13 Non-Ferrous Metals and Alloys 13. INTRODUCTION It is very common to broadly divide metallic materials into two classes, ferrous and non-ferrous materials. AS the name suggests, the latter class, the non-ferrous materials comprises of materials having some metal other than iron as the principal constituent. This class includes the common metals (and their alloys) like copper, aluminium, lead, nickel, magnesium, tin, zinc etc., and the precious metals like gold, platinum, silver, etc., and their alloys. Ferrous materials, i.e., iron and its alloys are the most widely employed engineering materials, and these out-number in applications all the non-ferrous metals and their alloys put together. This is the reason ff putting all the non-iron materials in the second class, But, this fact never-the-less can't decrease the ‘unique importance of non-ferrous metals and alloys. They have special properties, which entitles them to ‘have large applications where only these alloys can be used, though usually these are costlier. For example, copper, or aluminium electrical conductors cannot be substituted by iron and steel. The aeroplane could never have been developed to its present state without aluminium. Special alloys have been developed to meet the stringent requirements such as high strength, corrosion and oxidation resistance at high temperatures, to be used in jet-engines, gas-turbines, etc. Some important properties of non-ferrous metals and alloys, in general, are: 1, Excellent thermal and electrical conductivity: For example, silver, copper and aluminium: 2. Good ductility and maileability: Aluminium can be beaten to foil of less than 0.0009 em thickness. ‘One gram of gold can be drawn to give 2.7 kms of wite. Fabrication of components becomes easier by rolling, forging, etc. 3, Excellent corrosion resistance at room and higher temperatures, and in most environments. 4, Light in weight such as aluminium, magnesium, titanium. 5, Some low melting alloys can be used as solders, or can be easily die-cast in one operation. 6 1. Attractive colours such as golden colour of gold, brasses, bronzes, etc. High strength at high temperatures such as of Ni-Cr-Co alloys such as ‘Nimonie 9" (20 Cx, 16 Co, 23 Ti, 14 Al, bal. Ni) used for jet turbine aero-engines, etc. 8. Good wearresistance at high temperatures such as of Stelite (27 Cr, 3 Ni, 5 Mo, I Fe, bal. Co) for turbine-blades of jet-engines. 9. Good cutting properties at high speeds such as of Stellite 10. Good bearing properties of white metals, babbits, etc. LL, Non-sparking tools of Cu-Be alloys, et. 12. Sweet-inging musical-sound of bells (Cu-20% Sn)AGE-HARDENING 655 (ii) Peak hardness increases Why ? (it) Peak hardness is attained in less time. Why ? (®) What is ceversion ? If naturally age hardenable alloy is kept for a longer time at temperatures above its GP zone solvus, what isthe result ? What is the meaning of “reversion is reversible’ ? 6. (a) Discuss the possible hardening mechanisms operating due to age-hardening (®) Which mechanism is taking pace if particles are (50 A in size, (i?) $00 A in size, (© Which stage of precipitation leads to peak hardness by ageing ? 7. What is duplex ageing ? What is the meaning of critical temperature here ? What is eriical sized precipitate here? How does duplex-ageing removelreduce PF zones ? 8, State the different factors that must be saisied in order to obtain age-hardening in an alloy, 9. Choose the correct statement: In age-hardenable alloys, maximum ductility is obtained B. immediately after solution treatment and subsequent quenching . after optimum ageing D. after overageing. ByNON-FERROUS METALS AND ALLOYS 13.1. COPPER AND COPPER ALLOYS 67 ‘The reddish-brown metal is a very important engineering metal not only in the pure form but also in the form of alloys. Table 13.1 shows some properties of pure copper. Extra pure copper contains 99.999% Cu, used in scientific research, but commercial pure copper contains 0.1-0.5% of impurities. Alloying also changes the colour of the copper. Indeed few metals, if any, can be alloyed like copper, to achieve colours ranging from the reddish-hue of copper itself, to the rusty-gold of bronze, the yellow of brass, the silvery-white of the nickel-silvers and the purple of the “Regulus of venus’ (a copper-antimony alloy). Table 13. Propery Coystal Structure Melting point Boing point Density Coefficient of linear expansion (20-100°C) Electrical resistivity (20°C) Properties of Pure Copper Foc 1oa3°c 2600°C 8.94 glem® 168 x 10% per °C 1.7241 micro ohm-cm ‘Tue commercially pure copper is available in the following grades: 1, Electrolytic tough-pitch (ETP) Copper: It has 99.95% Cu, 0.04% O2 (present as tiny globules of CuO) with a cast microstructure as in Fig: 13.2 (a). Cold working and annealing removes the interdendritic eutectic to take up shapes as Cu,0 inclusions resulting in increased strength. This copper has 101.6% of electrical conductivity of pure copper. This is the standard clectrical-wire grade copper used for conductors, bus-bars, power- cu cables, motors, generators, switches. Also used for automobile 1160 1120 1083 1085 1040 Leys CuO.) 0025 075 10 0% ‘Temperature °C radiators and gaskets, kettles, vats, pressure vessels. Such a Fig, 13.1. Phase-diagram CuO, copper if heated in an atmosphere having hydrogen, suffers from cracking due to water-vapours exerting pressure. Hydrogen diffuses in to react with O2 to form water vapours. Fee. Fig. 13.2. Mirostuctare (a) of wough-ptch copper showing copper copper oxide eutectic. Etched with sodium dichromate, ¥ 500, (b) east Cu-02 Bi x 20068 PHYSICAL METALLURGY 2. Onygen-free high conductivity Copper (OFHC) has 99.95% Cu, and the electrical conductivity is 95% of pure copper, and is produced by special techniques by having non-oxidising atmospheres. I is used for electrical, electronics and electo-vacuum engineering. 