d t o a p e a k t e m p e r a t u r e , Tp, a n d h e l d f o r t i m e s r a n g i n g b e t w e e n 0 a n d 1500 s b e f o r e r a p i d strain a p p l i c a t i o n . T h e peak t e m p e r a t u r e in e v e r y case w a s r e a c h e d in 9 s, t h e s a m e t i m e i n t e r v a l used p r i o r t o l o a d i n g d u r i n g T i g a m a j i g testing. T h e m a g n i t u d e o f T w a s c h o s e n t o lie b e t w e e n t h e n o m i n a l s o l i d u s (2138 F, 1170 C) a n d t h e instantaneous temperature of the region to w h i c h cracking was observed to extend. The a p p r o x i m a t e e x t e n t o f this h o t - c r a c k i n g range w a s m e a s u r e d b y t h e r m o couples attached to Tigamajig specim e n s d u r i n g t e s t i n g . Final s e l e c t i o n o f T w a s based o n tests m a d e o n G l e e b l e

Fig. 8Backfilling in a Tigamajig hot crack. Line AB denotes electron-beam microprobe traverse. Modified Marbles reagent parallel to plate surface. X225 (reduced 27% on reproduction)

representative etch, section

o f 0.01 w t - % w e r e c o l d r o l l e d 20% t o 0.100 i n . (2.5 m m ) t h i c k n e s s . 2. A n o t h e r p l a t e , i n i t i a l l y 0.100 i n .

(2.5 m m ) t h i c k , w a s also m o d i f i e d t o 0.01 w t - % P but was not coldworked.

Nominal composition

-Backfilled region-

Backfilled region -

Fig. 9Electron-beam resu Its for Ni

microprobe

analysis

Fig. 10Electron-beam results for Fe

microprobe

analysis

Fig. 11Electron-beam results for Mn

microprobe

analysis

378-s I D E C E M B E R

1978

BOUNDARY

O.I n I

Fig. 12Transmission electron micrograph of as-welded Gleeble specimen showing distribution of dislocations: A (left)in the vicinity of a grain boundary; B (right)in a region removed from structural boundaries. X90.000 (reduced 35% on reproduction) specimens heated to temperatures within the hot-cracking range measured above. Specimens heated to 2113 F (1156 C) and 2097 F (1147 C) exhibited gross melting; t w o specimens heated to 2081 F (1138 C) exhibited approximately zero ductility, w i t h no extensive bulk melting. O n this basis, 2081 F (1138 C) was chosen as the peak temperature Tp. The straining rate of the Gleeble was made equal to the straining rate of the Tigamajig. Program B. Program B consisted of two separate operations. The first consisted of subjecting Gleeble specimens to a typical annealing cycle by heating to 1450 F (788 C) at the Tigamajig heating rate and holding at that temperature for various lengths of time (from 0 to 720 s), followed by free cooling to room temperature. The second part consisted of hotductility evaluation by heating of the specimens, at the Tigamajig heating rate, to T = 2081 F (1138 C), f o l l o w e d by rapid strain application. Transmission Electron Microscopy. TEM was employed to determine, qualitatively, the effect of the various thermo-mechanical histories on the distribution of dislocations about grain and/or substructure boundaries in the material. Three Gleeble specimens were studied: Specimen 1, in the as-welded condition, was representative of the composition-modified region of the Tigamajig specimens. Specimen 2, in the cold-worked condition, corresponded to approximately 20% reduction in sheet thickness. Specimen 3, originally cold worked, was recrystallized by a thermal excursion to 2081 F (1138 C) for 300 s, followed by free cooling. 5% level of significance), there is a 95% chance that the total crack length w i l l decrease by 0.023 in. (0.58 mm) relative to the unmodified alloy. Again considering the Sb-Mn treatment (e.g., the 1.2 average-crack-length value at 5% level), there is a 95% chance that the average crack length will decrease by 0.0012 in. (0.03 mm) relative to the unmodified alloy. For comparison purposes, the average values of the cracking parameters for the unmodified base alloy were: total crack length, 0.199 in. (5.1 mm); maximum crack length, 0.028 (0.7 mm); and average crack length, 0.016 in. (0.4 mm). Analyses of data taken following metallographic polishing of the specimens yielded no significant effects at the 1, 5, or 10% levels and, therefore, are not considered further in this discussion. The absence of statistically significant effects was related to the backfilling process which obscured the hot crack. For the as-welded data, effects of the factorial treatments on the totalcrack-length parameter were significant at the 1% level in the case of six treatments. In other words, in those six cases, there is no greater a probability than 0.01 that the effects measured were due to chance fluctuations in the data. The following summarizes the analysis of total-crack-length data at the 1% level: 1. P was detrimental to the w e l d ability of this alloy, especially in the presence of Sb; although Sb alone appears to be a beneficial addition. 2. Fe and Sb when present together are somewhat detrimental, while Sb alone appears to be beneficial and Fe alone does not have a significant effect.

