NACE Paper 03459 RECENT DEVELOPMENTS IN REACTIVE AND REFRACTORY METAL EXPLOSION CLAD TECHNOLOGY John G.

Banker DMC Clad Metal Div. 5405 Spine Road Boulder, CO 80301 USA ABSTRACT Several new developments in explosion clad technology of reactive and refractory metals offer significant cost reduction for highly corrosion-resistant chemical processing industry (CPI) equipment . These developments include: 1) technology for manufacturing large tantalum clad plates which are double traditional size, 2) simultaneous bonding of a beneficial interlayer with higher strength zirconium or titanium grades, and 3) qualification of the bonding process for producing Ti-Ru Grade 27 clad plate product. These developments and their commercial implications are discussed. Keywords: Clad Metal, Explosion Clad, Titanium, Tantalum, Zirconium INTRODUCTION Explosion welding (EXW), commonly called explosion cladding, is a solid state welding technology for manufacture of large clad metal plates. The technology was discovered around 1960 and codified in the following decade1,2. In subsequent years the technology has been developed into a robust and reliable manufacturing process. Explosion clad products are used extensively, worldwide in manufacture of corrosion resistant process equipment as well as other bi-metallic applications3. The cladding metal alloy can be selected for optimum corrosion performance. The base metal alloy can be specified to optimize strength, fabricability and cost. The high strength, durable explosion weld makes possible the construction of CPI equipment exhibiting the beneficial features of both. As with all manufacturing technologies, ongoing process development is required to improve the technology and keep it current with todays materials and service needs. This paper discusses developments which address three different types of clad product needs: 1) enlarging plate size

capabilities to reduce fabrication costs, 2) manufacturing process cost reductions, 3) qualification of explosion cladding technology for new alloys. TANTALUM-STEEL CLAD DEVELOPMENTS Tantalum is one of the most universally corrosion resistant metals4. If not for its exceptionally high cost, tantalum would be used extensively in corrosive environments. However, with a cost typically in the >$500./kg range, and a density of more than twice that of steel, tantalums use is limited to severe, high value applications. The cost of tantalum equipment can be lowered considerably through use of clad materials5. Consequently, manufacture of tantalum clad steel was one of the earliest applications for the newly emerging explosion cladding industry in the 1960s. Techniques were developed for manufacturing and fabricating plates with tantalum thickness in the 0.70 to 1.1 mm (0.025 to 0.045 inch) range. Nooter Corporation constructed the original tantalum clad equipment and patented batten strap welding technology for this product (patent expired). A thin copper interlayer was clad between the tantalum and the steel base metal to diffuse the very high heat from the tantalum welds. Due to tantalum size availability and cladding issues, clad plate sizes were limited to 900mm x 2500mm (36 x 100 inch) finished size. The high cost was further frustrated by the added work of fabricating vessels using the small clad plates. During the 1980s DuPont Detaclad developed a technique to make larger plates by a combination of: 1) explosion cladding a tantalum/copper billet, 2) rolling it to a larger size plate, and then 3) explosion bonding it to the steel. The yield loses from the rolling operation, combined with the high value of the tantalum in the scrap, resulted in an ultimately higher cost product. This, combined with the very long lead time of the multiple cladding and rolling operations, destined the process to the history books. Over the past five years DMC has worked to develop techniques to lower the cost of tantalum clad equipment manufacture, including technology to make larger clad plates by direct cladding. The problems to be overcome, relate not only to cladding technology but to a number of fabrication issues. In this effort, DMC teamed with AstroCosmos, Camarillo, CA, USA, a premier fabricator of tantalum and tantalum clad equipment. As a consequence of this mutual effort, DMC has manufactured production clad plates up to 1900 x 3500mm (75 x 138 inch) of 1mm (0.040 inch) tantalum clad to 50mm (2 inch) steel including a copper interlayer. TABLE 1 TYPICAL MECHANICAL PROPERTIES OF TA/CU/STEEL PLATES Copper/Steel Tantalum/Copper
Shear Strength, Room Temp. Shear Strength, 150C (300F) Tensile* Strength, Room Temp. Tensile* Strength, 150C (300F) 230 MPa (33,980 psi) 231 MPa (34,465 psi) 411 MPa (61,403 psi) 217 MPa (32,369 pai) 257 MPa (38,309 psi) 228 MPa (33,982 psi) 391 MPa (58,384 psi) 368 MPa (54,979 psi)