43. Deoxidised low-phosphorus Copper (DLP) has 99.92% Cu and 0.009% P. The deoxidised high phosphorus copper (DHP) has 99.95% Cu and 0.04% P. The presence of 0.04% P reduces electrical Conductivity to 75% of pure copper. Phosphorus is used as a deoxidiser. Such copper is easy to work land weld, and thus, finds applications for domestic water-pipes, boilers, heat-exchangers, automobile radiators, petrol and oil lines, etc 4, Arsenical tough pitch Copper has 0.4% As and 0.065% O2, whereas Deoxidised arsenical copper has 0.4% As and 0.04% P. These are tougher, stronger with beiter resistance to scaling. These find applications now in welded vessels, anks, condensers and heat-exchanger 5, Freeeutting Copper his about 0.6% Te, or S to improve its machinability, high resistance to corrosion with excellent surface finish, and is thus used for bolts, studs, welding-tips, contact-pns, Switch gears, relays, precision electrical equipments and magnetron valves. Electrical conductivity is 95% of pure copper. 6. Silver-bearing Copper has 99.9% Cu, 0.03% Ag. Silver increases the recrystalisation temperature, w the creep strength by inducing solid solution strengthening without adverse effect on the electrical ‘conductivity of copper. It finds applications for the manufacture of electric-motors for rail road and aircraft applications 7. Cadmium-Copper has 1% Cd, which increases strength without decreasing conductivity. The alloy is ideal for overhead lines, ie. for railways electrification 8, Zirconium-Copper: The heat-teatable alloy contains 0.15% Zr. It is used for electrical enginecring applications, Solution treated at 900°C, aged at 450°C results in strength of 460 Nimm? and 10% E. 9. Chromium-Copper: The heat-treatable alloy contains 0.5-1.0% Cr, and is used for applications demanding high strength and high conductivity CuO Cr: uTs Proof Stress %E Hardness, VPN Quenched from 1000°C, 463 Nimm? 340 Nim? 15 140 Aged, 430-500°C for 3 hrs. 3 It retains strength at 350-400°C even after prolonged periodsThus, used for spot-welding electrodes, seam-welding electrodes, discs, electrical switch gears. ‘Commercial coppers are available in various shapes such as rods, wires, sheets, strips, plates, pipes, tubes, etc, Ingot of most of these coppers can be obtained. All the elements decrease the electrical conductivity of copper particularly those which form solid solutions. The elements in increasing order of the effect are Ag, Au, Cd, Zn, Ni, Al, Be, As, Fe, Si, P etc ‘The most harmful impurities in copper are bismuth and lead. They are almost insoluble in copper and form low melting eutectics. The eutectic in Cu-Bi system contains 99.8% Bi and that in the Cu-Pb system 99.94% Po. Bismuth even in hundredths of one percent is present at the grain boundaries (dihedral angle = 0, sce chapter 2) (Fig. 13.2 5), and causes fracture to occur along the grain boundaries as bismuth (or its eutectic) is brittle, when cold worked, ie, causes cold-shortness of copper. In hot working, it melts and separates the grains causing hot-shoriness . Lead is present as globules and causes red-shortness, Although O> and sulphur too are almost insoluble in copper, but melting points of eutectics (165°C and 1067°C respectively) are higher than the hot-working-temperature of copper, and donot cause red-shoriness. 13.2. PROPERTIES OF COPPER Copper is one of the few metals which finds a large number of applications in the pure unalloyed form due (o its following unique properties zNON-FERROUS METALS AND ALLOYS 659 1, Excellent electrical-conductivity: Copper has the highest electrical conductivity of all the known substances except silver, which is slightly superior as compared in table 13.2. As a convention, conductivity of copper is taken as 100. The high electrical conductivity of copper is the reason why copper is being used extensively for electrical purposes, for conducting the clectrcity, for distribution, used in generators, bus-bars, powerlines, switches, electric-motors, electric-taction, telephone wires, and many more. ‘Table 13.2. Comparision of Conduct Property Silver: lecttical conductivity 106 ‘Thermal conductivity 108, 2, Excellent thermal conductivity: Copper has higher thermal conductivity than any substance known ‘except silver, which is slightly superior (Table 13.2). Copper conducts heat so well as to find applications in radiators, heat-exchangers, refrigerators, expansion pieces, condenser plates and tubes, boiler tubes and parts, thermal power stations, kettle, household utensits etc, 3. Good ductility and malleability: As copper has FCC crystal structure, itis easy to fabricate it as it has ‘good ductility and malleability. It is slightly inferior to gold and silver. Copper can be easily rolled down to strips of thickness less than 0.0025 cm without cracking, and can be drawn as wires of diameters less than 0.00025 cm. It can be easily pressed, forged, spun into simple and complex shapes. ‘As copper has low machinability and poor foundry properties (due to large shrinkage in castings), and low strength, it is used in the cast condition only when high electrical or thermal conductivity is required. During cold working processes, copper becomes hard, strong with the increase of cold work but less ductile, The ductility (as well as electrical conductivity) can be restored by recrystalisation annealing between 350-400°C. Some mechanical properties of copper are given in Table 13.3. ‘Table 13.3. Mechanical Properties of Copper Modulos of elasticity 112 & 10 Kent? Modus, of rigidity 40 x 10" Ke/mmn? Fagus strength 8 Kym? for 10 reversals Reezystalisation temperature 200°C Forging temperature 650"-900°C Site urs Hardness % Elongation Keim BAN Sem) As east 6 0 25 Hot worked a 50 45 Cold worked and annesied 2 45 50 Cold work: 10% reduction n a2 38 20% reduction 2 103 15 (60% reduction «0 ua 6 90% reduction 46 ns 3 4, Good corrosion resistance: Copper finds applications in water-lines, fuel and oil lines in aircraft, for ‘conducting food stuffs, beverages, pulp-mill pulp, chemicals. Also for roofing, window screens, coins, '5. Copper as well as its alloys can be easily joined by normal processes such as soldering, brazing, and weldingPHYSICAL METALLURGY 6 Copper is non-magnetic. It s very important for many applications. 