Fig. 13Transmission electron micrograph of a Gleeble specimen cold worked 20% following welding, showing distribution of dislocations in the vicinity of a structural boundary. X90,000

The resulting electron micrographs are reproduced in Figs. 12, 13, and 14, respectively. Results Hot-Cracking Results The method of analysis proposed by Yates-1 was applied to the cracking data. Statistical estimates of the effects of each treatment and estimates of error were calculated for the following three cracking parameters: total, maximum, and average crack length. The results of the calculations for the as-welded cracking parameters are summarized in Table 4. The values recorded in this table may be interpreted as follows. In the case of the Sb-Mn experimental treatment (e.g., the 23 total-crack-length value at the

W E L D I N G RESEARCH S U P P L E M E N T I 379-s

Fig. 14Plot of % reduction in area vs. time of Gleeble specimens subjected to programs A and B

IOO

400 500 T I M E (SECONDS)

3. In t h e p r e s e n c e o f M n , w h i c h a l o n e is d e t r i m e n t a l , t h e c o m b i n a t i o n o f Fe a n d Sb r e p r e s e n t s t h e w o r s t effect n o t e d . A s i m i l a r analysis o f d a t a f o r t h e maximum-crack-length parameter yielded the f o l l o w i n g : 1 . In t h e p r e s e n c e o f M n , the c o m b i n a t i o n o f Fe a n d Sb w a s d e t r i mental. 2. T h e e l e m e n t s P a n d Sb w h e n each w a s p r e s e n t w i t h Fe, w e r e i n j u rious to this cracking parameter, a l t h o u g h n o n e of these elements had a significant effect w h e n present alone. Finally, t h e f o l l o w i n g results w e r e n o t e d for t h e average-crack-length parameter: 1, Sb d e c r e a s e d t h e average c r a c k length. 2. T h e p r e s e n c e o f P w i t h e i t h e r Sb, Fe, or M n i n c r e a s e d t h e a v e r a g e crack length.

Electron-Beam M i c r o p r o b e Analysis Results M i c r o p r o b e data gave the f o l l o w i n g results: 1. M n s e g r e g a t e d t o t h e last l i q u i d t o solidify. The average c o m p o s i t i o n w i t h i n t h e b a c k f i l l e d h o t cracks w a s a b o u t 0.57 w t - % , w h i l e t h e a v e r a g e c o m p o s i t i o n o f t h e u n c r a c k e d , rem e l t e d r e g i o n w a s a b o u t 0.38 w t - % . 2. Fe s e g r e g a t e d a w a y f r o m t h e last s o l i d i f y i n g l i q u i d . W h i l e t h e average composition of the unaffected remelt r e g i o n w a s a b o u t 0.32 w t - % , t h e average c o m p o s i t i o n w i t h i n t h e b a c k f i l l e d h o t c r a c k s w a s a b o u t 0.16 w t - % . 3. T h e c o m p o s i t i o n o f N i w i t h i n t h e b a c k f i l l e d h o t cracks a v e r a g e d a b o u t 18 w t - % , w h i l e t h e c o m p o s i t i o n o f t h e r e m e l t e d r e g i o n a v e r a g e d a b o u t 30 wt-%. 4. T h e levels o f Sb a n d P did not

