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Metallography and Microstructures of Copper and Its Alloys

Introduction
COPPER AND COPPER ALLOYS have played an integral role in human technological progress since antiquity. Native copper and then bronze alloys were fashioned into the first metal tools and decorations. The combination of electrical and thermal conductivity, workability, corrosion resistance, strength, and its abundance makes this family of metals important to all industry.

Alloying Systems
Copper alloys have traditionally been classified by composition and as wrought or cast in the groups show in Table 1. The alloys are listed by UNS designation that is administered by the Copper Development Association. Selected alloys are listed for each group. Similar compositional grouping is present in international designation systems. Table 1 Nominal compositions of copper and copper alloys

Coppers. The alloys designated as coppers contain 99.3% or more copper. These have the highest electrical and thermal conductivity. Impurities such as phosphorus, tin, selenium, tellurium, and arsenic are detrimental to properties such as electrical conductivity and recrystallization temperature (Ref 1). If deliberately added, however, these alloying elements can enhance other desirable properties. Silver is the only impurity that does not significantly lower the conductivity of pure copper, so it is included in the percent weight of copper when calculating the minimum percent weight of an alloy. High-copper alloys contain between 96 and 99.3% Cu in wrought products that do not fall into any other special categories. For cast alloys, copper content above 94% is included. The chief alloying elements are cadmium, beryllium, and chromium. Copper-zinc alloys (brasses) have zinc as the prime alloying element. Wrought alloys are subdivided into Cu-Zn alloys, Cu-Zn-Pb (leaded brasses), and Cu-Zn-Sn alloys (tin brasses). Cast brasses have four subdivisions: Cu-Zn-Sn and Cu-Zn-Sn-Pb alloys (red and leaded red, semired and leaded semired, and yellow and leaded yellow brass); Cu-Mn-Zn and Cu-Mn-Zn-Pb (high-strength and leaded high-strength brass, also called manganese bronze and leaded manganese bronze); and Cu-Si (silicon brasses and bronzes); and Cu-Bi and Cu-Bi-Se (copper-bismuth and copper-bismuth-selenium alloys). Bronzes include copper alloys that do not have zinc or nickel as the major alloying element. The four subgroups of wrought alloys are: Cu-Sn-P (phosphor bronze), Cu-Sn-P-Pb (leaded phosphor bronze), Cu-Al (aluminum bronze), and Cu-Si (silicon bronze). Although called bronzes, the manganese bronzes that have zinc as the major alloying element are classed with the brasses. The cast bronzes are called Cu-Sn (tin bronze), Cu-Sn-Pb (leaded and high-leaded tin bronze), Cu-Sn-Ni (nickel-tin bronze), and Cu-Al-Fe and Cu-Al-Fe-Ni (aluminum bronze). Copper-nickels are available as wrought and cast alloys.

Copper-nickel-zinc alloys, wrought and cast, are known as nickel silvers. This name is based on their luster, not their composition, because they do not have silver as an intentional alloying element. Other alloys include specialty alloys, copper leads, and brazing alloys. Gas Solubility. Hydrogen and oxygen are quite soluble in liquid copper, but the solubility in solid copper is very small. The metal therefore rejects a considerable amount of these (and other) gases on solidification. Oxygen content must be carefully controlled so that detrimental quantities of Cu 2O, which decreases workability, are not formed. In molten copper, oxygen can react with dissolved hydrogen to form water vapor, which evolves as voids during solidification, called hydrogen illness. The voids cause hairline cracks that can lead to fracture during hot rolling and produce a variety of defects on the surface of wire rods (Ref 2). Oxygen and hydrogen interfere with conductivity; however, small and controlled amounts of oxygen are actually beneficial to conductivity in that they combine with and remove from solution impurities such as iron that are far more detrimental. A copper-oxygen phase diagram would show a eutectic at 0.4 wt% O (or 3.4 wt% Cu 2O). Figure 1, 2, 3, and 4 show hypoeutectic copper-oxygen alloys, where the primary dendrites (light color) are copper. Figure 5, 6, 7, and 8 are hypereutectic, where the structure consists of particles or dendrites of Cu2O (dark colored) and eutectic.

