Characterization of rod and wire defects produced during the manufacturing of copper

With the increasing use of multi-wiredrawing machines, properly identifying the source of a defect becomes more vital to determine the appropriate corrective measures,
By Dr. E. Henry Chia and Gautam R. Patel

C ontinuous casting and rolling of

copper rod has been widely used throughout the world since its introduction in the 1960s, with more than 90 percent of the world's copper rod supply currently produced by several continuous casting processes. These processes are wheel and belt, twin belt, Outokumpu upcast, and to a lesser degree, the Dip Form method. Electrolytic tough pitch (ETP) copper

i s produced by the wheel and belt and t win systems. The Outokumpu and Dip Form systems are mainly used for manufacturing oxygen-free copper rod.' Over the past 10 years, great technol ogical advances have been made in these systems and continue to be introduced to pursue the never-ending quest for quality in the production of copper rod suitable for use in multi-wiredraw-

i ng machines (world class quality). A great deal of effort has been dedicated to incorporate automatic process control devices to minimize or eliminate human error in the systems. Statistical process control techniques have been successfully introduced as have been reported elsewhere.(2) We have been able to identify and describe different types of rod and wire defects which originate from the melt-

Fig. 1. SEM micrograph of a wire break showing iron (Fe) inclusion. 100x

Fig. 2a. SEM micrograph of wire surface showing embedded iron particles associated with a longitudinal crack. 350x

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Fig. 2b. SEM micrograph of wire surface showing embedded iron particles associated with a longitudinal crack. 150x

Fig. 2c. SEM micrograph showing wire surface damaged by an inclusion introduced during the casting operation. 1030x

i ng, casting, rolling, pickling and wiredrawing processes. In order to properly i dentify these defects for their prevention or elimination, it is important that the morphology of the various types of defects be well understood and properly characterized. Three areas where wire defects can originate are melting and casting operations; rolling and pickling operations; and, finally, wiredrawing operations. Melting and casting operations Defects originating in the melting and casting operation include: metallic and nonmetallic inclusions; nonuniform distribution of cuprous oxide (Cu 2O) eutectic particles due to excessive microporosity and excessive oxygen content; excessive hydrogen in solution in the copper which results in excessive grain boundary microporosity and cracks in the bar and stock during hot rolling; bar surface cracks due to nonuniform cooling during solidification; nonuniform CU2O eutectic network i n several regions of the cast bar; entrapment of copper oxide slag; sharp cast bar edges which will be folded over, burying the oxidized surface under the copper. Metallic and nonmetallic inclusions. Metallic inclusions originating from the melting and casting operations are mainly ferrous. Small particles of iron

have been found in the wire breaks as shown in Fig. 1. The particles are embedded on the wire surface and are usually associated with a longitudinal crack (see Figs. 2a and 2b). The possible sources of plain iron inclusions in the melting or casting areas are furnace tapping rod, metal metering rod and casting band because these are made from plain carbon steel. Nonmetallic inclusions originate mainly from refractory materials in the furnace and launder systems. The wire break in Fig. 3 shows an aluminum oxide inclusion, and its source can be traced to the refractory lining of the launder. Small inclusions introduced during casting that become entrapped near the surface of the cast bar will produce a surface defect such as that shown in Fig. 2c when the wire is drawn to small diameters, even though they will not be sufficiently large to produce the wire break. Synergistic effect of hydrogen, impurities and oxygen. Electrolytically refined copper cathodes used as feed for tough pitch copper production contain less than 20 ppm of impurities. A higher than normal amount of impurities (>20 ppm) results in a poor quality rod. Impurities such as lead, bismuth, sulfur, tellurium, selenium, antimony and arsenic are very deleterious and can produce bar crack during casting and rolling if present in high amounts. Excessive amounts of hydrogen (>2

ppm) in the molten copper can lead to excessive grain boundary microporosity in the cast bar and resulting surface defects. High hydrogen-together with deleterious impurities such as lead, bismuth, tellurium, sulfur, selenium, antimony and arsenic-results in a synergistic effect making the cast bar's grain boundaries very susceptible to thermally and mechanically induced stresses which result in cracks during casting.
(continued)