7. Apart from gold, copper is the other metal which possesses natural attractive colour. Alloys produce atractive colours as explained earlier and aesthetic value leads to some applications. 8. Copper can be easily plated as a base on other metal like steels 9. Copper finds large applications in powder metallurgical products, where one ofthe above properties becomes an important requirement such as for copper-base-contact materials. 10. Alloys: Copper isthe base ofa large number of alloys, and i is also added to other metals to form the alloys. Copper-base alloy are very important pat of non-erous alloys. 13.3, ALLOYS OF COPPER Copper and copper-base alloys find greater applications than any other metal except iron and steels. In general, alloys of copper and zine are called brasses. The alloys of copper and elements other than zinc are called bronzes. The term ‘bronze’ was originally used for copper-tin alloys. Copper alloys find large applications because of the following superior properties: (@ Copper alloys possess greater strength and hardness along with increased ductility as compared to copper, The increased ductility helps in the easy production of different shapes by cold forming methods such as deep drawn tubes, cartridge-cases, etc. The process of age-hardening can increase the strength and hardness of some copper alloys such as of copper-beryllium. The, strength and hardness of copper can be increased by adding some alloying elements without uch decrease in its electrical conductivity to find applications for parts which have to resist wear as well as have high electrical conductivity: Cu-0.4/1.0 Ci alloy is used for trolley-wires. Cu-2/2.5 Be with some Co, Ni alloys find applications as springs, and welding electrodes. (i) Copper alloys such as brasses, bronzes can be more easily cast than copper. (iv) Corrosion resistance of copper alloys is better than that of copper. 133.1. BRASSES Brasses are essentially alloys of copper and zinc, where zinc could be present up to a maximum of SO%. Fig. 133 (a) illustrates industrially important part of Cu-Zn phase diagram. The complete diagram is a combination of five simple peritectic reactions. Table 13.4 illustrates important phases with properties in Cu-Zn diagram of commercial importance. ‘Table 13.4. Important Phases with Properties in Cu-Zn Diagram of Commercial Importance. Phase | Range of % Zn os | Sirucure ‘Nanure Propenies room temperature @ 0— 36 FOC | Solid sohtion of Zn in Cu, Swong but ductile, can be Solubility increases to 39% at |easily worked at room 454°C and then drops to 32.5% at | temperature ‘905°C 8 46.6 — 506 BCC — | Solid solution based on CuzZn | Harder, more britle at room compound. B’ ondered solid | gmperature, but becomes solution not above 454-470°C | plastic at higher temperatures = 800°C 1 585 — more _ | Complex cubic | CusZng electron compound (21/13) | Weak and very brite. ‘The slowly cooled Cu-Zn alloys have only single phase, o (alpha), when the zine content is up to a maximum of 36%, i.e., Cu-Zn alloys having Zn up to 36% are called alpha-brasses, ‘The alloys having Zn between 36% and 46.6% are called alpha-beta brasses. Alloys with 46.6 to 50.6% Zn are beta-brasses. ‘The properties of any brass depends on the volume of these phases present in it. The tensile strength andNON-FERROUS METALS AND ALLOYS elongation increase in alpha region with the increase of Zn content with the elongation reaching a maximum at 30% Zn (refer section 6.2). Alpha is ductile and strong, but beta- phase is strong and brittle at room temperature. When beta phase starts appearing, the strength continues to increase up to a maximum (at 45% Zn) till the alloy has all brittle beta ‘phase to show decrease in stre- rgth, Strength drops sharply with the appearance of weak ‘and brittle gamma. ‘The presence of beta phase causes considerable decrease in ducti- lity. The resistance to shock decreases while the hardness increases with the presence of beta. Beta-brasses have no practical applications. Gamma phase makes the alloys extre- mely brittle, and that is the reason that brasses with gamma phase have no commercial applications except the one containing 50% Zn, 50% Cu, which is used as a brazing sol- der because of its low melting point. Depending on the defor- mation behaviour and the structure, commercial basses ccan be classified into two cate- goties: (@ Alpha-brasses or Cold worked brasses. Temperature °C Bares 8 ! “0 1 B 20 30 40 50 60 (a) 7m, wh 60 5 a0 204 Zn, WO% a a % 1 vA ee @® ? Fig. 133, (a) Cu-Za phase diagram, (b) Effect of Zo on strength and ductility, (6) on hardness.662 PHYSICAL METALLURGY (B) Alpha-beta brasses, or Hot worked brasses. ‘Alpha-brasses: Single phase alpha-brasses contain up to 36% Zn. These have excellent cold formabilty (also hot formabilty), and thus, are often called cold-worked brasses. They have good corrosion resistance and rachinabilty. Alpha-brasses having up to 20% Zn are reddish in colour, and are often called red-brasss, while the colour becomes-yellow when Zn is between 20% to 36% and are called yellow--brasses. Yellow-brasses with higher strength and ductility are used for drastic cold working operations. Season-cracking occurs in alpha-brasses when intergranular corrosion occurs specially in ammonia atmosphere. As high residual stresses ae responsible for season cracking, the defect ean be avoided if alpha brasses are stress-annealed at about 250°C. ‘Some important alpha brasses are given in Table 13.5. The cartridge-brass if annealed at 750°C, develops coarse rains, and if then deep drawn, leads to inferior surfaces called ‘orange peel effect’, which is normally avoided. The grain size should not exceed 30 to 60 wm ‘Table 13.5. Important Alpha-Brasses ‘Name and Composition Uns, ys. ,| %E |Hardness| “Applications Kenn | Kein BN T. | Gilding Metal Coins, medals, plaques, tokens, fase caps, 95 Cu,5 Zn annealed | 25 8 50 | 60. | primers, cheap jewelry, imitation gold, ‘base for gold plating. 