Fig. 1 - The effect of oxygen content on the microstructure of a hypoeutectic ascast copper-oxygen alloy. Oxygen content of 0.024% results in primary dendrites of copper (light) plus eutectic (mottled areas of small, round oxide in copper). As-polished. 100

Fig. 2 The effect of oxygen content on the microstructure of a hypoeutectic as-cast copper-oxygen alloy. Oxygen content of 0.09% results in primary dendrites of copper (light) plus eutectic (mottled areas of small, round oxide in copper). As-polished. 100

Fig. 3 The effect of oxygen content on the microstructure of a hypoeutectic as-cast copper-oxygen alloy. Oxygen content of 0.18% results in primary dendrites of copper (light) plus a more connected area of eutectic than in Figure 2 As-polished. 100

Fig. 4 The effect of oxygen content on the microstructure of a hypoeutectic as-cast copper-oxygen alloy. Oxygen content of 0.23% results in less primary dendrites of copper (light) plus more connected areas of eutectic than in Figure 3 As-polished. 100

Fig. 5 The effect of oxygen content on the microstructure of a hypereutectic as-cast copper-oxygen alloy. Oxygen content of 0.44% results in particles or dendrites of oxide (dark) and light eutectic. As-polished. 100

Fig. 6 The effect of oxygen content on the microstructure of a hypereutectic as-cast copper-oxygen alloy. Oxygen content of 0.50% results in the increased amount of particles or dendrites of oxide (dark) in the light eutectic, as compared to Figure 5 As-polished. 100

Fig. 7 The effect of oxygen content on the microstructure of a hypereutectic as-cast copper-oxygen alloy. Oxygen content of 0.70% results in the increase of dendritic structure of oxide (dark) in the light eutectic matrix, as compared to Figure 6 As-polished. 100

Fig. 8 The effect of oxygen content on the microstructure of a hypereutectic as-cast copper-oxygen alloy. Oxygen content of 0.91% results in the increase of dendritic structure of oxide (dark) in the light eutectic matrix, as compared to Figure 7 As-polished. 100

Microstructures of Copper and Copper Alloys


Coppers and High-Copper Alloys. The pure coppers are commercially significant because they have the highest conductivity. The effect of hot and cold working and heat treatment of oxygen-free coppers is shown in Fig. 9, 10, and 11. Note in Fig. 11 that oxygen has been reintroduced into the previously oxygen-free metal by heating in a noninert atmosphere. The dendritic structure of electrolytic tough pitch copper is seen in the cast ingot of C11000 (Fig. 12). A macrograph of C12200, phosphorusdeoxidized copper (Fig. 13), reveals a typical solidification pattern of grains in a 102 mm (4 in.) continuously cast ingot. As is typical with relatively pure copper, the grain boundaries are well defined. The transverse and longitudinal sections of the ingot show that the grains grow perpendicular to the wall. Grain boundaries are parallel to the direction of heat flow. At the core, a columnar grain is along the axis of the ingot. Sections taken normal to the direction of heat flow near the wall (Fig. 14) and near the center (Fig. 15) show how the grain structure gets finer near the center. These images (Fig. 13, 14, and 15 illustrate the significance that the orientation of a specimen section has in determining the appearance of the grain structure.

Fig. 9 Copper C10200 (oxygen-free copper), hot-rolled bar. Large, equiaxed, twinned grains. Etchant 1, Table 2. 100

Table 2 Etchants and procedures for microetching of coppers and copper alloys

(a) The use of concentrated etchants is intended unless otherwise specified. (b) This etchant may be alternated with FeCl3. (c) Grard's No. 1 etchant. (d) Plus 1 g CrO3. (e) Grard's No. 2 etchant. (f) (f) Plus 1 g CuCl2 and 0.03 g SnCl2 (tin chloride)

Fig. 10 Copper C10200 (oxygen-free copper), cold worked, annealed 30 min at 850 C (1560 F). Equiaxed, recrystallized grains containing twinned areas. Etchant 4, Table 2. 250

Fig. 11 Copper C10200 (oxygen-free copper), hot-rolled bar, heated 1 h in air to 665 C (1225 F). Specimen taken from near the bar surface shows Cu2O (dark dots) caused by oxygen penetration during heating. Etchant 1, Table 2. 250