* Through-thickness bond tensile strength measured using Ram Tensile Specimen. One of the major hurdles in developing the new process was controlling tantalum flatness over the large sheet area. The explosion cladding process requires that the cladding metal and the base metal be fixtured parallel to each other but separated by a uniform planar spacing, or standoff distance. Using

traditional explosion cladding technology, the standoff is typically in the range of 2 times the cladding metal thickness. With a 1mm (0.040 inch) thick tantalum cladding sheet, the required standoff is 2mm (0.080 inch) with a tolerance in the range of +/- 0.5mm (0.020 inch). This means that the tantalum sheet must be flat within 1mm (0.040 inch) over its full area. The tantalum manufacturing companies are limited to 1000 mm (39 inch) maximum plate widths in the 1mm (0.040 inch) thickness range. With considerable effort and control, plates that meet the required flatness can be produced at this size. Increasing plate size required several significant developments. One was to establish techniques to butt weld tantalum sheets together prior to cladding, while maintaining acceptable flatness. Another was modifying cladding technology, to significantly increase the standoff tolerance. AstroCosmos was successful in achieving the former, DMC Clad Metal in achieving the latter. Through this effort, the companies have been successful in manufacturing and fabricating clad plates to produce several pressure vessels, some which are larger and heavier than ever constructed before. During this period the DMC manufacturing plants have manufactured over 150 tantalum clad plates, ranging up to 1800 x 3500mm (71 x 138 inch) , with tantalum thicknesses in the 0.75 to 1.0 mm (0.030 to 0.040 inch) thickness range. Some of these plates have been cold formed into ASME 2:1 elliptical heads with diameters ranging from 600 mm to over 3500 mm (24 to over 140 Tantalum inch). Special manufacturing processes were developed to assure that the very thin cladding thickness was not damaged in the sequence of manufacturing and fabricating operations. To confirm that Copper the tantalum thickness was not compromised, DMC teamed with a NDE equipment manufacturer to develop a eddy-current technique for nondestructive measurement of tantalum thickness of the finished clad product. Figure 1 presents a typical Steel photomicrograph of the Tantalum/Copper/Steel plates FIGURE 1: Tantalum clad photomicrograph. (above) manufactured in this effort. Figure 2 shows several large tantalum clad plates in the DMC factory prior to shipment to AstroCosmos. Figure 3 shows a tantalum clad replacement section of a column. The can is constructed of 1mm (0.040 inch) tantalum clad onto 10mm (0.39 inch) thick Alloy C276 (with a copper interlayer). The original column which was constructed entirely of Alloy C276 had experienced significant corrosion in a short section of FIGURE 2: Five Tantalum clad plates, 1800 x 3000 mm (71 x 118 inches), left.

its length. Tantalum was determined to be the best solution for corrosion control. The aggressive operating conditions, including vacuum service, drove the selection of clad over loose lining. This new column section has been in service for over two years in a petrochemical plant owned by a major oil company. Figure 4 shows a large, jacketed horizontal tantalum-steel clad vessel manufactured for a manor petrochemical products manufacturer. The clad vessel replaced glass lined equipment of essentially the same design. Problems from frequent glass failures were causing significant problems regarding product quality, cost, and delivery reliability. The tantalum clad replacement was determined to be the best solution to eliminate these problems. The vessel is constructed of fourteen clad shell plates, two clad segmental heads, six clad covers and various other clad components.

