GALFAN® GALVANIZING OFFERS IMPROVED CORROSION RESISTANCE FOR WIRE by Marc Dewitte, N. V. Bekaert S.A. Rolf Nunninghoff, Bergische University, Wuppertal John L. Hostetler, ILZRO for Wire Association International Mexico Technical Conference October 9-12, 1994 Mexico City, Mexico Introduction The world-wide use of Galfan® galvanized wire for diverse end-use applications has been steadily increasing since its introduction in Europe in 1984. Its superior corrosion resistance has led to acceptance in uses such as wire ropes, fencing, springs, gabions, nails, ACSR, automotive parts, vineyard wire and guy wire. Although Galfan has the reputation of longer life, the explanation for is not as widely known. Extensive research has led to a description of Galfan's unique corrosion mechanism that explains its improved performance and allows better understanding of the influence of the hot-dip process on its performance. The research has shown increased magnitudes of superiority for three characteristics that were underestimated before: (1) Galfan's ability to maintain its best corrosion resistance at weld areas, (2) Galfan’s remarkable galvanic properties, and (3) the improvement of Galfan's passivity as it corrodes. Welded Galfan® Wire Mesh Investigations by TrefilARBED and N.V. Bekaert show significant advantages of wire mesh made by welding wire pre-coated with Galfan as compared to weldinguncoated wire into a mesh followed by galvanizing. Table 1 shows comparative times to red rust with salt spray tests (marine environment simulation) and with SO2 tests, (industrial environment simulation) for mesh as used in two different applications. Figure 1 shows that after 35 cycles in SOz, the Galfan mesh shows only white rust at the welds and other areas, whereas the regularly galvanized mesh shows severe red rusting.()) Testing by EFIM, an Italian Institute writing specifications for highway materials, shows similar results that has led to greater use of Galfan wire for gabions and highway fence.2) Research at Bekaert has discovered the reason the corrosion resistance of Galfan is not lost at weld areas. Typical optical micrographs through a weld section are shown in Figures 2 and 3. It can be seen that part of the weld nugget and even part of the wire near the nugget is not covered by a coating layer after welding.(1) AES measurements made on numerous weld sections identify the bright phases as essentially pure Fe while the surrounding material is 20%AI-75%Fe, and interface between the wire and the rest of the Galfan coating. This interface is an intermetallic with very low Zn, so its behavior will be similar to one of the Fe-Al compounds, FeAl, Fe2Als or FeAls, all of which have melting points above 1150°C. Even with the small amount of Zn in the intermetallic, its melting point will be well above the welding temperature. This means that the distance from the uncoated wire and the intermetallic Galfan interface is very small, allowing effective cathodic protection of the steel.) This is not the case when welding regular galvanized wires because their Fe-Zn_ intermetallic alloys present at the interface have melting points below 800°C that is lower than the welding temperature. The welding heat causes them to be melted away. The uncoated wire areas at the weld nugget are inadequately protected because the distances from much of the nugget surface to the nearest coating surface are too great. Not only is the cathodic potential greater because of the shorter distances over which cathodic protection is required, but the electrical resistance of Galfan's intermetallic (Al-Fe-Zn) is also lower than for regular galvanized (Fe-Zn). Therefore, its cathodic efficiency is also greater.Nails Cathodic protection also improves the performance of nails made from Galfan galvanized wire. Even though the points and heads are not coated, the Galfan nails can outperform nails that are regular galvanized after shaping. Moreover, they offer the advantage of possessing a more uniform coating thickness and are smoother and more ductile. These benefits are especially important for automatic nailing machines. ‘When nails with different coatings of about 45 im thickness were exposed to 15, cycles in a SO> test, the Galfan wire nail showed less corrosion on the heads and points than aluminized, regular galvanized or sheradized nails.) Ropes Another application that can turn Galfan’s features into significant economic benefits is ropes, especially marine and mining ropes because of the effects of greases used for lubricating. Table 2 shows a performance comparison between regular and Galfan galvanized fishing ropes in salt spray tests while Table 3 shows the comparison including the effect of grease in a cyclical sea water test.(4) Corrosion Mechanism Galfan is one of several zinc-aluminum alloys introduced during the last two decades. All have been attempts to provide more corrosion protection for the wire than offered by regular galvanizing or aluminizing. Galfan is the eutectic ratio of the two elements. That means it has the lowest melting: temperature and what is more important, means that the two elements do not grossly separate during solidification. Galfan solidifies into a lamellar microstructure consisting of alternating very thin (<1 um) Al-rich and Zn-rich plates within randomly oriented cells,®) as illustrated in Figure 4. In this kind of microstructure, the more active zinc will corrode first, leaving the aluminum to slowly oxidize and gradually form the corrosion products such as ZngAl(OH)1¢ which are much harder, less porous and less easily washed away than those from corrosion of regular galvanizing. An