An alloy is a metal product containing two or more elements as a solid solution, as an inter-metallic compound, or as a mixture of metallic phases. Except for native copper and gold, the first metals of technological importance were alloys. Bronze, an alloy of copper and tin, is appreciably harder than copper. This quality made bronze so important an alloy that it left a permanent imprint on the civilization of several millennia ago now known as the Bronze Age.
Alloys are used because they have specific properties or production characteristics that are more attractive than those of the pure, elemental metals. For example, some alloys possess high strength, others have low melting points, others are refractory with high melting temperatures, some are especially resistant to corrosion, and others have desirable magnetic, thermal, or electrical properties. These characteristics arise from both the internal and the electronic structure of the alloy. In recent years, the term plastic alloy also has been applied to plastics.
Metal alloys are more specifically described with reference to the major element by weight, which is also called the base metal or parent metal. Thus, the terms aluminum alloy, copper alloy, etc. Elements present in lesser quantities are called alloying elements. When one or more alloying elements are present in substantial quantity or, regardless of their amount, have a pronounced effect on the alloy, they, too, may be reflected in generic designations.
Metal alloys are also often designated by trade names or by trade association or society designations. Among the more common of the latter are the three-digit designations for the major families of stainless steels and the four-digit ones for aluminum alloys.
Structurally there are two kinds of metal alloys — single phase and multiphase. Single-phase alloys are composed of crystals with the same type of structure. They are formed by "dissolving" together different elements to produce a solid solution. The crystal structure of a solid solution is normally that of the base metal.
In contrast to single-phase alloys, multiphase alloys are mixtures rather than solid solutions. They are composed of aggregates of two or more different phases. The individual phases making up the alloy are different from one another in their composition or structure. Solder, in which the metals lead and tin are present as a mechanical mixture of two separate phases, is an example of the simplest kind of multiphase alloy. In contrast, steel is a complex alloy composed of different phases, some of which are solid solutions. Multiphase alloys far outnumber single-phase alloys in the industrial material field, chiefly because they provide greater property flexibility. Thus, properties of multiphase alloys are dependent upon many factors, including the composition of the individual phases, the relative amounts of the different phases, and the positions of the various phases relative to one another.
When two different thermoplastic resins are blended, a plastic alloy is obtained. Alloying permits resin polymers to be blended that cannot be polymerized. Not all plastics are amenable to alloying. Only resins that are compatible with each other — those that have similar melt traits — can be successfully blended.
Types of Alloys Bearing Alloys
These alloys are used for metals that encounter sliding contact under pressure with another surface; the steel of a rotating shaft is a common example. Most bearing alloys contain particles of a hard intermetallic cornpound that resists wear. These particles, however, are embedded in a matrix of softer material that adjusts to the hard particles so that the shaft is uniformly loaded over the total surface. The most familiar bearing alloy is babbitt metal, which contains 83 to 91% tin (Sn); the remainder is made up of equal parts of antimony (Sb) and copper (Cu), which form hard particles of the compounds SbSn and CuSn in a soft tin matrix. Other bearing alloys are based on cadmium (Cd), copper, or silver (Ag). For example, an alloy of 70% copper and 30% lead (Pb) is used extensively for heavily loaded bearings. Bearings made by powder metallurgy techniques are widely used. These techniques are valuable because they permit the combination of materials that are incompatible as liquids, for example, bronze and graphite. Powder techniques also permit controlled porosity within the bearings so that they can be saturated with oil before being used, the so-called oilless bearings.