FIGURE 3: Ta/Cu/C276 clad column section 2130 dia. x 3660mm (7 x 12 feet)

FIGURE 4: Ta/Su/Steel clad vessel, 2130 dia. x 12,600 mm long (7 x 42 feet)

Conclusions: Through this team effort, techniques have been mastered for manufacture of larger tantalum clad plates. These have been successfully fabricated into some of the largest tantalum clad pressure vessels ever constructed. ZIRCONIUM CLAD COST REDUCTION Zirconium-steel explosion clad has been used in a number of chemical process applications over the past two decades6. The Zr clad plates have been primarily used in construction of large pressure vessels, or for heat exchanger tubesheets. During this period, clad plate manufacturing techniques and vessel fabrication techniques have been well developed. However, the zirconium-steel combination has proven to be one of the most difficult metal combinations for explosion cladding. As with the titanium alloys, low strength and high ductility of the zirconium cladding plates is crucial for reliable clad manufacture. This has been achieved by specifying a low oxygen content (1000 ppm) in the zirconium cladding plates, commonly called Low Ox. When Low Ox Zr has not been available, explosion cladders have typically used an interlayer of titanium between the zirconium and steel7. Although both Low Ox and a titanium interlayer provide reliable solutions for clad manufacture, they each have drawbacks. There are few commercial applications for Low Ox Zr plates; consequently, the availability of the alloy is limited. For large pressure vessel jobs requiring a few thousand kg of plates, mill production is

an easy solution. For small heat exchanger jobs, requiring possibly only 100 kg (220 lb), or so, availability of Zr plate of the needed size and thickness can be a real problem. The titanium interlayer approach permits the clad manufacturer to use standard Zr 702. This alloy is more readily available. For many small, fast delivery applications, it is the only option. However, the titanium interlayer solution has traditionally had two inherent cost negatives: the titanium interlayer is not cheap and the clad manufacturing process requires two explosion steps . During the past five years the DMC Nobelclad Division has mastered the technology of bonding the zirconium + titanium interlayer to steel in a single explosion cladding operation. The cladding approach, which is schematically depicted in Figure 5, requires a unique and precise positioning of the zirconium cladding metal and the interlayer. Standoff (plate separation distance) tolerances are critical. In general the cost reduction benefits from eliminating the second cladding shot and the lower cost of Standard Zr 702 counterbalances the added cost of the titanium Explosive interlayer. Thus, total costs are comparable to direct Detonation Explosive cladding with LowOx Zr. Over the past five years, the DMC Nobelclad Div. (France) and the DMC Clad Metal Div (USA) have manufactured plate for about 40 tubesheets using the new technology. The largest being 2500mm (100 inch) dia. x (100+2+10) [4 + 0.08 + 0.4] thick. Figure 5 presents shear strength data on several production jobs, comparing three manufacturing options: 1) direct bond of Low Ox Zr to steel, no interlayer, 2) Standard Zr with a titanium interlayer, bonded in two shots, 3) Standard Zr with a titanium interlayer simultaneously

Zirconium Titanium Jets Steel

FIGURE 5: Schematic of simultaneous zirconium-ti-steel cladding process.

350

300 Shear Strength (MPai)

250

200

150

100

50
0 30

Time, 1999 to 2002

Ti Interlayer, 1 Shot

Low Ox, No Interlayer

Ti Interlayer, 2 Shots

FIGURE 6: Shear strength of zirconium-steel clad as a function of manufacture method.