unusual feature is that the aluminum 3enrichment continues with exposure so that the longer the exposure, the more corrosion-resistant the coating becomes. Figure 5 shows a Scanning Auger Microprobe (SAM) analysis of the outer surface of an uncorroded Galfan coating. Compare this with Figure 6 showing a SAM indicating enriched aluminum levels on a corroded surface. (4) Because of this unique microstructure and continuous aluminum enrichment of the surface, Galfan’s surface becomes more passive with time, not less as will happen with regular galvanizing. Given this, it is not surprising to see that Galfan's weight loss vs. time is not linear as other coatings are, but parabolic as seen in Figure 7.9) This is confirmed by other investigations of long-term exposure tests. (5) The thickness of the remaining coating at the time of first appearance of red rust is still another difference due to the corrosion mechanisms. Regular galvanized wires show red rust while there is still 15 to 20 um of residual coating left whereas Galfan galvanized wires do not show red rust until the coating thickness is 5 um or less. See Table 4.(4) The explanation for this mechanism characteristic is found in the galvanic potential difference between the coating’s intermetallic layer and the free (eta) coating layer. The difference in regular galvanizing is very small so that the corrodent can penetrate directly toward the wire. The difference between Galfan's intermetallic and eutectic layers is much higher so the less sacrificial intermetallic does not corrode until the eutectic is completely consumed. Producing Galfan Galvanized Wire Steel sheet and tube are galvanized with Galfan using a single-dip process similar to those used for regular hot-dip galvanizing. Although ILZRO has patented a flux system for a single-dip process (SDEF), all Galfan galvanized wire has been produced by a double-dip (2-D) process in which the wires are first hot-dipped in a regular galvanizing bath, then immediately re-dipped in a Galfan bath. Wires galvanized with Galfan using a 2-D process will have a different coating microstructure than those done with the SDEF process. The classical Fe-Zn alloys form the interface in the first dip. When the newly galvanized wires are immersed in the Galfan bath however, aluminum from the bath rapidly diffuses through the Fe-Zn alloys, transforming them into a more-or-less homogeneous Al-Fe-Zn intermetallic compound as seen in Figure 8.Whereas Fe-Zn alloy layers are brittle and quick to show red rust, the Galfan Al- Fe-Zn intermetallic is very ductile, exceptionally corrosion-resistant, and is slow to show red rust. Future Demand Galfan galvanized wire, both low-carbon and high-carbon, have been produced in Belgium, France, Germany, Luxembourg and the United States since the mid- eighties. Production by each licensee is increasing steadily. As more specifications are modified to include Galfan, the demand should grow rapidly. Many new production facilities in all parts of the world where galvanized wire is used will be licensed by ILZRO to use the patented Galfan alloy . The 2-D process will continue to be a popular method because it allows both regular and Galfan galvanizing on the same line and because it has certain unique coating microstructure characteristics. The SDEF process will also be used widely because of its lower initial cost, simpler operating process, and lower production costs. The technology for Galfan galvanizing small parts that are needed as accessories for many of the wire products is developing rapidly so that Galfan systems can be offered to the marketplace. References 1. M. Dewitte and P. Lippens, N.V. Bekaert Co. Corrosion Resistance Study of Post-Welded Galfan Wires, 2. Prof. R. Nunninghoff, Bergische Universitat, Wuppertal, Germany Report to the Galfan Licensees Meeting, Tokyo, Japan, Oct., 1992 Part of this report includes work done by Dr. Volker Hagebilling at Bergische Universitat. 3. Scott R. Bluni, Lehigh University, Report to the Galfan Licensees Meeting, Linz, Austria, Oct., 1993. ‘i 4. M. Dewitte, S. DeBondt, etal, N.V. Bekaert Co., Galfan’s Efficient Galoanic Action Provides Corrosion Protection. 5. Y. Hirose, Nisshin Steel Co., Ltd., Ten Year Atmospheric Corrosion Test Results of Galfan Coated Steel.TABI TABLE 1 COMPARING REGULAR AND GALFAN GALVANIZED WELDED MESH ‘as SECURITY FENCING | J vox 34mm dia wee | Pecan | arenes RecN tee (GALVANZED GALVANIZED. COATING WEIGHT, gma 355 SALT SPRAY TEST (NaCh}: Hours per gma Gatan Ratio KESTERNIGH TEST (S02}- Number of cycles to 5% red rust Cycles per g/m2 “Gallan Ratio. Page 1TAB2 TABLE 2 COMPARING REGULAR AND GALFAN GALUANIZED FISHING ROPES IN SALT SPRAY TEST COATING | SALT SPRAY TEST WEIGHT | RESISTANCE IN HRS G2 TO 5% RED RUST ROPE CONSTRUCTION: CORE FABRIC CORD +647 REGULAR GALV. 140 216 1.54 130 1272 9.78 ‘STRANDS: 7 # 1 167 456 2.73 GALFAN 150 1248 3.32 | 3.05:1 COATING STRAND WIRE (before drawing) 410-436, 504 1.19 429-434 4272 2.94 | 2.471 Page 1TABS. TABLE 3 COMPARING REGULAR AND GALFAN GALUANIZING IN CYCLICAL SEA WATER TEST GALVANIZING TRE WITH NO GREASE 230 453 1.97 108 2558 35.17 WITH GREASE 230 208 0.90 108 296 2.74 TEST CONDITIONS MAKE-UP OF SEAWATER. DAILY CYCLE NaCl 28 gf 17 hrs immersed MgSO4-7H20 _7/g/l 2 hrs dry MgCi2 - 6H20 5 gf 3 hrs immersed Cace 1.22 gf 2 hrs dry NaHCO3 0.2 gf Page 1TAB 4 TABLE 4 RESIDUAL WIRE COATING THICKNESS __AT'5% RED RUST IN SALT SPRAY TEST INITIAL, INITIAL RESIDUAL COATING GALVANIZING| INTERMETALLIC | TOTAL COATING THICKNESS TYPE LAYER, THICKNESS, MICRONS MICRONS: MICRONS: LOW CARBON WIRE 8 to 10 41 to 62 GALFAN 4 to S 51 to 60 3 HIGH CARBON WIRE 64 to 78 1048 Page 1