Corrosion-Resisting Alloys
Certain alloys resist corrosion because they are noble metals. Among these alloys are the precious metal alloys, which will be discussed separately. Other alloys resist corrosion because a protective film develops on the metal surface. This passive film is an oxide that separates the metal from the corrosive environment. Stainless steels and aluminum alloys exemplify metals with this type of protection. Stainless steels are iron alloys containing more than 12% chromium (Cr). Steels with 18% Cr and 8% nickel (Ni) are the best known and possess a high degree of resistance to many corrosive environments. Aluminum (Al) alloys gain their corrosion-deterring characteristics by the formation of a very thin surface layer of aluminum oxide (Al2O3), which is inert to many environmental liquids. This layer is intentionally thickened in commercial anodizing processes to give a more permanent Al2O3 coating. Monel, an alloy of approximately 70% nickel and 30% copper, is a well-known corrosion-resisting alloy that also has high strength. Another nickel-base alloy is Inconel, which contains 14% chromium and 6% iron (Fe). The bronzes, alloys of copper and tin, also may be considered to be corrosion resisting.
Dental Alloys
Amalgams are predominantly alloys of silver and mercury, but they may contain minor amounts of tin, copper, and zinc for hardening purposes, for example, 33% silver, 52% mercury, 12% tin, 2% copper, and less than 1% zinc. Liquid mercury is added to a powder of a precursor alloy of the other metals. After compaction, the mercury diffuses into the silver-base metal to give a completely solid alloy. Gold-base dental alloys are preferred over pure gold because gold is relatively soft. The most common dental gold alloy contains gold (80 to 90%), silver (3 to 12%), and copper (2 to 4%). For higher strengths and hardnesses, palladium and platinum (up to 3%) are added, and the copper and silver are increased so that the gold content drops to 60 to 70%. Vitallium, an alloy of cobalt (65%), chromium (5%), molybdenum (3%), and nickel (3%), and other corrosion-resistant alloys are used for bridgework and special applications.
Die-Casting Alloys
These alloys have melting temperatures low enough so that in the liquid form they can be injected under pressure into steel dies. Such castings are used for automotive parts and for office and household appliances that have moderately complex shapes. This processing procedure eliminates the need for expensive machining and forming operations. Most die castings are made from zinc-base or aluminum-base alloys. Magnesium-base alloys also find some application when weight reduction is paramount. Low-melting alloys of lead and tin are not common because they lack the necessary strength for the above applications. A common zinc-base alloy contains approximately 4% aluminum and up to 1% copper. These additions provide a second phase in the metal to give added strength. The alloy must be free of even minor amounts (less than 100 ppm) of impurities such as lead, cadmium, or tin, because impurities increase the rate of corrosion. Common aluminum-base alloys contain 5 to 12% silicon, which introduces hard-silicon particles into the tough aluminum matrix. Unlike zinc-base alloys, aluminum-base alloys cannot be electroplated; however, they may be burnished or coated with enamel or lacquer.
Advances in high-temperature die-mold materials have focused attention on the die-casting of copper-base and iron-base alloys. However, the high casting temperatures introduce costly production requirements, which must be justified on the basis of reduced machining costs.
Eutectic Alloys
In certain alloy systems a liquid of a fixed composition freezes to form a mixture of two basically different solids or phases. An alloy that undergoes this type of solidification process is called a eutectic alloy. A typical eutectic alloy is formed by combining 28.1% of copper with 71.9% of silver. A homogeneous liquid of this composition on slow cooling freezes to form a mixture of particles of nearly pure copper embedded in a matrix (background) of nearly pure silver.
The advantageous mechanical properties inherent in composite materials such as plywood composed of sheets or lamellae of wood bonded together and fiberglass in which glass fibers are used to reinforce a plastic matrix have been known for many years. Attention is being given to eutectic alloys because they are basically natural composite materials. This is particularly true when they are directionally solidified to yield structures with parallel plates of the two phases (lamellar structure) or long fibers of one phase embedded in the other phase (fibrous structure). Directionally solidified eutectic alloys are being given serious consideration for use in fabricating jet engine turbine blades. For this purpose eutectic alloys that freeze to form tantalum carbide (TaC) fibers in a matrix of a cobalt-rich alloy have been heavily studied.