differ significantly f r o m the unaffected to t h e c r a c k e d r e g i o n s . T h e levels at w h i c h t h e s e e l e m e n t s w e r e p r e s e n t in the composition-modified region w e r e t o o l o w for accurate measurements. 5. W h e n Fe a n d M n w e r e p r e s e n t t o g e t h e r at t h e i r h i g h levels, n o d i f f e r e n c e in t h e t y p e o f s e g r e g a t i o n e a c h exhibited individually was noticed. Results of Gleeble Investigation The data resulting f r o m the Gleeble s t u d i e s are p l o t t e d i n Fig. 15. T h e f o l l o w i n g p o i n t s are e v i d e n t : 1. The recovery of d u c t i l i t y m e a s u r e d at 2081 F (1138 C) w a s m o s t p r o n o u n c e d in t h e case o f m a t e r i a l c o l d r o l l e d 20% b e t w e e n w e l d i n g a n d t e s t i n g o p e r a t i o n s a n d least n o t i c e a b l e in t h e m a t e r i a l t e s t e d i n t h e a s - w e l d e d condition. 2. T h e h o t d u c t i l i t y o f a c o l d - r o l l e d specimen tested immediately on r e a c h i n g 2081 F (1138 C) is 8%, w h i l e the ductility of the as-welded specim e n s t e s t e d at t h e s a m e p o i n t is e s s e n tially zero. 3. A n n e a l i n g o f c o l d - r o l l e d s p e c i m e n s at 1450 F (788 C) f o l l o w i n g w e l d i n g also leads t o an i m p r o v e m e n t in d u c t i l i t y w i t h t i m e at a n n e a l i n g t e m p e r a t u r e , b u t t h e rate of d u c t i l i t y r e c o v e r y is s l o w e r t h a n in t h e case o f specimens exposed to higher temperatures for t h e same times. Discussion of Results

Table 4Results of Yates Analyses for Indicated Parameters (Values Given in Thousandths of an Inch at the 1%, 5%, and 10% Levels of Significance) Total Crack length Treatment P Sb PSb Fe PFe SbFe PSbFe Mn PMn SbMn PSbMn FeMn PFeMn SbFeMn PSbFeMn 1% 5% Maximum crack length Average crack length

10%

1%

5%

10%
+ 2.1

1%

5%

10%

+ 37 -50 + 71 + 3.5 + 3.6

+ 2.5 -23

-2.6 + 2.7
+ 1.5 -1.0

+ 28 + 62

+ 1.7 -2.3 -1.2 Hot-Cracking Studies F o l l o w i n g e s t a b l i s h m e n t o f t h e arc spot d u r i n g Tigamajig testing, the resulting instantaneous temperature gradient encompasses a p o r t i o n of the remelted region w h e r e the actual

-19
-21 -74 + 6.0 -2.4

+ 2.0 -2.2

-2.5

380-s | D E C E M B E R

1978

Table 5-Distribution Coefficients of Indicated Elements Equilibrium value from diagram 1.4 0.75 1.2 Calculated (microprobe data) 2.0 0.67 1.66 Reported in literature 3.8-5.2 0.45 1.9-2.4 1.6

Element Fe Mn Ni

Fig. 15Transmission electron micrograph of a Gleeble specimen cold worked 20% following welding and subjected to 2081 F for 300 s, followed by a free cool to ambient temperature. X90.000 (reduced 55% on reproduction)

temperatures lie between the effective liquidus and solidus. Because of the point-to-point variation in the effective solidus resulting from microsegregation, those portions solidifying last during the remelt operation (i.e., interdendritic regions) experience actual temperatures above their effective melting points. This region of partial melting, 8 which is characterized by liquid-covered interdendritic surfaces, exists at the instant of augmented strain application. A large majority of the cracks observed in this investigation had the appearance illustrated in Fig. 8. It was noted that: 1. Initiation of cracking occurred in the partially melted region. 2. The cracking was intimately related to the solidification substructure boundaries. 3. The cracks, most of which were backfilled, seemed to have extended well beyond the partially melted region. It is proposed that the hot cracking observed depended on three contributing factors, which occurred on sudden loading during Tigamajig testing: 1. Sliding of liquid-covered interdendritic boundaries under shear stresses. 2. Separation of liquated boundaries under the influence of normal stresses. 3. Crack extension through unliquated boundaries in the solidification substructure. The first two events may be identified w i t h the crack-initiation event, while the last factor is related to crack propagation. This crack-extension process may be expected to continue until the crack is effectively stopped through the change in crack-tip geometry and/or the inability of the crack to extend through an unliquated boundary by