Chia

Patel

Dr. E. Henry Chia is president of Dr. Henry Chia & Associates, Selma, Alabama, USA, a consulting firm for the casting, rolling and drawing of metals. Gautam Patel is a materials engineer at the Materials Analysis Center at Georgia Tech Research Institute, Atlanta, Georgia, USA. This paper was presented at the 65th Annual Convention of the Wire Association International, Atlanta, March 1995.
JUNE 1996 51

Fig. 3. SEM micrograph of a wire break showing aluminum oxide inclusion. 500x

Fig. 4. Cast bar showing excessive porosity along the Cu2O grain boundaries (dark field image, optical micrograph). 100x

Fig. 5. Optical micrograph showing porosity void area contains high concentration of Cu2O particles. 100x

Fig. b. Optical micrograph showing compressed void and high concentration of Cu,O particles. 200x

Fig. 7a. Optical micrograph showing internal V-shaped rupture caused by void and high concentration of Cu2O particles. 100x
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Fig. 7b. Optical micrograph showing internal V-shaped rupture caused by void and high concentration of Cu2O particles. 400x

Fig. 8. Optical micrograph showing large and small irregularly shaped copper oxide particles originated from copper oxide slag. 300x

Fig. 9. Optical micrograph showing longitudinal crack in the rod. 400x

Fig. 10. Optical micrograph showing embedded copper oxide particle in the rod. 400x

Fig. 11. Optical micrograph showing a fine crack in the rod. 400x

As the cast bar is hot rolled, the cracks the rod. An area of high concentration open up, propagate internally and of CU2O eutectic particles is shown in become heavily oxidized. Hydrogen can Fig. 6. The micrograph also shows a be introduced into the copper as void or pore which has been comentrapped electrolyte (organic additives pressed during hot working. A copper such as glue or thiourea) or during rod having a high concentration of melting by using excessive reducing Cu2O particles in the center will usuall y result in V-shaped internal ruptures flames.' Excessive grain boundary microp- or central bursting during wiredrawing. orosity in the cast bar is shown in This phenomenon which results in Fig. 4. Surrounding the void, areas of cuppy wire is shown in Figs. 7a and 7b. Copper oxide slag. Defects which high concentration of Cu,O particles can be found as shown in Fig. 5. result from the introduction of copper During hot working of the cast bar, the oxide slag can be found in the early grain boundary network of Cu,O eutec- stages of the wiredrawing operation tic particles will be aligned forming (rod breakdown and coarse wiredrawdangerous particle banding. In other ing). The main symptom is that the words, this type of structure (see wire shows various degrees of brittleFig. 5) will not produce a uniform dis- ness, and the fractured area shows a tribution of Cu 2O eutectic particles in high concentration of metallic oxides

i ncluding copper oxide patches. Copper oxide slag is usually a combination of oxides and refractory pieces which become entrapped at the entrance of the caster in the molten metal pool. This condition will exhibit areas of very high concentration of copper oxide particles in the cast bar. These particles will be of irregular shape and larger than the normal eutectic Cu,O particles. A copper rod specimen havi ng a high concentration of copper oxide particles which originated from copper oxide slag is shown in Fig. &. Rod rolling/pickling operations Defects arising from the rolling and pickling operation are usually related to: surface cracks resulting from
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Fig. 12. Optical micrograph showing reduced copper particle from surface copper oxide. 400x

Fig. 13. Optical micrograph showing unattacked copper oxide beneath the copper rod surface. 400x

