Development of Nickel-Chromium-Silicon Base Filler Metals Alloying with small amounts of phosphorus decreases melting temperatures during development on low melting boron-free brazing filler metals for high temperature service BY E. LUGSCHEIDER, O. KNOTEK A N D K. KLOHN Introduction For some applications—mainly in the nuclear industries—boron-free nickel base filler metals are prefered. O n e of the important filler metals used in these fields in West Germany is the nickel-chromium-silicon filler metal BNi-5. This nickel base filler metal, containing 19 wt-% chromium and 10.2 wt-% silicon, has a considerably high liquidus temperature of about 1408 K or 1135 C (2075 F) in comparison to boron-containing filler metals such as BNi-2, BNi-3 or BNi-4. 1 Although the suggested brazing temperature of BNi-5 is high, this filler metal is used in non-nuclear industries because of the possibility to get very ductile joints using a heat treatment after brazing. The brittle silicide hard phases of the brazing gap can be eliminated during the diffusion heat treatment because of the high solid solubility of silicon in the base metal. 2 This most important improvement of joint ductility for high strength components is very difficult in cases using boridecontaining filler metals because of the very low solid solubility of boron in the base metal.In developing boron-free low melting nickel base filler metals, the melting behavior of nickel-chromium silicon alloys (depending on the chromium and silicon content) has been investigated systematically. Further, the influence of low content of phosphorus on the melting and flowing behavior has been examined. Selected Ni-Cr-Si and Ni-Cr-Si-P alloys were used for brazing experiments. Their strength properties were tested using the AWS single-lap standard method. 1 The ability of the investigated alloys for high temperature brazing filler metal is discussed. Properties of Ni-Cr-Si and Ni-Cr-Si-P Alloys Melting Behavior of Ni-Cr-Si Alloys In the nickel-rich part of the Ni-Cr-Si system, the filler metal BNi-5 is the only alloy used in high temperature brazing. BNi-5 (19 wt-% Cr, 10.2 wt-% Si, bal. Ni) has a liquidus temperature of 1408 K or 1135 C (2075 F). Systematic investigations on the melting behavior of ternary alloys dependent on the chromium and silicon content should show if there are concentration areas of lower melting temperatures. The element silicon is essentially responsible for reducing the melting point of Ni-Cr-Si alloys. O n the other hand, silicon stabilizes brittle silicide hard phases distributed in the nickel solid solution. 3 Therefore, a compromise has to be made between lowering the melting point and raising the volume of hard phases; this leads to an upper limit corresponding to a silicon content of about 10 to 15 wt-% in the filler metal. The decrease of the melt- Paper presented during the Ninth International AWS-WRC Brazing Conference held in New Orleans, Louisiana, during April 4-6, 1978. E. LUGSCHEIDER, O. KNOTEK AND K. KLOHN are with the Institut fur Werkstoffkunde, Technical University, Aachen, West Germany. ing points of ternary Ni-Cr-Si alloys can only be given by nonvariant reactions influenced by eutectic reactions of the binary systems. In the nickel-silicon binary system one eutectic reaction exists at significant silicon concentrations. The eutectic is formed between nickel solid solution and the silicide Ni.,Si at 11.5 wt-% silicon and 1423 K or 1150 C (2102 F). Ni3Si results by a peritectic reaction between the melt and the silicide Ni-,Si, at a temperature of 1438 K or 1165 C (2129 F).1 In the nickel-chromium binary system, only one eutectic reaction exists between the solid solutions of nickel and chromium at 49 wt-% chromium and at a temperature of about 1618 K or 1345 C (2453 F).3 Besides its