bonded in a single shot. Due to the size availability and flatness constraints of the titanium interlayer sheets, simultaneous Zr/Ti/steel clads are limited to approximately 3000 x 3000 mm (118 x 118 inch) maximum plate sizes. The titanium interlayer does not appear to offer any product technical benefits, other than improving cladding conditions with higher strength zirconium. The decision whether to use an interlayer is primarily a clad manufacturing consideration which is best left to the clad manufacturer to be based on quality, reliability, delivery, and cost. The issues addressed in this section regarding cladding of Standard Zr 702, are essentially the same as when cladding the higher strength Titanium alloys, for example ASTM B265 Gr. 2,5, 7,9, 12, 16, 26. The process of employing the simultaneous pick-up of a thin Grade 1 interlayer is equally as applicable for these alloys as it is for Standard Zr 702. In the past two years DMC has manufactured clad product of several of these alloys bonded to steel with a simultaneous interlayer technique. Conclusions: As a result of this work, DMC typically recommends the following. Cladding with Low Ox zirconium and NO interlayer is technically and commercially preferable when all three of the following apply: Low Ox Zr is available, AND The base metal is carbon steel, AND The Zr is 9 mm nominal thickness or less. When any one of these factors is not applicable, a titanium interlayer is recommended. For plates up to 3000 x 3000 mm (118 x 118 inch), the simultaneous bonding approach is reliable and reduces cost in comparison to the older 2 shot process. QUALIFICATION OF EXPLOSION-WELDED TI-RU ALLOY CLAD STEEL PLATE FOR PRESSURE ACID LEACH PROCESS EQUIPMENT Titanium clad is the corrosion resistant metal of choice for the construction of pressure acid leaching (PAL) autoclaves8. This hydrometallurgy process extracts selected metal ions (such as nickel and cobalt) from ore by dissolving them. The conditions to accomplish this feat are extremely high pressure, high temperature and very low pH (around 5% sulfuric acid). Equipment such as piping, pumps, tanks, valves and the autoclave must be designed to reliably survive these harsh conditions. Additionally, large volumes of ore are processed. This drives the size and complexity of the hydrometallugical process equipment to scales not previously used by this industry. Many cutting edge developments have evolved to deal with the harsh environment. One of the problems is crevice corrosion in the presence of chlorides. Precious metal enhanced, titanium alloys offer superior performance under these conditions. This alloy family has traditionally been limited to the Titanium-0.2% Palladium alloys, ASTM B265 Grades 7 and 11. These alloys provide excellent corrosion resistance, including where the combination of chlorides and crevices are present, and are readily available and fabricable. However, in recent years the cost of palladium has been subject to drastic swings in the commodity market. Over the period of 1996 to 2002, the price of palladium ranged form $200. USD/t-oz to nearly $1,200./t-oz. The impact was a threefold increase in the price of Grades 7 and 11.

When the palladium price began to climb dramatically, titanium producers began development and testing of the leaner titanium-palladium alloys and the titanium-ruthenium alloys 9,10. Two new alloy groups resulted from this work. The first to reach significant production levels were the two leaner TiPd alloys, Grades 16 and 17, which have a nominal composition of 0.05% Pd (sometimes referred to as Pd-lite) . More recently the Ti-Ru alloys, Grades 26 and 27, which exhibit a nominal composition of 0.10% Ru have been commercialized (RMI trade name TIRU). Explosion clad plates of Ti-Pd Grade 11 and steel have been manufactured for the chemical process industry since the 1960s. The first major commercial use of Ti Grade 17 clad steel was for the construction of a nickel ore leaching autoclaves in 1997. The first significant commercial applications of the Ti-Ru alloys, Grades 26 and 27, have occurred over the past three years. At this time, commercial use of Ti-Ru clad plates has been limited to some small heat exchanger tubesheet applications. The objective of the explosion cladding development program discussed in this paper was to qualify the manufacture of large explosion clad plates of Ti Grade 27 bonded to steel, and to evaluate the suitability of these plates for fabrication into the heads and cylinders required for the large autoclaves, Figure 7.

FIGURE 7: Titanium clad steel autoclave for leaching of nickel ore 4600 ID x 31,000 long x (100 mm steel + 8mm Ti Gr 17) [15 x 102 feet x (4 + 0.315 inch). Photograph provided by ASC Engineering. EXPLOSION CLADDING OF TI-RU ALLOYS TO STEEL Depending upon processing and heat chemistry, the Ti-Ru alloys may exhibit somewhat higher strength and ductility than their palladium equivalents. The increased strength presents a potential concern for manufacturing technology details of the explosion cladding process. However, the higher ductility is beneficial to EXW. When explosion cladding titanium to steel, it is well accepted within the industry that superior bond strength and ductility is achieved when titanium, exhibiting low strength and high ductility, is clad to steel with similar properties. Explosion clad manufacturers typically restrict production of large clad plates to the lower strength family of alloys, Grades 1, 11 and 1711. In the Ti-0.10% Ru family, Grade 27 is the low strength alloy, Grade 26 is its higher strength equivalent.