2, | Commercial bronze Costume jewelry, compacts, Lipstick 90Cu, 10 Zn Annealed | 26 | 85 | ss | 60 cases, maine hardwares, rivet, screws, Spring | 50 | 43 4 | 185. | gritwork screen-cloch, It has golden colour. 3. | Red brass Electrical conduit sockets, architectural 85Cu 15 Zn Annealed} 278 | 10 | 60 | 65. |rims, condenser tubes, heat-exchanger tubes, plumbing pipes, éompact cases, lipstick cases, name plates, Tags, radiator cores, corrosion resisting tubes, drawn containers, bullet envelops. 4. | Low brass, CCofd drawn shapes, musical instruments, Duteh metal Flexible hoses, omamental work, medal- 80.Cu 20Zn Annealed} 223 | 10 | 48 | — | tions, thermostat bellows; Hammered as a substitute to gold leaf. Condenser tubes, Cartridge Brass ‘The classical 7030, cartridge brass used 70 Cu 30 Za for making cartridge cases, has highest ‘Annealed 34 | 12 | 70 | 65° | ductility with good strength, suitable for Cold worked | 648 | 447 | 3 190 | drastic cold working like deep drawn parts such as radiator cores, tanks, head light feflectors for automobiles; Flashlight shells, condenser tubes, electric sockels, lamp fixtures, hardware eyelets, rivets, springs, fasteners; ammunition parts such as catridge cases, shells; plumbing accessories. Thin sheets, strips for further shaping. 6. | Admiralty Brass ar | = | 65 | — J Addition of Sn improves resistance 10 70 Cu 29 Zn 1 Sa corosion, arid the strength. Condenser tubes, heat-exchanger tubes in steam power plans, ‘Aluminium Brass at | — | ss | = | Addition of At improves the corrosion 6 Cu 22 Zn 2 AL resistance more than Sn addition as the former forms a tenacious self-healing protective-film on the surface to replace ‘admiralty brass for marine and land power pants,[NON-FERROUS METALS AND ALLOYS os ‘Alpha-beta brasses: Brasses having 36% to 46.6% Zn have two phase structure containing 01 + B’. As BB phase is harder and more brittle at room temperature, a+ BY brasses are stronger having higher wear resistance, but have low ductility at room temperature, and thus, ate more difficult to cold-work, As beta phase is soft and ductile at high temperatures, the o +B brasses (for example-60 Cu 40 Zn), when heated to temperatures around 800°C, become single phase beta-brass, Fig. 13.3, when it can be easily hot-worked. ‘Thus, & + B brasses have excellent hot-working properties, and are also called hot-worked brasses, These basses are also used in cast as well as in slight cold worked state ‘The & +B brasses have only single beta-phase at temperatures higher than 800°C, and o-phase precipitates on cooling at beta phase boundaries in between 770° to 500°C. The relative amounts of ct and Bephases can be varied by the rate of cooling in air, or water (also to remove the scale). Faster cooling Telains larger amounts of beta phase, which has higher hardness and machinability, whereas slower cooling fesults in larger amounts of alpha phase resulting in larger ductility for cold-working operations. If the hot ‘working is continued down to 600°C, the brass has fine grain structure. The grain size of 60/40 brass can be Tefined by first heating to temperature where it is all B-phase. This temperature should be lowest possible, find time of holding should be minimum, otherwise grain growth is rapid once a- phase dissolves. It is then Cooled slowly. Some ot +B brasses are given in Table 13.6, These are cheaper brasses than acbrasses. ‘Table 13,6, Important Alpha-beta Brasses Name and Composition | UTS | vs. | %E aie Applications \Keyn| Ke/mnt BIN T. | Muntz MetalYellow brass “This is the most important of brasses with fou 40 Zn Annealed | 37 | 15 | 45 | 35 |excellent hot working properties and high Hard 54 | 34 | 10 | 149. | strength, Easily hot rolled, extruded, forged at 800°C. Used as sheets in ship-sheathing, condenser heads, architectural work, perforated ‘metal, Large nuts and bolts, valve stems. 2, | Freecutting brass | 1 has excellent machinability to be used for 61,5 Cu 355 Zn 3 PD gears, hardwares, serew. machine parts. 3, | Naval bras/Tobin bronze Tin improves corrosion resistance of Muntz {60 Cu 39 Zn 1Sn, 4s | — | 47 | — | metal Suitable in salt water, in marine hardware fs condenser plates propeller shafts, piston rods, valve stems. 4. | Architectural bronze It has excellent forging properties to find 57 Cu 40 Zn 3 PD applications for lock bodies, handrails, grills | industrial forgings. 5, | Manganese Bronze ‘Mn acts as scavenger, improves mechanical 58Cu 39Zn 1.4Fe, 1Sn, properties and corrosion resisience. OA, 0.2Mn. (a) Weought 52 | 24 | 25 | 120. | Best worked in hot state. Clutch disks, extruded shapes, pump rods, shafting rods, valve stems, ‘water "turbine runners, auto-clave valves: propeller blades of all sizes, rudders and other ship fcings. Cast 443] 172 20 | Good resistance to sea-water to find use for 58Cu 385Zn 1Mn 1.25Fe | MNm-?| MN? ‘marine engine pumps, ship propellers, gears, 1251 railway axle boxes. (©) 60-68 Cu, 0.20 Sn,| 690] 414 18/21 | Important high stress brass. (0.20Pp, 25-5.0Mn_2-4Fe, |MNmv?] MNm™ . 