importance for the melting characteristic of the alloys, silicon improves the flowing behavior and-similarly to the chromium—the corrosion and 'oxidation resistance. The determination of the melting behavior of nickel-base alloys was done by differential thermal analysis. The test conditions were an argon atmosphere and heating and cooling rates of 5 K (i.e., 5 C or 9 F) per minute. The results, are shown in Fig. 1, w h i c h indicates the relationship between the liquidus temperature and the concentration of the alloying elements in the nickel-rich part of the system nickelchromium-silicon. About 350 samples prepared by induction heat melting under argon inert gas atmosphere were investigated. Raw materials for the preparation of these alloys were nickel, chromium, nickel silicides and chrom- W E L D I N G RESEARCH S U P P L E M E N T I 319-s 14 28 • A 0 40 55 45 40 45 chromium —— Ni BNi-5 BNi21.5Cr11.6Si ot - % 60 55-wt.-% 60 Fig. 1—Liquidus temperature of nickel-chromium-silicon alloys dependent on the composition in the concentration range of 0-40 wt-% chromium and 0-14 wt-% silicon. Dark lines are projections of melting grooves ium silicides, all of at least 99.8% purity. Figure 1 shows that—in the investigated concentration range of 0-40 wt-% chromium, 0-14 wt-% silicon, and the balance nickel—a ternary eutectic exists at a temperature below 1350 K or 1077 C (1971 F). The ternary eutectic is given by the point of intersection between melting grooves (dark lines in Fig. 1) and was found at 20 at.-% chromium and 21.3 at.-% silicon; this corresponds to 20.5 wt-% chromium and 11.8 wt-% silicon. a 2600 F 2500 The melting grooves are the lines of intersection of the melting planes (planes of primary crystallization). The plane of the primary crystallization of the nickel solid solution slopes steadily from the melting temperature of nickel to the temperature of the ternary eutectic for 376 K/C (676 F). In other words, the temperature of the primary crystallization of the nickel solid solution decreases with increasing concentrations of silicon and c h r o m i u m , but the influence of silicon is much more pronounced as shown by the isoliqui- Figure 2 shows such sections at constant chromium content of 19 wt-% containing the filler metal c o n centration of BNi-5—and of 20 and 21 wt-% chromium. All sections are near the concentration of the ternary eutectic. The dependence of the liquidus temperature on the silicon content in Fig. 2 indicates that a small change of Cr = const 19 wt. - % o Cr = const. 2 0 w t . - % A Cr = const 21 w t - % dus curves drawn in steps of 50 K, i.e., 50 C (90 F). The melting planes in concentration areas with silicon contents of more than about 11 wt-% show a slope similar to the part of the melting plane at high nickel concentration. Of great importance for developing Ni-Cr-Si filler metals is the strong influence of the composition on the liquidus temperature in concentration ranges near the ternary eutectic. This fact can be better demonstrated by concentration-temperature sections. 15 2400 2300 2200 F CD 2200 2100 a i 2100 | 2000 QJ 2000 n-5 1900 1300 BNi 21.5Cr 11.6Si 1900h 1300 0 _L 4 _L 8 12 0 2 4 6 A BNi20.3Cr11.5Si 0.5P 1800h _L 16 8 20 a t . - % silicon — » - 28 10 - w t - % 14 s i l i c o n —— Fig. 2—Liquidus temperature of nickel-chromium-silicon alloys with constant chromium content ol 19, 20 and 21 wt-%, dependent on the silicon content 320-s I O C T O B E R 1978 1700 1200 J L 2 3 wt. % 4 phosphorus —•»- Fig. 3—The influence of phosphorus on the liquidus temperature oi an alloy with 20.4 wt-% chromium, 11.6 wt-% silicon, balance nickel 1500 2003 199; 1832 - 1500 F 1368 1363 1273 K 1000 CD 1000 F/g. 4—Wett/ng ang/e of f///er meta/ 8N/ 20.30 77.55/ 0.5P on stainless steel at 1343 K, 1070 C (1958 E) 500 " 500 3? - the composition of filler metal BNi-5 leads to alloys w i t h liquidus temperatures of about 58 K/C (104 F) below the liquidus temperature of BNi-5. For further investigations an alloy near the ternary eutectic w i t h 21.5 wt-% chromium, 11.6 wt-% silicon and balance nickel was selected. Melting Behavior of Ni-Cr-Si-P Alloys Besides the elements silicon and boron, phosphorus is also an effective element to lower the melting temperature of nickel base alloys as it is k n o w n from the melting behavior of the filler metals BNi-6 and BNi-7. 