conventional fracture mechanisms. The degree of crack extension tended to increase in those regions where a solute element solution strengthened an alloy, yet at the same time impaired the ductility and toughness. For example, the expected segregation of P to the last-solidifying liquid in the remelt region should be responsible, based on the literature, for the solid-solution strengthening of that region, with a concurrent notable loss in ductility, relative to regions of lower P concentration. This combination of properties may reasonably be expected, therefore, to result in an increase in the degree of crack extension, as noted in this experiment. Hot-Ductility Studies Figure 12A, an electron micrograph, illustrates the distribution of dislocations in the vicinity of a grain boundary in the P-modified region of an aswelded Tigamajig specimen. Figure 12B represents the situation in regions removed from such boundaries. Comparison of these figures leads to the identification of the following features: 1. Dislocations are present in greater density in the vicinity of the boundary. 2. In several locations, dislocations appear to be anchored at various points along the dislocation length. While this pinning may be attributed to interaction w i t h " t r e e " dislocations located on intersecting slip planes, this feature probably also reflects the effect of solution strengthening. 3. The above hypothesis is strengthened by the zig-zag dislocation configuration which is thought to reflect the interaction of an otherwise straight dislocation line with solute-atom atmospheres.- 2 The above-mentioned features tend to confirm the proposal that relatively low ductility may be expected in the vincinity of solidification-substructure boundaries in the remelted region of Tigamajig specimens. W h e n an aswelded specimen was rapidly strained in the Gleeble upon reaching a temperature representative of the cracking range expected in the Tigamajig specimen, essentially zero reduction in area was noted. Following a mild cold working of a

specimen having the prior history described above, the density of dislocations, as illustrated in Fig. 13, increased significantly, as w o u l d be expected, relative to Figs. 12A and 12B. More importantly, no features identified w i t h solution strengthening were apparent in the vicinity of the b o u n d aries. A Gleeble specimen of this description, when heated to 2081 F (1138 C) and strained immediately, showed a reduction in area of approximately 8% (Fig. 14). This recovery in ductility is attributed both to the disruption of the solute atmospheres and to recrystallization. The microstructure in Fig. 15 represents a cold-worked specimen which was heated to 2081 F (1138 C), maintained for 300 s and allowed to free cool in the Gleeble. The transmission electron micrograph shows a marked decrease in dislocation density relative to the cold-worked structure (Fig. 13). In addition, there is again a general absence of those features associated w i t h solution-hardening in the vicinity of grain boundaries, as shown previously in Fig. 12A. As supported by optical metallography, the combination of time and temperature employed was sufficient to cause recrystallization and the separation of grain and subgrain boundaries from the regions of microsegregation. As might be expected, the ductility of this specimen measured following rapid loading after 300 s at 2081 F (1138 C), approximately 46% reduction in area as shown in Fig. 14, was considerably improved over that of the previous t w o specimens. The results of this section suggest a practical means by which this improvement in ductility might be applied to decrease hot-cracking sensitivity during multipass welding. It has been shown that a relatively mild cold working of the previous pass was responsible for the ductility recovery. This mechanical deformation could be effected by shot peening, hammer peening, or roll planishing between welding passes. Selection of welding conditions which could effectively increase the time spent at elevated temperatures (e.g., slower travel speed) could be expected to decrease, further, the hot-cracking susceptibility during multipass welding.

W E L D I N G RESEARCH S U P P L E M E N T I 381-s

Calculation of Effective Distribution Coefficients Cs, t h e c o n c e n t r a t i o n o f a s o l u t e in t h e last r e g i o n s o f a w e l d t o s o l i d i f y , is e q u a l t o t h e e x p r e s s i o n C / k e , w h e r e ke is an e f f e c t i v e d i s t r i b u t i o n c o e f f i c i e n t f o r t h e p a r t i c u l a r s o l u t e , a n d C is t h e nominal c o m p o s i t i o n of the alloy. A m e a s u r e o f ke m a y b e c a l c u l a t e d b y d i v i d i n g t h e average c o n c e n t r a t i o n o f t h e s o l u t e in t h e r e g i o n e x t e r i o r t o t h e c r a c k , C 0 , by t h e average c o n c e n t r a t i o n of the solute w i t h i n the confines of the c r a c k , Cs. The m i c r o p r o b e data generated in this investigation a l l o w e d calculation of effective distribution coefficients f o r Fe, M n , a n d N i , as s h o w n in C o l u m n 2 o f T a b l e 5. V a l u e s g i v e n in C o l u m n s 1 and 3 indicate, respectively, t h e e q u i l i b r i u m v a l u e o f k m e a s u r e d f r o m phase diagrams and t h e value of k as m e a s u r e d by o t h e r i n v e s t i g a tors. 8 - 2 ' In t h e case o f Fe a n d N i , t h e d e v i a t i o n of t h e reported values f r o m t h e e q u i l i b r i u m v a l u e s is p o s i t i v e ; in t h e case o f M n t h e d e v i a t i o n is n e g a tive. O n e w o u l d expect these deviat i o n s b e c a u s e o f t h e s u p p r e s s i o n of t h e s o l i d u s l i n e as a r e s u l t of r a p i d cooling. 2 3 - 2 4