3-7SAl, Bal. Zn 6. | Forging brass 60Cu38 — | — | —| — | Has excellent hotworking properties. Used for 2n2Pb hot forgings, hardware and plumbling parts68 PHYSICAL METALLURGY Fig. 134, Microstructures of brasses (a) 7030 bras, () Chil-cas, showing coring x 60, (i) Cold worked and annealed showing annealing twins x 60, (b) 6O/40 brass. Cill-cast oclight, dark > 150 CAST BRASSES As the liquidus and the solidus are very close to each other in o + B" range of compositions, casting properties of these brasses are good as these have high fluidity and less segregation. Normally these brasses ‘contain other elements to improve properties like strength. Their effect on microstructure is as if these increase the zinc content, except nickel which has the opposite effect. Guillet established zinc equivalence of some of the elements present in brass to estimate the phases present in it ie., whether it is a, or o + B brass as: Hlement 7 AL Sn Mg [ca P| i Ma [Ni Zine Equivalent | 10 5 2 2 t 1 o9 [os | -12 For example, 1% AI has same effect as 5% Zn, while 1% Ni has same effect as 1.2% Cu. 133.2, BRONZES ‘The name ‘bronze’ was originally used to denote the copper-tin alloys, and is still used, though they are also called as tin-bronzes. This term bronze is now broadly used for any copper alloy with the exception ofNON-FERROUS METALS AND ALLOYS. 66s copper-zine alloys. Alloys such as copper-aluminium are called aluminium bronzes; copper-beryllium alloys are called beryllium bronzes, and so on. The‘tensile strength and elongation in-single phase compositions of the bronzes increase with the increase of the solute metal. ‘TIN-BRONZES Cu-Sn is a phase diagram consisting of several peritectic reactions, and two eutectoid reactions. A portion of it of industrial importance is illustrated in Fig. 13.5 (a). The solid solubility of tin in copper 1083 ‘a= Solid Solution of Sn in Ou 1900 [B= Solid solution (Cu,Sn. 3/2 ato. {= Electron Compound CussSna, 21/13 ratio { ‘¢= Electron compound CusSn (7/4 rath 800 1= Sold solution ® a E600 e 480 Fa ia 384 i 400 & 210 70 Fig. 135. (a) Cu-Sa phase diagram of industial importance, (b) Effect of Sn on mechanical properties of Cu. decreases from 11% at 350°C to around 1% at room temperature. At 520°C, y undergoes eutectoid reaction to form a mixture of a + 8. Then, 5 decomposes to produce a mixture of ct + € by eutectoid reaction at 350°C. The reactions occurring at lower temperatures are very slow in nature and, equilibrium is not easily attained even at 600°C. In commercial bronzes, the phase € (epsilon) is normally nonexistent, and cast alloys have a structure of a + (a. + 8) eutectoid, The S-phase, based on electron compound CusiSns, is pale-blue in colour, hard and brittle. This decreases the strength and clongation. However, alloys up to 8%tin usually show single phase, a. solid solution at room temperature, But, bronzes with higher than 8% tin are neither rolled nor forged as 8 makes them brittle, and are used only foFcastings. ‘The addition of tin increases the strength significantly as well as ductility of copper but a steep drop in ductility takes place around 8% Sn. The strength falls drastically at 25% Sn, when the structure contains too much of britle 6-phase. The presence of hard eutectoid in the cast structure ensures a high resistance to wear and abrasion. 10% Sn alloy is best antifiction material, and is widely used as a ball-bearing alloy. Cast tin-bronzes invariably show pronounced coring as there isa wide separation of the liquidus and solidus curves, and the diffusion takes place very slowly. Cast alloys containing more than 8% Sn show cored dendrites of 0: and (a + 8) eutectoid as illustrated in Fig. 13.6. Annealing removes the cored structure. There are few666 PHYSICAL METALLURGY a w Fig. 136. (a) Cored structure of cas bronze x 100, (6) Cold worked and annealed 250, bronzes which are pure copper-tin alloys as the addition of certain elements improves the characteristics of bronzes. The elements usually added are Zn, Fe, P, Ni, Pb etc. Zine improves the processing properties of bronze and lowers the cost. Phosphorus improves the foundry properties (increases soundness and cleanliness of castings) with improvement in hardness, strength and antifriction properties. Nickel improves mechanical properties and corrosion resistance with reduction in segregation. Lead, as rounded particles due to its Insolubility in copper, increases density of castings with improved machinability as it breaks the metal turnings into chips, but decreases mechanical properties. It improves antfriction properties. While melting bronzes, tin oxide forms, which is heavy and insoluble. Phosphorus, a more powerful deoxidiser than zinc, is added to produce sound and clean casting. It is added as phosphor-copper prior to addition of tin in copper. Industrial alloys have a maximum of 20% tin. The bronzes can be classified into ‘wo major groups: 1. Wrought bronzes: These contain tin up to 8%. These are single phase alpha solid solution-bronzes, having good ductility and malleability, and, thus can be easily cold worked by rolling to sheets, bars. or by drawing to wires (for springs), and mint coins. Coinage bronze: has a composition of 95 Cu, 3.5 Sn, 1.5 Zn and has been used for coins and medals. 2. Cast bronzes: These bronzes have Sn from 8 10 20% and can be produced only in the cast-form as these have two phase structures, 0 + (0 + 8), and thus, cannot be easily cold-worked. These bronzes ‘may have larger content of zine and phosphorus. These have high corrosion resistance, low shrinkage and high anti-friction proprieties, The good castability of these bronzes is mainly due to their exceptionally low shrinkage so that most intricate castings (including art castings) are made from them, These bronzes can be divided into three classes: 1. Cast bronzes having 8 to 12% tin: These are used for casting pumps, gears, machine parts, heavily loaded bearings, and marine parts to resist sea-water corrosion, GUN METAL UTS Kg/nu %E BHN 88Cu 10Sn 2Zn 32 20 90 Zine acts as a deoxidiser and increases the fluidity. Gun-metal was known from early times when it was used in cannons, and