1 In Fig. 3 the influence of phosphorus on the liquidus temperature of the approximate ternary eutectic alloy w i t h 20.4 wt-% chromium, 11.6 wt-% silicon and balance nickel is shown. The graph demonstrates that only small amounts of phosphorus of about 0.5 wt-% give an additional decrease of the melting point of alloys in concentration areas of the ternary eutectic. The alloy w i t h 20.3 wt-% chromium, 11.5 wt-% silicon, 0.5 wt-% phosphorus, and balance nickel has a liquidus temperature of 1333 K or 1060 C (1940 F). This means that this boron-free filler metal BNi 20.3Cr 11.6Si 0.5P which was selected for further investigations has a 75 C or 75 K (135 F) lower liquidus temperature than the filler metal BNi-5 and a similar melting behavior in comparison to used boron-containing filler metals. Further investigations in alloying NiCr-Si alloys with phosphorus show that a decrease of the silicon content in the alloy in respect to lowering the hard phases requires higher amounts of phosphorus of about 3 wt-% to give similar melting behavior to alloy BNi 20.3Q H.6Si 0.5P. For instance, an alloy with 14.8Q 8Si 3Fe 3P balance nickel has a melting range of 1269 K or 996 C (1825 F) to 1336 K or 1063 C (1945 F). Flow Behavior and Structure of BNi 21.5Cr 11.6Si and BNi 20.30 11.5Si 0.5P Besides melting characteristic, the 273 0 30 60 90 120 time — 150 mm 180 Fig. 5.—Time-temperature cycle during vacuum brazing flow behavior is a very important property for the manufacturing of high temperature filler metals." As a characteristic value for the wettability, the contact angle was measured between the liquid filler metal and a plain base metal surface at different temperatures. The investigations were made under vacuum ( < 10~* torr) in the temperature range of 1323 K or 1050 C (1922 F) to 1383 K or 1110 C (2030 F). The base metal was stainless steel (W. No. 1.4541, X 10 CrNiTi 18 9). The filler metals BNi 21.5Cr 11.6Si and BNi 20.3Cr 11.5Si 0.5P w i t h liquidus temperatures of 1358 K or 1085 C (1985 F) and 1333 K or 1060 C (1940 F) show good wettability even at temperatures below their liquidus temperature, whereby the phosphorus-containing alloy indicates a slightly better flow behavior. The wetting angles in the investigated temperature range for both alloys in any case were below 3 deg as seen in Fig. 4. The structure of the alloy BNi 21.5Cr 11.6Si is the same as that of filler metal BNi-5. The main silicide Ni 5 Si 2 is distributed in the nickel solid solution. Additionally, very small amounts of a ternary silicide Cr 3 Ni 5 Si a (n-phase) like in the case of BNi-5 were found. 7 The phosphorus-containing alloy BNi 20.3Cr 11.5Si 0.5P has a structure similar to that of BNi-5. Also, small amounts of the nickel phosphide Ni,P are added because of the very little solid solubility of phosphorus in the nickel matrix. 2 Brazing Experiments W i t h selected filler metals BNi 21.5Cr 11.6Si and BNi 20.3Cr 11.5Si 0.5P, brazing experiments were made to get the optimuTn brazing temperature in regard to their diffusion behavior and joint strength. The AWS single-lap standard method was used to determine strength properties. 