Fig. 14. Optical micrograph showing inclusion particle in the wire break identified as tool steel. 90x

nonuniform reduction of the bar stock; sub-surface defects resulting from oxidized cracks and sharp edges of the bar that are folded over by rolling; rolled-in oxides resulting from excessive accumulation of oxide on the roll surface; introduction of metallic particles from deteriorated or cracked rolling rolls surface, incomplete reduction of copper oxide on the rod surface during the pickling operation; "checks" or V-shaped ruptures due to high concentration of copper oxide particles on the rod surface; and overfills due to improper roll gap. Sometimes it is difficult to distin54 WIRE JOURNAL INTERNATIONAL

guish between defects that originate from the bar surface cracks and cracks that result from rolling the stock. Examining the rod defects at high magnification and theorizing the mechanism of defect formation is very important in determining the source of the defects. Different types of defects (bar surface cracks or rolling mill cracks) found on the rod surface are discussed here and shown in Figs. 9, 10 and 11. Roc! cracks. Cracks can be formed on the bar surface either due to nonuniform cooling during solidification or porosity due to high hydrogen content and higher-than-normal impurity content. These cracks will oxidize as the cast bar l eaves the caster and is exposed to air at

high temperature. The oxidized cracks will be deformed, smeared and folded over by layers of copper during further hot rolling. The cracks contain layers of copper oxide internally on their walls, but these will be embedded below the rod surface. These types of defects on the rod are shown in Figs. 9 and 10. During the rolling operation, surface cracks can sometimes be formed due to nonuniform reduction of the bar stock. As the cast bar is rolled, the temperature of the stock is progressively decreased due to increased cooling by the lubricating solution. The cracks formed probably will not be as oxidized as cracks formed at high temperature during the casting operation and the first reduction passes. A micrograph revealing this type of defect is shown in Fig. 11. Sub-surface de eels. Excessive buildup on the roll surface can also result in the defects on the rod surface. Copper and copper oxide can progressively accumulate on the roll surface -depending on the surface texture (smoothness or roughness) and the degree of reducing solution in the rod mill lubricant or coolant-and eventually will break away from the roll surface, becoming embedded and rolled onto the stock surface. If the rod surface contains excessive amounts of embedded copper oxide, the pickling operation might not be able to reduce or eliminate them completely.

Fig. 15a. SEM micrograph showing "check on the wire bar rod surface. 30x

Fig. 15b. Optical micrograph showing high concentration of CU2O particles in the "check." 400x
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Fig. 16. Macrograph showing overfills on two sides on the rod. 4x

Fig. 17. SEM macrograph showing folds on the wire surface resulting from overfills. 1480x

Examples of reduced copper oxide and embedded copper oxide on the rod surface are shown in Figs. 12 and 13, respectively. Ferrous inclusions. Rolling mill rolls are made of H-13 tool steel and generally have long roll life. However, the roll surface eventually deteriorates due to severe thermal shocks under continuous compressive stresses. This will ultimately result in pitting and cracki ng. Improper heat treatment and i mproper surface finish can lead to early deterioration of the rolls. Pitting is a result of an electrochemical reaction between the rolls and the copper in the presence of temperature and rolling mill lubricant. Additions of reducing chemicals to the lubricant solution could enhance this effect and must be carefully controlled. Steel particles can

be detached from the roll surface and be introduced onto the bar surface. An i ron detector has been introduced recently in the continuous rolling systems to detect ferrous inclusions. The detector probably will detect the ferrous particles more effectively if they are shallow on the rod surface. This type of inclusion is found in wire breaks (shown in Fig. 14) and can be easily identified by energy dispersive X-ray analysis because tool steel contains molybdenum and vanadium. Surface checks or cracks. Surface "checks" or V-shaped ruptures due to high concentration of copper oxide particles on the wire surface have been found in rods manufactured from conventionally cast wire bars. Wire bars have high concentrations of copper oxide particles on .the surface resulting

from the "set surface." Rod which is rolled from wire bar contains a significantly greater amount of copper oxide on the surface than in the copper matrix. The wire drawn from this type of rod contains "checks" or V-shaped ruptures (Fig. 15a) due to the higher work hardening in the area containing the high concentration of copper oxide eutectic which leads to high brittleness (Fig. 15b). This type of defect is not present in continuously cast and rolled rod since the cast bar does not contain a "set surface." Overfills. Overfills form during the rolling operation and are caused by i mproper or incorrect roll gaps which allow copper to protrude between the rolls. Instead of having a uniform diameter, the rod exhibits distinct corners or edges. An example of a large JUNE 1996 55