as Fe h a d n o e f f e c t , a n d Sb w a s b e n e ficial. Second-order c o m b i n a t i o n s of P-Fe a n d Sb-Fe w e r e d e t r i m e n t a l , a n d t h e c o m b i n a t i o n P-Sb w a s t h e m o s t d e t r i m e n t a l o f all. O n t h e o t h e r h a n d , the c o m b i n a t i o n S b - M n was beneficial. 6. A G l e e b l e - s i m u l a t i o n t e c h n i q u e s h o w e d t h a t , f o l l o w i n g an i n t e r p a s s cold reduction of the w e l d m e n t , a s i g n i f i c a n t i m p r o v e m e n t c o u l d be exp e c t e d i n t h e h o t d u c t i l i t y of a r e g i o n in w h i c h Tigamajig cracking was o b s e r v e d . In this case, a P - m o d i f i e d specimen exhibited zero ductility when strained immediately upon reaching a t e m p e r a t u r e typical of the p a r t i a l l y - m e l t e d region. A similar speci m e n , r e d u c e d 20% in t h i c k n e s s b e f o r e b e i n g tested u n d e r t h e same c o n d i t i o n s , s h o w e d a r e d u c t i o n i n area o f 8%. L o n g e r t i m e s p r i o r t o t h e a p p l i c a t i o n o f l o a d r e s u l t e d in larger r e c o v e r ies i n h o t d u c t i l i t y . 7. E f f e c t i v e d i s t r i b u t i o n c o e f f i c i e n t s in t h e 70 C u - 3 0 Ni alloy were measured by e l e c t r o n - b e a m microp r o b e traverses across b a c k - f i l l e d h o t cracks f o r t h e e l e m e n t s Fe, M n , a n d Ni. Acknowledgments

Conclusions 1. T h e r e m e l t o p e r a t i o n , used to modify the m i n o r - e l e m e n t c o m p o s i t i o n o f t h e a s - r e c e i v e d 70 C u - 3 0 N i base m a t e r i a l , p r o v i d e d a r e a s o n a b l y reproducible solidification substructure u p o n w h i c h w e l d a b i l i t y evaluations c o u l d be based. 2. A f u l l - f a c t o r i a l e x p e r i m e n t a l d e sign a l l o w e d c a l c u l a t i o n o f c o m p o s i tional effects o n the hot-cracking p r o p e n s i t y . Statistical levels o f c o n f i d e n c e f o r t h o s e e f f e c t s w e r e also determined. 3. T h e h o t c r a c k i n g o b s e r v e d in t h e T i g a m a j i g test s p e c i m e n s a p p e a r e d t o have o r i g i n a t e d in l i q u a t e d b o u n d a r i e s adjacent to t h e GTA spot. H o w e v e r , t h e cracks e x t e n d e d b e y o n d t h e a p p a r ent limits of the partially-melted region. 4. T h e w e l d a b i l i t y o f t h e c o m p o s i t i o n - m o d i f i e d r e g i o n w a s i m p a i r e d by the presence of m i n o r alloying elements w h i c h lowered the effective s o l i d u s t e m p e r a t u r e a n d h a d an d i s p r o p o r t i o n a t e l y adverse effect o n the ductility. 5. S p e c i f i c c r a c k i n g t e n d e n c i e s in t h e 70 C u - 3 0 N i a l l o y w e r e n o t e d f r o m a Yates analysis o f a s - w e l d e d c r a c k i n g d a t a . As e x a m p l e s , P a n d M n w e r e detrimental to the weldability, where-

T h e a u t h o r s w i s h t o express t h e i r gratitude to the International Copper Research A s s o c i a t i o n f o r f i n a n c i a l s u p p o r t o f t h i s i n v e s t i g a t i o n . Particular a c k n o w l e d g m e n t is d u e D r . L. M c D . Schetky and the W e l d a b i l i t y C o m m i t tee, S u b c o m m i t t e e on Copper Nickel A l l o y s , o f t h e W e l d i n g Research C o u n cil f o r t h e i r c o n t i n u e d i n t e r e s t a n d guidance. References 1. Baker, R., and N e w m a n , R., "Cracking in Welds," Met. Const, and Brit. Wld. I., 1, p. 2s, Papers 1 and 2, February 1969. 2. Savage, W . F., Lundin, C. D., and Aronson, A. H., " W e l d Metal Solidification Mechanics," Welding lournal, 44 (4), April 1965, Research Suppf, pp. 175-s to 181-s. 3. Savage, W. F., Lundin, C. D., Chase, T. F., "Solidification of Fusion Welds in FaceCentered Cubic Metals," Welding Journal, 47 (11), Nov. 1968, Research Suppf, pp. 522-s to 526-s. 4. Savage, W. F., and Aronson, A. H., "Preferred Orientation in the W e l d Fusion Zone," Welding journal, 45 (2), Feb. 1966, Research Suppf, pp. 85-s to 89-s. 5. Pease, C , "The Practical W e l d i n g Metallurgy of Nickel and High Nickel Alloys," Welding lournal, 36 (7), July 1957, Research Suppl., pp. 330-s to 334-s. 6. W i t h e r e l l , C. E., "Some Factors Affecting the Weldability of the Cupronickels," Welding lournal, 39 (9), Sept. 1960, Research Suppl., pp. 411-s to 416-s.