1 The ratios of overlap to thickness were 0.5 to 6. The clearance was 25 /tm (0.001 in.). The brazing was done in an electric heated vacuum furnace at a vacuum better than 1.33 X 10 '2 Pa ( 1 0 J torr) according to the brazing cycle shown in Fig. 5. This brazing cycle w i t h a brazing time of 10 min and a diffusion heat treatment at 1273 K or 1000 C (1832 F) for 60 min after brazing, is typical for processing the filler metal BNi-5 in nuclear industries to get ductile joints. 8 The base metal used was stainless steel (W. No. 1.4541, X 10 CrNiTi 18 9) w i t h a yield strength of 214 N / m m 2 (31 ksi) and an ultimate tensile strength of 575 N / m m 2 (83.4 ksi). Both values were determined after the base metal was heat treated in the same way as the brazed joints. The filler metals were used as powders and placed w i t h cement. The results of the strength tests of joints brazed w i t h the filler metal BNi 21.5Cr11.6Si at temperatures of 1363 K or 1090 C (1994 F) and 1368 K or 1095 C (2003 F) are shown in Fig. 6. It can be seen that, at both brazing temperatures, the tensile stress of the joints is slightly above the ultimate tensile strength of the base metal at ratios of overlap to thickness greater than about 1.5. At the brazing temperature of 1368 K or 1095 C (2003 F), the joints fail at any ratios in the base metal except the joints with ratios of 2 and 6 where w e find brazing defects in the brazing gap. In any case, the tensile stress of the joints is above the yield strength of the base metal w h i c h indicates a good ductility of the brazing seam. loints brazed at a temperature of 1343 K or 1070 C (1958 F) have tensile stresses above the yield strength of the base metal. However, the values are in general lower. The reason can be that this brazing temperature in connection w i t h the diffusion heat treatment is not sufficient to eliminate silicide W E L D I N G RESEARCH S U P P L E M E N T I 321-s i 100 I KSI 80 « • 600 N mm2 \ V / xf 200 p YS. base metal ^ •£>•••••£ A _ n > - " • V•'SSklgfe4 K 40 0L 1 • I / 400 20 / f I A I i i 1 i 1 2 3 4 5 6 overlap distance, ratio of overlap to thickness —— Fig. 7-M'tcrograph of a joint brazed at 1343 K, 1070 C (1958 F). Base metal-stainless steel; filler metal-BNi 21.5Cr 77.65/; clearance-25 nm (0.001 in.) Fig. 6—AWS single-lap standard method. Base metal—stainless steel (W. No. 1.4541, X 10 CrNiTi 18 9); filler metal-BNi 21.5Cr 11.6SI; clearance-25 nm (0.001 in.); vacuum < 1.33 x 10 - Pa (10-' torr); brazing cycle-See Fig. 5: Brazing Average unit shear stress Average unit tensile stress 'v-'. V temperature 1363 K, 1090 C (1994 F) 7368 K, 1095 C (2003 F) V A D Open symbols represent failure in the filler metal; filled symbols represent in the base metal ,. . V failure *-1 * j * :-. 11.5Si 0.5P at 1363 K o r 1090 C (1994 F) a n d 1368 K, 1095 C (2003 F) are s h o w n in Fig. 9. It seems t h a t t h e t e n s i l e stress of these j o i n t s also at a r a t i o o f o v e r l a p t o t h i c k n e s s o f 1.5 is e q u a l t o t h e u l t i m a t e t e n s i l e s t r e n g t h o f t h e base metal ( c o m p a r e to Fig. 6 ) . Because o f t h e fact t h a t s a m p l e s w i t h r a t i o s o f 2, 4 and 6 f a i l e d in t h e f i l l e r m e t a l , f u r t h e r tests s h o u l d be m a d e t o c o n f i r m t h e d e p e n d e n c e s h o w n in Fig. 10. O n t h e other h a n d , joints w i t h o v e r l a p ratios b e l o w 1 s h o w f a i l u r e i n t h e base m e t a l . A l t h o u g h b r a z i n g tests at l o w e r b r a z - 100 KSI :^j&-'•-•"- ,-' r ::-.m - .:,,-•' .: -'Iff-'--. •>••'. phases o f t h e b r a z i n g g a p b y d i f f u sion—Fig. 7. For t h e m o s t p a r t , j o i n t s b r a z e d at a t e m p e r a t u r e o f 1363 K, 1090 C (1994 F) or 1368 K, 1095 C (2003 F) a c c o r d i n g t o t h e b r a z i n g c y c l e in Fig. 5 s h o w n o s i l i c i d e phases in t h e b r a z i n g g a p - F i g . 