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Fig. 18. SEM micrograph of the wire surface showing a micro sliver originated during the wiredrawing process. 1860x

Fig. 19. Macrograph showing "checks" on the wire surface. 50x

overfill in the rod is shown in Fig. 16. When the rod is drawn, it will have one side peeled off or folded, resulting in a folded metal piece on the wire surface. This type of defect is shown in Fig. 17 and is characterized as a sliver. The slivers caused by overfills will appear i n the early stage of wiredrawing (coarse wiredrawing) and can be differentiated from slivers caused by the wiredrawing operation (Fig. 18). It is important to point out that copper rod containing excessive amounts of defects relating to high-oxide concentration (which could be properly called "poor rod quality") is responsi-

ble for excessive amounts of wire breaks in multi-wiredrawing machines and should be avoided in this equipment. Wiredrawing operation Defects arising from the wiredrawing operation are: "checked" wire (surface cracks); "cuppy" wire (central bursting); scratched wire (galling); flakes or slivers; embedded metallic fines; and pulled wire (tension) caused by plugging of the dies by excessive accumulation of metallic fines.

i mproper wiredrawing practices can lead to defects in the wire even if the rod contains minimal or no defects (grade A). Special attention should be given to all parameters of the wiredrawing operation to avoid the generation of any defects on the wire surface. "Checked" wire. One type of defect, which is produced by improper wiredrawing practices, can be classified as "checks" or V-shaped ruptures, and it is shown in Fig. 19. It should be noted that "checks" are located at regular intervals and are caused mostly by die misalignment, especially at a non-aligned die entrance. Micro cracks develop on the wire surface when excessive compression is exerted on one side of the wire. These excessive stresses cause high work hardening (excessive dislocation multiplication) and differential metal movement from the surface to the inside. A common cause of this defect is the incorrect entrance of the wire into the die during drawing. These cracks form "check" or V-shaped ruptures as the wire is further drawn.
Central bursting or

" cu ppy " wire. A

Fig. 20. Schematic showing central bursting mechanism. 56 WIRE JOURNAL INTERNATIONAL

second type of defect which is produced by incorrect die geometry and improper reduction per pass is classified as "cuppy" wire. In this type of defect, fine micro cracks develop in the center of the wire. The cracks become progressively

Fig. 21. SEM micrograph showing cup and cone ends of the central burst wire break. 80x

Fig. 22. Optical micrograph of center of the wire exhibiting severe central rupturing. 50x

Fig. 23a. Stereo micrograph showing excessive scratches on the wire surface. 30x

Fig. 23b. Optical micrograph showing excessively scratched tension wire break. 200x

Fig. 24a. SENT micrograph showing fine flakes or slivers on the wire surface. 620x

Fig. 24b. SEM micrograph showing fine flakes or slivers on the wire surface. 750x
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Fig. 25. SEM micrograph showing severely scratched wire resulting from lubricant starvation. 740x

Fig. 26. SEM micrograph showing accumulated' copper fines on the wire surface. 27x

Fig. 27. Optical micrograph showing plugged die wire break due to accumulated copper fines. 26x

l arger, elongated and form V-shaped ruptures during subsequent reduction in the dies. The mechanism of central bursting is shown schematically in Fig. 20. The V-shaped ruptures are present in the center of the wire and are not observed on the surface until the wire breaks. A typical "central burst" or "cuppy" wire break is shown in Fig. 21. It will exhibit the cone portion on one end having a shear lip covering 180 degrees of the wire circumference and a hollow portion on the other end. Optical examination of the wire break is necessary in order to determine whether the break is related to wiredrawing practice or the casting practice. The "central burst" or V-shaped ruptures caused by i mproper wiredrawing practice will not
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show high concentration of Cu2O particles in the center. It should be noted that