Fusible Alloys
These alloys generally have melting temperatures below that of tin (450°F, or 232°C), and in some cases as low as 120°F (50°C). Using eutectic compositions of metals such as lead, cadmium, bismuth, tin, antimony, and indium achieves these low melting temperatures. These alloys are used for many purposes, for example, in fusible elements in automatic sprinklers, forming and stretching dies, filler for thin-walled tubing that is being bent, and anchoring dies, punches, and parts being machined. Alloys rich in bismuth were formerly used for type metal because these low-melting metals exhibited a slight expansion on solidification, thus replicating the font perfectly for printing and publication.
High-Temperature Alloys
Energy conversion is more efficient at high temperatures than at low; thus the need in power-generating plants, jet engines, and gas turbines for metals that have high strengths at high temperatures is obvious. In addition to having strength, these alloys must resist oxidation by fuel-air mixtures and by steam vapor. At temperatures up to about 1380°F (750°C), the aus-tenitic stainless steels (18% Cr-8% Ni) serve well. An additional 180°F (100°C) may be realized if the steels also contain 3% molybdenum. Both nickel-base and copper-base alloys, commonly categorized as superalloys, may serve useful functions up to 2000°F (1100°C). Nichrome, a nickel-base alloy containing 12 to 15% chromium and 25% iron, is a fairly simple superalloy. More sophisticated alloys invariably contain five, six, or more components; for example, an alloy called Rene-41 contains approximately 19% Cr, 1.5% Al, 3% Ti, 11% Co, 10% Mo, 3% Fe, 0.1% C, 0.005% B, and the balance Ni. Other alloys are equally complex. The major contributor to strength in these alloys is the solution-precipitate phase of Ni3 (TiAl). It provides strength because it is coherent with the nickel-rich phase. Cobalt-base superalloy may be even more complex and generally contain carbon, which combines with the tungsten (W) and chromium to produce carbides that serve as the strengthening agent. In general, the cobalt-base superalloys are more resistant to oxidation than the nickel-base alloys are, but they are not as strong. Molybdenum-base alloys have exceptionally high strength at high temperatures, but their brittleness at lower temperatures and their poor oxidation resistance at high temperatures have limited their use. However, coatings permit the use of such alloys in an oxidizing atmosphere, and they are finding increased application. A group of materials called cermets, which are mixtures of metals and compounds such as oxides and carbides, have high strength at high temperatures, and although their ductility is low, they have been found to be usable. One of the better-known cermets consists of a mixture of TiC and nickel, the nickel acting as a binder or cement for the carbide.
Joining Alloys
Metals are bonded by three principal procedures: welding, brazing, and soldering. Welded joints melt the contact region of the adjacent metal; thus, the filler material is chosen to approximate the composition of the parts being joined. Brazing and soldering alloys are chosen to provide filler metal with an appreciably lower melting point than that of the joined parts. Typically, brazing alloys melt above 750°F (400°C) whereas solders melt at lower temperatures. A 57% Cu-42% Zn-1% Sn brass is a general-purpose alloy for brazing steel and many non-ferrous metals. A Si-Al eutectic alloy is used for brazing aluminum, and an aluminum-containing magnesium eutectic alloy brazes magnesium parts. The most common solders are based on Pb-Sn alloys. The prevalent 60% Sn-40% Pb solder is eutectic in composition and is used extensively for electrical circuit production, in which temperature limitations are critical. A 35% Sn-65% Pb alloy has a range of solidification and is thus preferred as a wiping solder by plumbers.
Light-Metal Alloys
Aluminum and magnesium, with densities of 2.7 and 1.75 g/cm3), respectively, are the bases for most of the light-metal alloys. Titanium (4.5 g/cm3) may also be regarded as a light-metal alloy if comparisons are made with metals such as steel and copper. Aluminum and magnesium must be hardened to receive extensive application. Age-hardening processes are used for this purpose. Typical alloys are 90% Al-10% Mg, 95% Al-5% Cu, and 90% Mg-10% Al. Ternary (three element) and more complex alloys are very important light-metal alloys because of their better properties. The Al-Zn-Mg system of alloys, used extensively in aircraft applications, is a prime example of one such alloy system.