8. T h e r e f o r e , f o r t h e f i l l e r m e t a l B N i 21.5Cr 11.6Si a b r a z i n g t e m p e r a t u r e of 1368 K, 1095 C (2003 F) s h o u l d be s u g g e s t e d if h i g h j o i n t s t r e n g t h has t o b e r e q u i r e d . T h e results o f t h e s t r e n g t h tests o f joints brazed w i t h t h e p h o s p h o r u s containing filler metal BNi 20.3Q " ^ . ' * -~ <!)•& • Fig. 8—Micrograph of a joint brazed at 1363 K, 1090 C (1994 F). Base metal-stainless steel; filler metal-BNi 21.SO 11.6SI; clearance-25 nm (0.001 in.) ing t e m p e r a t u r e s — f o r i n s t a n c e , at 1343 K, 1070 C (1958 F ) - d e m o n s t r a t e d a g o o d f i l l i n g o f j o i n t s at gaps o f 25 jitm (0.001 in.) (Fig. 1 0 ) , t h e s u g g e s t e d b r a z ing t e m p e r a t u r e f o r t h e f i l l e r m e t a l B N i 2 0 . 3 Q 11.5Si 0.5P s h o u l d b e 1363 K or 1090 C (1994 F) t o 1368 K o r 1095 C (2003 F). In a n y case, n o o p t i m i z a t i o n o f t h e v a l u e o f t h e c l e a r a n c e has been done. bOO 80 - N mm2 60 400 Summary In d e v e l o p i n g b o r o n - f r e e n i c k e l base l o w m e l t i n g , h i g h t e m p e r a t u r e 40 200 '"',£& *. • 20 0 °0 1 2 3 4 5 overlap distance, ratio of overlap to thickness —— Fig. 9- -AWS single-lap standard method. 7.4547 X 10 CrNiTi 18 9); filler metal-BNi (0.007 in.); vacuum < 7.33 X 10- Pa (10* Base metal—stainless steel (W. 20.30 77.55/ 0.5P; clearance-25 torr); brazing cycle-see Fig. 5: Brazing 1363 K, 1090 C Average unit shear stress Average unit tensile stress (1994 F) v o temperature 7368 K, 1095 C (2003 F) D Open symbols represent failure in the filler metal; filled symbols represent in the base metal 322-s I OCTOBER 1978 No. ju/n failure Fig. 10— Micrograph of a joint brazed at 1343 K, 1070 C (1958 F). Base metal-stainless steel; filler metal-BNi 20.30 77.55/ 0.5P; clearance—25 jim (0.001 in.) Table 1-Characterization of New Filler Metals in Comparison to BNi-5 and BNi-1 Suggested Tern perature"" Filler metal Nominal c o m p o s i t i o n , wt-% Solidus BNi 21.5Cr11.65i 21.5Cr, 11.6Si, bal. Ni BNi 20.3Cr11.5SiO.5P 20.3Cr, 11.5Si, 0.5P, bal. Ni BNi -5 19Cr, 10.2Si, bal. Ni BNi -1 14Cr, 3B, 4.5Si 4.5Fe, 0.7C, bal. Ni 1335 (1944 1317 (1911 1353 (1975 1250 (1790 brazing filler metals for applications in nuclear industries, the melting behaviors of nickel-chromium-silicon alloys in the concentration range of 0-40 wt-% chromium, 0-14 wt-% silicon, and the balance nickel were investigated systematically. The lowest liquidus temperature of 1350 K or 1077 C (1971 F) in this nickel-rich area was found at a ternary eutectic concentration of 20.5 wt-% chromium, 11.8 wt-% silicon, the balance nickel. This means that a small change of the concentration of filler metal BNi-5 [19 wt-% Cr, 10.2 wt-% Si, the balance Ni; T L = 1408 K, 1135 C (2075 F) ] leads to a 58 K/C (104 F) lower melting filler metal. Alloying with small amounts of phosphorus indicates an additional decrease of the melting temperature to values of 1333 K or 1060 C (1940 F). For testing the brazing behavior and the joint strength, t w o alloys—BNi 21.5 Cr 11.6Si and BNi 20.3O 11.5Si 0.5P—which are characterized in Table 1—were selected. Both alloys have a structure and diffusion behavior similar to that of BNi-5 and show good flowing behavior on stainless steel with wetting angles between 0-3 deg K F) K F) K F) K F) Brazing range"" Liquidus 1358 (1985 1333 (1940 1408 (2075 1311 (1900 1343-1383 (1958-2030 1343-1383 (1958-2030 1423-1478 (2100-2200 1338-1478 (1950-2200 K F) K F) K F) K F) dependent on the temperature. Strength tests using the AWS single lap standard method show that, at higher overlap ratios for joints of stainless steel brazed w i t h both filler metals, tensile stresses equal the ultimate tensile strength of the base