the V-shaped ruptures are located at regular intervals in the center of the wire (see Fig. 22). Surface markings. In a normal drawi ng practice with proper control of drawing parameters, the wire surface will show fine striations or grooves caused by the surface morphology of polycrytalline diamond dies. However, when the wire surface is severely scratched, it is usually caused by (1) worn dies, (2) insufficient lubrication at the die entrance, (3) accumulation of metallic fines at the die entrance, (4) wire touching the metallic components of the drawing machine and/or (5) breakdown of lubricant. A clear exam-

ple of scratched wire is shown in Fig. 23a. Depending upon the severity of the scratches, this type of defect can cause tension wire breaks (see Fig. 236). The above-mentioned drawing parameters to a lesser degree will cause fine flakes and slivers on the wire surface (see Figs. 24a and 24b). The fine flakes and slivers will not cause breaks until the wire is drawn to very fine size where the tensile stresses become critical. The fine flakes and slivers will cause severe problems during the enameling operation for magnet wire applications. The surface quality of wire is critical, since, after enameling, the presence of flakes and.. slivers will l ead to surface discontinuities. Copper fines. Copper fines are generated in the wiredrawing operation due to abrasion of the wire surface in the die. Copper fines generated during wiredrawing can affect the surface quality of wire as the fines reenter the l ubricating system and accumulate at the die entrance. Although filtering systems are capable of filtering particles as small as five microns, particles l ess than five microns will pass through the filter paper and could reenter the l ubricating system. Accumulation of the copper fines at the die entrance will block the lubricant entering the die causing lubricant starvation.(4) This can result in severe scratches on the wire surface (see Fig. 25). The copper fines can enter the die and become embed-

ded onto the wire surface (see Fig. 26). They also can result in a tension wire break called "plugged die" wire break (see Fig. 27). The amount of generation of copper fines depends on the rod surface quality and the wiredrawing practice. The rod surface and subsurface defectssuch as oxidized cracks, embedded copper oxide, seams and mechanical damage-generate significant amounts of copper fines. The copper fines are also found to contain significant amounts of copper oxide particles. With the growing use of multi-wiredrawing machines, it is of utmost i mportance to control these defects (cracks, embedded copper oxide) in the rod to minimize die wear and to obtain a high quality fine and ultra-fine wire and, more importantly, to decrease costly wire breaks.
Conclusions

A detailed characterization and examination of the main wire defects arising from the casting, rolling and drawing operation have been provided

i n this paper. Proper identification of these defects at the manufacturing site i s germane to correctly determine the cause and source of the defects as well as to implement the proper corrective action procedures for their elimination. Even though wire manufacturers depend heavily on rod producers to supply a high quality product, the drawing operation could, in many i nstances, add new defects in the processing of the wire. In other instances it could enhance small existing defects to the point where they become significant in the final wire product, A great synergism exists between the quality l evel of the rod and the processing parameters during wiredrawing (including the lubricating systems) which would result in a "world class" wire quality material. A high quality rod would be more forgiving during drawing and thus could tolerate greater punishment due to improper drawing conditions, but a lower quality rod would require near perfect drawing conditions to avoid the formation of defects. However, many

defects could be generated during the drawing of a high quality rod which would result in a lower quality wire product.
References 1. Nonferrous Wire Handbook, Vol.

I, The Wire Association International, Inc., Guilford, Connecticut (1977). 2. G. Meseha, "Fundamentals of Applied Artificial Intelligence in Manufacturing Rod at Phelps Dodge," The Wire Association International, Inc., 1992 Annual Convention. 3. E.H. Chia and G. Patel, "Copper Rod and Cathode Quality as Affected by Hydrogen and Organic Additives," Wire Journal International, November 1992, pp. 67-75. 4. G. Patel and-E.H. Chia, "Characterization of Copper Fines and its I mpact on Filtration," Wire Journal International, April 1992, pp. 49-56.