Fig. 12 Alloy C11000 (electrolytic tough pitch copper), static cast. Excellent definition of dendritic structure. Etchant 10, Table 2. 5

Fig. 13 Alloy C12200 (deoxidized high-phosphorus copper), continuously cast in a 102 mm (4 in.) diameter ingot. Top, transverse section showing radial grain growth. Bottom, longitudinal section. Dark center is columnar grains oriented along the axis of the ingot. Waterbury reagent was used, which has same constituents as etchant 7, Table 3. 0.6

Fig. 14 The same C12200 (deoxidized high-phosphorus copper) continuously cast alloy in a 102 mm (4 in.) diameter ingot as in Figure 13 Section taken near the ingot surface normal to the radial grain growth. The structure is coarse, unbranched dendrites. Waterbury reagent was used, which has the same constituents as etchant 7, Table 3. 150

Fig. 15 The same C12200 (deoxidized high-phosphorus copper) continuously cast alloy in a 102 mm (4 in.) diameter ingot as in Fig. 14 Section taken near the ingot core normal to the radial grain growth. The dendrite structure is much finer than in Fig. 14. Waterbury reagent was used, which has the same constituents as etchant 7, Table 3. 150

Fig. 16 Copper C12200 (deoxidized high-phosphorus copper). Internal oxidation (presence of dark dots of P2O5). Etchant 4, Table 2. 75

Fig. 17 Copper C14520 (DPTE), hot-rolled and drawn rod. Dark particles elongated in the rolling direction are copper telluride, which improves machinability. Etchant 7, Table 3. 250

Alloy C12200 (deoxidized high-phosphorus copper) contains high-residual phosphorus, a common deoxidizer, that improves weldability. The micrograph (Fig. 16) shows the presence of P 2O5. The addition of tellurium to copper-phosphorus alloy improves machinability. Figure 17, a micrograph of C14520, designated DPTE, shows the effect of hot working. The copper-telluride is present in the dark particles. The addition of sulfur likewise improves machinability. A cold-worked sample of C14700 is given in Fig. 18.

The greatest tonnage of copper alloys are those consisting of solid solutions. The high-copper alloys, copperberyllium, copper-chromium, and copper-zirconium, have limited solid solubility, however. These systems can be precipitation hardened. The phenomenon, which is also called precipitation strengthening and age hardening, is possible because the limit of solid solubility contracts with decreasing temperature, a condition known as retrograde solubility (Ref 1). Copper-beryllium alloys (Fig. 19, 20, and 21can be heat treated to remarkably high strengths, as evidenced by their hardnesses. The precipitation process increases the copper content of the surrounding matrix and improves the conductivity of the alloy. This combination of strength and conductivity makes these alloys useful as electrical contact components.

Fig. 18 - Copper C14700 (sulfur-bearing copper) rod, cold worked to 50% reduction. Transverse section shows dispersion of round particles of CuS, which improves machinability. Etchant 7, Table 3. 200

Fig. 19 - Alloy C17200 (beryllium-copper), solution treated 10 min at 790 C (1450 F) and water quenched. Typical hardness is 62 HRB. Structure is equiaxed grains of supersaturated solid solution of beryllium in copper. Etchant 3, Table 2. 300

Fig. 20 Same alloy (C17200) and processing as in Figure 19 but aged 3 h at 360 C (680 F) after solution treatment. Typical hardness is 37 HRC. Copper-beryllium precipitates at grain boundaries and within grains. Etchant 3, Table 2. 300

Fig. 21 Same alloy and processing as in Figure 19 except reduced 11% by cold rolling to quarter-hard temper. Typical hardness is 79 HRB. Alpha grains are elongated in the direction of rolling. Etchant 3, Table 2. 300

Brasses. The phase diagram of the copper-zinc system (Fig. 22) has the compositional ranges of five common brasses superimposed. It is seen that the -solid-solution region extends to 32.5 wt% Zn and includes red brasses (C23000), low brass (C24000), and cartridge brass (C26000). These have formability similar to pure copper. The dendritic structure of C26000 (Fig. 23, 24) and the annealed grains of Fig. 24 are similar to the