7. Welding, Brazing and Soldering of Copper and its Alloys, Publication No. 47, Copper Development Association, London, England, 1958. 8. Savage, W . F., Nippes, E. F., and Miller, T. W., "Microsegregation in Partially Melted Regions of 70 Cu-30 Ni W e l d m e n t s , " Welding lournal, 55 (7), July 1976, Research Suppf, pp. 181-s to 187-s. 9. Inglis, N., and M i c h i e , C , " W e l d i n g of Copper and Its Alloys; Difficulties, Possible Improvements and their Economic Implicat i o n , " INCRA Report IRD 67-62, October 1967. 10. Savage, W. F., Nippes, E. F., and G o o d w i n , G. M., "Effect of M i n o r Elements on Hot-Cracking Tendencies of Inconel 600," Welding lournal, 56 (8), August 1977, Research Suppf, pp. 245-s to 253-s. 11. Jackson, R., Edge, D., and Moore, D., " A Preliminary Assessment of the Value of Minor Alloying Additions in Counteracting the Harmful Effect of Impurities on the Hot Workability of Some Copper A l l o y s , " / . Inst. Metals, 98, p. 193, 1970. 12. French, R and Hibbard, W., "Effect of Solute Elements on the Tensile Deformation of Copper," Trans. AIME, 188. p. 53, 1950. 13. Brick, R., M a r t i n , D., and Angier, P., "Effects of Various Solute Elements on the Hardness and Rolling Texture of Copper," Trans. ASM, 31, p. 675, 1943. 14. Kraai, D., and Floreen, S., " H o t Ductility of N i c k e l , " Trans. AIME, 230, p. 833, 1964. 15. Lee, J. W., Nichols, E. E., and G o o d w i n , S., "VARESTRAINT Testing of Cast 70 Cu-30 Ni Alloy," Welding lournal, 47 (8), August 1968, Research Suppl., pp. 371-s to 377-s. 16. Hanson, D., Archbutt, S., and Ford, G., "Investigation of the Effects of Impurities in Copper, Part 6 The Effect of Phosphorous on Copper," /. Inst. Metals, 43, p. 41, 1930. 17. Archbutt, S., and Prytherch, W., " i n vestigation of the Effects of Impurities in Copper, Part 7, The Effect of A n t i m o n y on Copper," I. Inst. Metals, 45, p. 265, 1931. 18. Hanson, D., and Ford, G., "Investigation of the Effects of Impurities in Copper, Part 2, The Effect of Iron on Copper," /. Inst. Metals, 32, p. 335, 1924. 19. Cook, M., and Davy, E., " H o t W o r k ing of Copper and Copper Alloys," I. Inst. Metals, 76, p. 501, 1949-50. 20. Nippes, E. F., and Savage, W. F., " D e velopment of a Specimen Simulating the Weld Heat Affected Z o n e , " Welding lournal, 28 (11), Nov. 1949, Research Suppl., pp. 534-s to 546-s. 21. Cochran, W., and Cox, O , Experimental Designs, Wiley and Sons, New York, N. Y. 1957. 22. Friedel J., Dislocations, Pergamon Press, New York, N. Y., 1964, pp. 380-381. 23. Bastow, A., and K i r k w o o d , D., " S o l i d / Liquid Equilibrium in Copper-Nickel-Tin Systems Determined by Microprobe Analysis," ). Inst. Metals, 99, p. 271, 1971. 24. Olsen, W. and Hultgren, R., "Effect of Rate of Freezing on the Degree of Segregation in Alloys," Trans. AIME, 158, 1950.

382-sl DECEMBER

1978