guns. It is no more used for ordnance as steel has replaced it, but is used when strong heavy castings are to be made. Often this alloy is called Government bronze. It has good strength, hardness, ¥y, plasticity, adaptability, excellent resistance to sea water corrosion. Cast structure is heavily coredNON-FERROUS METALS AND ALLOYS a 1 & + (a + 8) cutectoid. It is used for marine castings such as pumps, valve bodies, bearings, bushings (when lubrication is good at heavy loads), high pressure steam plants. It is quite a general purpose casting alloy. RED BRASS OR OUNCE METAL UTS Key? %E BHN 85 CuS Sn 5 Zn 5 Pb 19 25 1s 60-70 It is a cheaper substitute of gun-metal, and is easily castable to give sound castings. It has good machinability and mechanical properties with good resistance to atmospheric and water corrosion. It is a general casting alloy for steam pressures up to 0.7 N/mm” at temperatures below 205°C and for bearings hhaving good support, low pressure valves, pipe fittings, sinall gears, ornamental fixtures, plumbing fixtures. 86/7/3/3 (CulSn/ZniPb) too is for medium,steam pressures above 0.7 N/mm at temperatures below 260°C and for hydraulic pressure up to 14 Nimm? and for light loaded bearings. 2. Cast bronzes having 12 to 20% tin. These are mainly used for bearings. (discussed later) 3. Broizes having 20 to 25% tin. Bell metals (75-80 Cu, 25-20 Sn) are used for making bells. They are very hard and relatively brittle. These can only be’ cast. PHOSPHOR BRONZE {As said earlier, phosphorus being a powerful deoxidiser is almost always used while casting bronzes as it removes oxygen from melt as P20s in slag, which results in sound and clean castings. Almost all tin-bronzes contain less than 0.1% phosphorus as residual clement to have freedom from oxide. The strength and ductility of the bronze is improved by even this small presence of phosphorus. Phosphor-bronzes contain more than 0.3% phosphorus when it acis as an alloying element. Such phosphor-bronzes can be divided into two classes: 1. Wrought Phosphor bronze UTS Ke/nn? %E BHN (93.8 Cu, 6 Sn, 0.2P) Cast 2B 18 90. Annealed 38 65 120 Cold drawn 85 5 ms Phosphorus improves soundness and cleanliness of castings, which causes improvement in strength and ductility. The retention of 0.2% phosphorus further inereases the strength and hardness of the alloy. The alloy has good resistance to sea-water corrosion Ieis a single phase acbronze, which has good ductility. Thus, this alloy can be rolled to sheets, strips: can be drawn into wires, rods “Tis alloy is used for making springs, wire brushes, condenser tubes, gears, marine fittings. diaphrams, bellows, lock-washers, coter pins 2. Cast Phosphor-bronze UTS Ke/nm? %E BHN (1280, 0.31.08, bal. Cu) n 5 100 The higher phophorus content forms the hard phase FesP, which inereases the hardness and strength of the alloy, but decreases ductility. The presence of a hard phase in a soft matrix makes this alloy to be a good tearing material because of its low coefficient of friction, The alloy has good toughness with good corrosion resistance (0 sea-water It is used for electrical contacts, gear whocls,slde-valves, bushings boiler fittings, cluteh-disks, Turbine blades, wire brushes, etc, Springs are made of bronze (93.7 Cu, 6 Sm 3 P) which in drawn and annealed state ha strength of 40 Kg/mm with % elongation of 65%. Cast gear blade (13 Sn, 0.3 P) has 13% Sn and 03% P. BEARING BRONZES Choosing an alloy out of a wide variety of bearing materials needs consideration of factors-tike: Shaft ‘material and its speed, load and impact, conditions of lubrication, alignment and temperature of working. Bronzes are preferred over white metals for high loads. Here also, a double-phase structure is preferred, i.e. either soft particles embedded in hard matrix. or hard particles embedded in soft matrix.668 PHYSICAL METALLURGY 1. Plastic bronzes have soft insoluble globules of lead in hard bronze matrix. (@)75.Ca5 Sn 20PH —«SOBHN. 2 — 15 9% E Used with soft stcl shafts where alignment is needed (b) 77 Cu 8 Sn 15 PO © BHN — 4— 10% E_and lubrication is imperfect. These carry 20% higher (© 80.Cu10Sn 10 Pb «GS BHN 4 10% EB _loads with higher speeds than white metas. Gun metal with 2% Pb has improved machinability, plasticity and adaptability to bearing surfaces. High leaded tin bronze (88/10/10 CwSwPb) is extensively used for high speed, heavy pressure bearing and bushings. 85/5/5/5 (Cu/Sn/Zn/Pb) is also used extensively. 2. Phosphor bronzes have hard particles of delta and Cus P embedded in a softer matrix (@ 85 Cu75 S035 P05P 90 130BHN 2— 15% E 89 Cu 10 Sn P 90 —130BHN 2—IS%E (©) 85 Cu 15 Sn to 120 BHN 2% ‘Slide valves and bearings for turntables '5-15% Pb is present where lubrication, or alignment is liable to be somewhat unsatisfactory but alloys have limited ductility. 3, Wrought chromium bronzes 25 Sn, 1.7 Fe 1.2 Cr, bal. Co 90 —130BHN 25 — 40% E ‘The alloy has hard particles of complex tin-iron-chromium compound in a tough, low tin copper matrix. It has high wear resistance even in severe conditions of applications such as high temperature needing high thermal conductivity, toughness and high fatigue resistance. It finds applications in percussion rock dill twist ruts, valve guides for LC. engines, bushes for grinding spindle and for worm wheels. 13.3.3. ALUMINIUM BRONZES Copper-aluminium alloys are called aluminium bronzes. Most alloys contain aluminium between 4 to 1083 1000 800 = Fas 80%407 Elongation & 2 60%30} a oar < F zomiok 00: er ae % Aw 500 » oso ga (a) Al wo Fig. 137. (a) Cu-Al phase diagram, (b) Mechanical properties.