Explosion Cladding Development Trials: Two explosion cladding trials were performed with Ti Grade 26 and 27. The first, Test A, involved a small plate of Grade 26 to confirm basic explosion bonding parameters. The second, Test B, utilized a larger plate of Grade 27, simulating the size required for PAL autoclave vessel plates. The titanium for Test A exhibited mechanical properties that were somewhat higher than would normally be considered acceptable for cladding. The plate for Test B exhibited significantly lower strength in the longitudinal direction but only slightly lower yield strength in the transverse direction. The properties of the two titanium plates are presented in Table 2. Test A: The clad plate produced in Test A was 1000 x 1000mm (39.4 x 39.4 inch) consisting of 9mm (0.35 inch) thick Ti Gr 26 clad to 50mm (2.0 inch) thick carbon steel, A516 Gr 70 (yield strength 355 MPa [51,500 psi].) Ultrasonic inspection of the clad plate, in accordance with the procedures of ASTM A578, indicated bonding over much of the clad surface, except for an area near the edge, approximately 150 x 100mm (6.0 x 4.0 inch) and an unusually large area at the initiator. The bond strength is measured by shear strength testing using the specimen design of ASTM B898 (the Reactive Metal Clad Specification). The test values which are presented in Table 3 indicate good bond shear strength in comparison to the minimum specified in ASTM B898. Side bend tests exhibited TABLE 2 Properties of titanium plates used in cladding trials. Property Longitudinal Transverse ASTM B265 Allowables Ultimate Tensile 440 435 345 min. Strength (MPa) [psi] [63,700] [63,000] [50,000] Yield Strength 285 301 275-450 (MPa) [psi] [41,300] [43,600] [40,000-65,000] Elongation (%) 30 28 20 min. Oxygen content 1300 ppm 2500 ppm max Ultimate Tensile 386 386 240 min. Strength (MPa)[psi] [55,900] [55,900] [35,000] Yield Strength (MPa) 228 289 170-310 [33,043] [41,880] [25,000-45,000] Elongation (%) 36 38 24 min. Oxygen content 700 ppm 1800 ppm max

Test Ti Grade A 26

27

no indication of bond separation. A 700 mm (27.5 inch) diameter disk was cut from the plate for head forming evaluation. The disk was warm formed into a dished-only head by Antonius Vessel Heads, Netherlands. Ultrasonic inspection after forming confirmed that no disbonding had occurred during this operation. The clad bond mechanical properties of this plate were acceptable, but the nonbond areas covering 12% of the clad area was unacceptable. The non-bonds are typical of problems that can result when cladding higher strength titanium. Test B: Plate size is a key consideration in the explosion cladding process. Cladding becomes more difficult with increasing run length (the distance from the initiation point to the furthest point on the plate). In Test A, the run length was only 1400mm (55 inch). For a typical hydrometallurgical autoclave shell plate, it is 4000mm (160 inch). Test B was designed to evaluate the effect of increasing clad run length. The plate was 1500 x 4000mm (59 x 160 inch). The explosion bonding was initiated in a corner, providing a run length similar to that of a 2500 x 8000mm (100 x

TABLE 3 Test results from trial clad plates. Test A Location Corner Side Bend Test Acceptable Bond Shear Strength (MPa)*[psi] As-Clad 207 291 [30,000-42,100] Stress 210 - 246 Relieved** [31,300,35,600] Sound Bond (%) 88% 88%

Stress 170 184 99.99+% Relieved** [24,600-26,700] Corner 2 Not Stress 160 184 99.99+% Performed Relieved** [23,200-26,700] Specification Not specified Stress 137 99% B898 Minimum Relieved [20,000] (UT Class A) * Shear tests design is as specified in ASTM B898 ** Specimens were given a stress relief heat treatment of 2 hr at 605 C (1,120F) which is standard practice for titanium-steel clad plates 2 315 inch) centrally initiated clad plate (typical for autoclave manufacture.) 12 The steel was 50mm (2.0 inch) thick, ASTM A516 Gr 70 plate, yield strength 329 MPa (49,000 psi). Titanium was 9.5mm (0.375 inch) thick Gr 27 plate. The Test B clad plate was ultrasonically inspected over 100% of the surface using the procedures of ASTM A578. Testing was performed by fully automated, computer aided, equipment with precision of 5mm (0.20 inch). The only non-bond indication observed was a 15mm x 40mm (0.6 x 1.6 inch) region beneath the initiator. Figure 7 shows the layout of the Test B plate and the test specimen locations. Test specimens were taken from the corners that were furthest from the initiation. Bond test results are presented in Table 3. Side bend tests taken from the trailing end of the plate demonstrate good bond ductility and showed no indication of bond separation.
Side Bend Shear Test #1