Low-Expansion Alloys
This group of alloys includes Invar (64% Fe-36% Ni), the dimensions of which do not vary over the atmospheric temperature range. It has special applications in watches and other temperature-sensitive devices. Glass-to-metal seals for electronic and related devices require a matching of the thermal-expansion characteristics of the two materials. Kovar (54% Fe-29% Ni-17% Co) is widely used because its expansion is low enough to match that of glass.
Magnetic Alloys
Soft and hard magnetic materials involve two distinct categories of alloys. The former consists of materials used for magnetic cores of transformers and motors, and must be magnetized and demagnetized easily. For AC applications, silicon-ferrite is commonly used. This is an alloy of iron containing as much as 5% silicon. The silicon has little influence on the magnetic properties of the iron, but it increases the electric resistance appreciably and thereby decreases the core loss by induced currents. A higher magnetic permeability, and therefore greater transformer efficiency, is achieved if these silicon steels are grain-oriented so that the crystal axes are closely aligned with the magnetic field. Permalloy (78.5% Ni-21.5% Fe) and some comparable cobalt-base alloys have very high permeabilities at low field strengths, and thus are used in the communications industry. Ceramic ferrites, although not strictly alloys, are widely used in high-frequency applications because of their low electrical conductivity and negligible induced energy losses in the magnetic field. Permanent or hard magnets may be made from steels that are mechanically hardened, either by deformation or by quenching. Some precipitation-hardening, iron-base alloys are widely used for magnets. Typical of these are the Alnicos, for example, Alnico-4 (55% Fe-28% Ni-12% Al-5% Co). Since these alloys cannot be forged, they must be produced in the form of castings. Hard magnets are being produced from alloys of cobalt and the rare earth type of metals. The compound RCo5, where R is samarium (Sm), lanthanum (La), cerium (Ce), and so on, has extremely high coercivity.
Precious-Metal Alloys
In addition to their use in coins and jewelry, precious metals such as silver, gold, and the heavier platinum (Pt) metals are used extensively in electrical devices in which contact resistances must remain low, in catalytic applications to aid chemical reactions, and in temperature-measuring devices such as resistance thermometers and thermocouples. The unit of alloy impurity is commonly expressed in karats, when each karat is 1/24 part. The most common precious-metal alloy is sterling silver (92.5% Ag, with the remainder being unspecified, but usually copper). The copper is very beneficial in that it makes the alloy harder and stronger than pure silver. Yellow gold is an Au-Ag-Cu alloy with approximately a 2:1:1 ratio. White gold is an alloy that ranges from 10 to 18 karats, the remainder being additions of nickel, silver, or zinc, which change the color from yellow to white. The alloy 87% platinum-13% rhodium (Rh), when joined with pure platinum, provides a widely used thermocouple for temperature measurements in the 1830 to 3000°F (1000 to 1650°C) temperature range.
Shape Memory Alloys
These alloys have a very interesting and desirable property. In a typical case, a metallic object of a given shape is cooled from a given temperature T1, to a lower temperature T2, where it is deformed to change its shape. Upon reheating from T2 to T1, the shape change accomplished at T2 is recovered so that the object returns to its original configuration. This thermoelastic property of the shape memory alloys is associated with the fact that they undergo a marten-sitic phase transformation (that is, a reversible change in crystal structure that does not involve diffusion) when they are cooled or heated between T1 and T2.
For a number of years the shape memory materials were essentially scientific curiosities. Among the first alloys shown to possess these properties was one of gold alloyed with 47.5% cadmium. Considerable attention has been given to an alloy of nickel and titanium known as Nitinol. The interest in shape memory alloys has increased because it has been realized that these alloys are capable of being employed in a number of useful applications. One example is for thermostats; another is for couplings on hydraulic lines or electrical circuits. The ther-moelastic properties can also be used, at least in principle, to construct heat engines that will operate over a small temperature differential and will thus be of interest in the area of energy conversion.