metal. The suggested brazing temperature for the investigated filler metals is 1368 K or 1095 C (2003 F). This means that these boron-free filler metals give ductile high strength joints at a brazing temperature 95 K/C (171 F) and 80 K/C (144 F) below the brazing temperature normally used for processing the boron-free filler metal BNi-5 or the boron-containing filler metal BNi-1. Compared to other well k n o w n boron-containing filler metals, the alloys BNi 21.5Q 11.6Si and BNi 20.3Q 11.5Si 0.5P should have higher oxidation and corrosion resistance because of the higher content of chromium and silicon. Acknowledgments This paper is based on work performed under research and devel- brazing temperature'"' K F) K F) K F) K F) 1368 (2003 1368 (2003 1463 (2175 1448 (2150 K F) K F) K F) K F) opment administration contract No. 3584 of the Arbeitsgemeinschaft Industrieller Forschungsvereinigungen e. V., West Germany. References 1. Brazing Manual, American Welding Society, 3rd Edition, 1976. 2. Hansen, M., and Anderko, K., Const, of Binary Alloys, McGraw Hill, 1958. 3. Knotek, O., Lugscheider, E., and Eschnauer, H., Hartlegierungen zum Verschleissschutz, Stahleisen, DCisseldorf FRG, 1975. 4. Lugscheider, E., Reimann, H., and Knotek, O., Monatsh. f. Chem. 106 (1975), p. 1155. 5. Shunk, F. A., Const, of Binary Alloys, McGraw Hill, 1969. 6. Lugscheider, E., and Iversen, K., "Investigations on the Capillary Flow of Brazing Filler Metal BNi 5," Welding lournal, 56 (10), Oct. 1977, Research Suppl., pp. 319-s to 324-s. 7. Gladishevskii, E. I., and Borusevic, L. K., Russ. I. Inorg. Chem., 8 (1963) p. 998. 8. Iversen, K„ and Lohe, H., DVS-Bericht No. 15 (1970). 9. Nicrobraz, Eng. Data Sheet No. 2.1.1. Rev. H, Wall Colmonoy Corp., Detroit, Mich., 1974. AWS Filler Metal Specifications AWS A5.25-78, Specification for Consumables Used for Electroslag Welding of Carbon and High Strength Low Alloy Steels and AWS A5.26-78, Specification for Consumables Used for Electrogas Welding of Carbon and High Strength Low Alloy Steels are now available. The classification system used in the specifications follows as closely as possible the standard pattern used in other AWS filler metal specifications. This allows the user to more readily select the proper filler materials. However, the inherent nature of electroslag and electrogas welding has necessitated specific changes to more ably classify the electrodes. Each specification contains 24 pages and they are saddle-stitched, soft cover, 8V2 x 11 in., three-hole punched, priced at $5.00 per copy. Discounts: 25% to A and B members; 20% to book stores, public libraries and schools; 15% to C and D members. Send your orders to the American Welding Society, 2501 N.W. 7th St., Miami, FL 33125. Florida residents add 4 % sales tax. W E L D I N G RESEARCH S U P P L E M E N T I 323-s plan now plan n o w p l a n n O W t O a t t e n d to a t t e n d to attend The 10th International AWS-WRC Brazing Conference at Cobo Hall in Detroit, Michigan during Tuesday, Wednesday and Thursday April 3-5, 1979 — Co-Sponsors— American Welding Society Welding Research Council —Organized By— The AWS C3 Committee on Brazing and Soldering And held in conjunction with the 60th Annual Meeting of the American Welding Society and the 1979 AWS Welding Show Featured at the C o n f e r e n c e : presentations by experts on n e w a p p l i c a t i o n s and significant research and d e v e l o p m e n t findings. Featured at the 1979 A W S W e l d i n g Show: exhibits and d e m o n s t r a t i o n s stressing n e w brazing e q u i p m e n t and process d e v e l o p m e n t s 4- a b o o t h m a n n e d by AWS brazing experts to assist the visitor in the s o l u t i o n of brazing f a b r i c a t i o n problems. 324-s I OCTOBER 1978
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