\NON-FERROUS METALS AND ALLOYS 69 11% as alloys become extremely brittle beyond this. Aluminum bronzes are inferior to tin-bronzes as regards casting shrinkage, but have better mechanical properties and corrosion resistance, and are cheaper. Better foundry practice can overcome casting problems. These bronzes have good ductility in single phase alloys, good fatigue and wear resistance, and can be given heat treatment just like steels. Fig. 13.7. gives Cu-Al phase diagram of industrial important alloys alongwith the effect on mechanical properties. Ideally, alpha the solid solution of aluminium in copper can dissolve up to 9.4% All. It can be hot, fr cold worked but is difficult to machine. Beta-phase is a solid solution, based on CusAl (ratio 3/2), and is harder and more brittle, and can only be hot worked. On slow cooling of beta phase, eutectoid mixture of o + yp is obtained, which resembles pearlite in steel. The phase yp is very hard but brittle, and its presence in small quantities increases the strength of the alloy, but presence in larger amounts embrittles the material ‘Thus, alloys donot have more than 11% Al. ‘The decomposition products of beta-phase become more finely dispersed, and more hard as the rate of cooling increases. Heat treatment of aluminium bronzes is similar to that of steels to result in °C’ shaped SSS Fig 138. Aluminium bronze with 10.5% Al, (a) Slowly cooled hypoeutectoid structure: as bi (a+ 72) dark, x 500 (6) Martensite. x 100, curve, and martensite is obtained if rate of cooling is faster than the critical cooling rate, Fig. 13.8 illustrates (@) hypoeutectoid structure on slow cooling (b) martensite on water quenching. Alloy (1OAI4Fe4Ni) is hardened from 980°C and tempered at 400°C resulting in increase of hardness from 170-200 BHN to 400. ‘Aluminium bronzes can be divided into two classes depending on the number of phases present 1. Wrought alloys: These are single phase alloys containing up to 7.5% aluminium. Alloys can be easily ‘cold or hot-worked. Alloys are hard, have high tensile strength, ductility, good wear, impact, fatigue and Corrosion resistance (than -brasses). The colour of the alloy is similar to 18-carat gold, and thus finds applications in cigarett-cases and decorative purposes, coins, jewelry, architectural and ornamental pieces, pickling erates, ships fitings, condenser tubes, nut, bolts, heat exchanger tubes. The alloy has: 93.Cu7 Al urs %E BHN Kefmn’ Cast 21 Cc — Cold rolled 40 18 195 Annealed, 650°C 28 1 16 2. Double-phase (ct + 7): These are mostly used in cast state, but can be hot-worked. Alloys have high hardness, strength and good resistance to corrosion. The alloys can be hardened and tempered as steels. 90 Cu 10 Al urs %E BHN Kenn? Cast 31 20 2 Q 900°C 4 2 4 9 900 T 650°C 38 B 16 Hot work, Q 900 T 650°C 4a 8670 PHYSICAL METALLURGY Complex aluminium bronzes: Aluminium bronzes invariably have other clements also to improve the properties such as iron (0.5-5.0%), nickel (up to 5%), manganese (up to 4%), some lead and silicon. Iron refine the grains to increase the strength and hardness. Nickel also refines the grains to increase the strength. Manganese takes care of gases, refines the grains to increase the strength. Silicon and lead help to improve the machinability. Normally, these alloys are hot worked, or cast. Alloys have good resistance to cavitation erosion, impingement attack, oxidation, scaling, wear and abrasion with high strength and hardpess ‘Apia sea Ni Ma UTS, Kymm&E 10 5 50-25 Hotwoked 48-50. 15-25 10 45 45 025 Cast 40-45 2-20 [Alloys are used for valve-stems, bolts, nuts, propellers-hubs & blades for marine service, tanks, pressure vessels, condenser tubes, plates, pump parts, valve guides, gears, feed nuts, gears for heavy machinery, gear selector forks, non-sparking tools, cold working dies, electrical contacts, bushings and bearings, large ship propellers; electrical switch mechanism. 133.4, SILICON BRONZES Copper-silicon alloys are called silicon bronzes, and normally have up to 4.0 percent silicon. The solubility of silicon decreases from about 5.3% at 845°C to less than 4% at room temperature. Silicon inereases both strength and ductility and alloys are than tin-bronzes. Normally, small additions of manganese, iron and zinc are made, These have excellent corrosion resistance combined with high strength and toughness. These bronzes can be easily hot or cold-worked, machined and welded. These are used in chemical plants in the form strips, plates, wires, rods, tubes, bolts, rivets, springs, propeller shafts and bells. Springs and other elastic component of instruments and radio apparatus operating up to 250°C in mediums like fresh and sea-water are made from it. Two alloys are: G a Ma [Fe te [OS Ken? [8 Frer & 36 3 7 = = B 6 PMG. can _| 915 4 os | 20 | 20 21 1s 1335. BERYLLIUM BRONZES 1100 Copper-beryllium alloys, the beryl- eal lium bronzes are heat teaable type of 1000 alloys, where precipitation hardening is the mechanism to avenge te alloys, 900 ‘he solid solubility of berylium dee- gy ren ftom 2.1% a 868°C to less than 800] 025% at room tomperatue. This be- 5 haviour as shown in Fig. 139 indicates & 700 esis of age hardening in alloys, & Romally thee alloys contain 0.2.0.5 8 600 Cobalt (or nickel) to increase the stability of supercooled solid solu- tion. 500) ‘he alloys can be easily cast and col | worked. These alloys have: ay 1. Highest stength and hardness 300, 2. 3 (of copper alloys. Good corrosion resistance. Good fatigue resistance, 1. Good wear resistance. OR eas 2 Se 4 ae aa eo] Beryllium wt. % -—e 70 Fig, 139. Cu-Be phase dagramNON-FERROUS METALS AND ALLOYS . Good creep resistance. Good electrical conductivity. . Non magnetic and non-sparking characteristics. Beryllium is an expensive metal Good machinability and weldability 10. Resists softening up to about 250°C. ‘One important alloy: on 973 CuaBe 0500 UTS, K/min @E T. Solutionised at 780°C-800°C for 2 hours, and water 34 aS quenched 2 Solutionised 800°C, WO, aged 300°-350°C 125 5 3.