Corner 1

Acceptable

Run Length 4.3 m (169 in)

Explosive Initiation Point

Shear Test #2

FIGURE 7: Test B. The only nonbond indication was 15 x 40mm (0.6 x 1.6 inch) indication at the startup. Conclusions: Overall evaluation of the Test B clad indicates that the Ti Gr 27 alloy can be reliably explosion bonded to A516 Grade 70 steel in sizes typically required for autoclave fabrication.

The side bend tests of both trial clads and the head forming trail of Test A demonstrate that the clad product can be readily formed without cracking or bond separation. The high nonbond area of Test A confirms concerns over use of this Grade 26 for direct explosion cladding to steel. (Higher strength titanium grades are readily clad by using a thin interlayer of commercially pure (CP) titanium between the alloy titanium and the steel.) ACKNOWLEDGMENTS The author wishes to express is appreciation to David Frey, AstroCosmos Metallurgical, Camarillo, CA, deserves special credit for providing significant support in the Tantalum clad development effort, and to Ron Schutz, RTI Titanium, Niles, Ohio, deserves special credit for his support in the TitaniumRuthenium work and in preparation of that section of the paper. REFERENCES 1. A. Pocalyko, Explosively Clad Metals Encyclopedia of Chemical Technology, Vol 15, third Edition, John Wiley & Sons, 1981, pp 275-296.
2. Banker, J.G., Reineke, E.G., Explosion Welding, ASM Handbook, Vol. 6, Welding, Brazing, and Soldering, 1993, pp 303-305. 3. Patterspm. A., Fundamentals of Explosion Welding, ASM Handbook, Vol. 6, Welding, Brazing, and Soldering, 1993, pp 160-164. 4. Hunkler, F.J., Tantalum and Niobium in Process Industry Corrosion, Ed by B. Moniz and W. Pollock, NACE, Houston, TX 1986. 5. Gramber, U. et al, Tantalum as a Material of Construction for the Chemical Processing IndusterA Critical Survey, International Symposium on Tantalum and Niobium Symposium, Sept. 27-29, 1995, Tantalum-Niobium International Study Center (T.I.C.) Brussels, Belgium, Goslar. 6. Banker, J.G., Commercial Applications of Zirconium Explosion Clad, Journal of Testing and Evaluation, ASTM, W. Conshohocken, PA, 1996, pp 91-95. 7. Banker, J.G., Nobili, A., Zirconium Explosion Clad for Cost Effective Process Equipment: Applications, Design, Fabrication, Proceedings, Zirconium/Organics Conference, Wah Chang, Albany, OR, 1997, pp 71-78.

8. Banker, J.G., Schutz, R.W., Nobili, A., Qualification of Explosion-Bonded T-Ru Alloy Clad Steel
Plate for Pressure Acid Leach Process Equipment, Proceedings ALTA 2002 Nickel/Cobalt Conference#8, ALTA Metallurgical Services, Melbourne, VI, Au. 2002, pp

9. E. van der Lingen, "The Effect of Minor Ruthenium Alloying Additions on the Metallographic Properties of Titanium Alloys", Communication C2468M, Mintek, Randburg, S. Africa, Nov. 1996. 10. R.W. Schutz and R.L. Porter, "TIRU-26TM and -27TM: Lower-Cost, Corrosion-Resistant Titanium Alloys for Hydrometallurgical Process Equipment", ALTA 2000 Nickel/Cobalt-6 Technical Sessions Proceedings, May 2000.

11. Banker, J.G. Explosion Welded Transition Joints for Structural Welds between Titanium and Dissimilar Metals, Proceedings from the 1994 International Conference, Titanium 1994, International Titanium Association, Broomfiled, CO, Oct. 1994. 12. Banker, J.G., Winsky, J.P, Titanium/Steel Explosion Bonded Clad for Autoclaves and Vessels, ALTA 1999 Autoclave Design & Operation Symposium, Alta Metallurgical Services, Melbourne, Australia, May 1999.