__Solutionised, 30% cold worked, aged 140 2 Beryllium bronzes are used for springs, Bourdon tubes, corrugated-diaphrams, flexible-bellows, gears, bearings, electrical contacts; mould for forming plastics, hammers and other tools when non-magnetic and nnon-sparking properties are needed, surgical instru- ments, bolts, screws, firing pins, dies. 133.6. COPPER-NICKEL ALLOYS Copper-nickel alloys having nickel upto 30% are called cupronickels. Copper-nickel alloys, form com- plete series of solid solutions, i., all the alloys have only one phase, and thus, are ductile and malleable, and ccan be worked in cold and hot conditions. Alloys have low temperature-coefficient of electrical resistance having = 45% Ni, and some alloys have high ity. The corrosion resistance increases with the increase of nickel content. The tensile strength, proof stress and fatigue strength increase rapidly with the increase of nickel content to reach to a maximum at around 70% nickel. As the amount of nickel increases, the colour becomes increasingly whiter until at 20% nickel, it is practically white, The alloy having 45% nickel has high resistivity with very low temperature coefficient of (in range of 20° to 350°C) resistivity ‘This alloy is known as constantan (45NiSSCu) and is used extensively for thermocouples. Copper-nickel alloys can be hardened only by cold working. These can be annealed at 550° to Elongation Fig. 13.10, Properties of Cu-Ni alloys {690°C and are not heated above 800°C. Cupronickels are very sensitive to oxygen, lead, sulphur and carbon, ‘ ‘Table 13.7. Alloys of Copper and Nickel Wi Urs, E ‘Applications Nha? 2 301 2 » 355 41 Highly malleable: bullet envelops, condenser tubes. 2s 385 39 Coinage (25 cent coin) 5 430 3 High electrical resistors (Constantan) 68 (Fe 2) 570 40 Monel: Turbine bladeson PHYSICAL METALLURGY which embrittle them, Manganese acts as a deoxidiser. Iron (1-2%) increases the corrosion resistance to moving-sea-water (0 find applications in naval-vessels and coastal power plants. Cupronickels (80/20, 70/30) tan be hot or cold worked. These have excellent malleability at room temperature. Table 13.7 gives some ‘compositions with their properties. 133.7. NICKEL SILVERS Nickel silvers are temary alloys of copper, nickel and zine having copper 50-70%, nickel 5 to 30% and zinc 5 to 40%, Depending on the number of phases present, nickel silvers can be divided into two classes { Singlesphase alpha alloys: ‘These alloys have 60-63% copper, 7-30% nickel and rest zinc. The audition of nickel has remarkable decolourising effect on the brass so that at about 20% nickel, alloy has pleasing silvercblue white colour with good corrosion resistance to food chemicals, water and mospheres, and are known as German silvers or nickel silvers, although there is no silver in them. ‘Although these alloys show only fair hot-working properties, but are ductile and can be easily cold-worked at room temperature (0 attain a strength of 617-927 ‘Nimm?, Annealing is done at €50-800°C. These alloys serve as excellent base metals for plating with chromium, nickel, or silver. ‘The brilliant polish of german-silvers and good resistance to corrosion find their use for gift wares, table wares (epoons and forks) with silver plating, automobile radiator shell, fitings for ships, lavatories and shops, extensively used in telephone and wireless industries for contactors and springs; in the form of tapes and wites for electical resistance; spectacle parts, zip fasteners, latch keys, Sootume jewelry, name plates, radio dials, rivets and screws. Lead is added sometimes to improve Snachinabilty. Many plumbing fixtures are also made out of them. Typical alloy with properties in the annealed condition are: German Silver IBNi 62Cu 20zZn urs Em BHN Nom 370 50 15 Gi) (c+ B) alloy: It has about 45% Cu, 45% Zn and 10% Ni, This is easily hot-worked into intricate Shapes. It is used for hardware, omamental purposes and other architectural, decorative and functional items due to silvery-colour. This cannot be cold-worked much. Addition of 2% lead improves machinability but interferes with hot-working operations except extrusion. Extruded sections are produced more. Many times, these alloys are called nickel brass or ‘silver bronzes. 13.4. NICKEL AND NICKEL ALLOYS [Nickel is one of the most important metals in modern engineering design and construction. Nickel is @ white, malleable, ductile (FCC structure), non-corrodible metal (in caustic alkalis, ammonia, salt solutions, and organic acids), having high strength, relatively high heat conductivity and good heat- resisting properties. On an average, 60% of the nickel produced is used in producing stainless and nickel-alloy steels. The rest is almost ‘used in high nickel-alloys and for electroplating, Small additions of silicon (= 1.54) and manganese are made to produce sound and ductile castings of nickel Silicon improves its fluidity and castability. [Nickel is available as five specific grades of commercial nickel such as, “A Nickel, ‘D Nickel’, “E Nickel, “Duranickel’ and ‘permanickel’ of which the last two are age-hardenable high nickel alloys as given in Table 13.8, ‘i ‘A nickel: It is a commercially pure basic malleable material having 99.4% Ni (+ Co). Its cast form has 1.5% Si to improve its fluidity and castability. It can be shaped by all methods of fabrication, can be joined by soldering, brazing and welding. It has strength of mild stecls, good resistance to corrosion to hydrogen chloride, chlorine, caustic soda, resistance to oxidation and scaling, retains strength at elevated temperatures, fand also good ductility, toughness, strength at sub-zero temperatures, and freedom from season-cracking etc Tt is used where strength combined with resistance to corrosion and oxidation is required such as in chemical, soap industries, where rolled forms are used for making evaporators, jacketed Keitles, tanks, heating coils, support wire and other parts of incandescent lamps and hot cathodes: in radio tubes.