Thermocouple Alloys
These include Chromel, containing 90% Ni and 10% Cr, and Alumel, containing 94% Ni, 2% Al, 3% Cr, and 1% Si. These two alloys together form the widely used Chromel-Alumel thermocouple, which can measure temperatures up to 2200°F (1204°C). Another common thermocouple alloy is Con-stantan, consisting of 45% Ni and 55% Cu. It is used to form iron-Constantan and copper-Constantan couples, used at lower temperatures. For precise temperature measurements and for measuring temperatures up to 3000°F (1650°C), thermocouples are used in which one metal is platinum and the other metal is platinum plus either 10 or 13% rhodium.
Prosthetic Alloys
Prosthetic alloys are alloys used in internal prostheses, that is, surgical implants such as artificial hips and knees. External prostheses are devices that are worn by patients outside the body; alloy selection criteria are different from those for internal prostheses. In the United States, surgeons use about 250,000 artificial hips and knees and about 30,000 dental implants per year.
Alloy selection criteria for surgical implants can be stringent primarily because of biomechanical and chemical aspects of the service environment. Mechanically, the properties and shape of an implant must meet anticipated functional demands; for example, hip joint replacements are routinely subjected to cyclic forces that can be several times body weight. Therefore, intrinsic mechanical properties of an alloy, for example, elastic modulus, yield strength, fatigue strength, ultimate tensile strength, and wear resistance, must all be considered. Similarly, because the pH and ionic conditions within a living organism define a relatively hostile corrosion environment for metals, corrosion properties are an important consideration. Corrosion must be avoided not only because of alloy deterioration but also because of the possible physiological effects of harmful or even cytotoxic corrosion products that may be released into the body. (Study of the biological effects of biomaterials is a broad subject in itself, often referred to as biocompatibility.) The corrosion resistance of all modern alloys stems primarily from strongly adherent and passivating surface oxides, such as TiO2 on titanium-based alloys and Cr2O3 on cobalt-base alloys.
The most widely used prosthetic alloys therefore include high-strength, corrosion-resistant ferrous, cobalt-base, or titanium-base alloys. Examples include cold-worked stainless steel; cast Vitallium, a wrought alloy of cobalt, nickel, chromium, molybdenum, and titanium; titanium alloyed with aluminum and vanadium; and commercial-purity titanium. Specifications for nominal alloy compositions are designated by the American Society for Testing and Materials (ASTM).
Prosthetic alloys have a range of properties. Some are easier than others to fabricate into the complicated shapes dictated by anatomical constraints. Fabrication techniques include investment casting (solidifying molten metal in a mold), forging (forming metal by deformation), machining (forming by machine-shop processes, including computer-aided design and manufacturing), and hot isostatic pressing (compacting fine powders of alloy into desired shapes under heat and pressure). Cobalt-base alloys are difficult to machine and are therefore usually made by casting or hot isostatic pressing. Some newer implant designs are porous coated; that is, they are made from the standard ASTM alloys but are coated with alloy beads or mesh applied to the surface by sintering or other methods. The rationale for such coatings is implant fixation by bone in growth.
Some alloys are modified by nitriding or ion-implantation of surface layers of enhanced surface properties. A key point is that prosthetic alloys of identical composition can differ substantially in terms of structure and properties, depending on fabrication history. For example, the fatigue strength approximately triples for hot isostatically pressing vs. as-cast Co-Cr-Mo alloy, primarily because of a much smaller grain size in the microstructure of the former.
No single alloy is vastly superior to all others; existing prosthetic alloys have all been used in successful and, indeed, unsuccessful implant designs. Alloy selection is only one determinant of performance of the implanted device.
Superconducting Alloys
Superconductors are materials that have zero resistance to the flow of electric current at low temperatures. There are more than 6000 elements, alloys, and compounds that are known superconductors. This remarkable property of zero resistance offers unprecedented technological advances such as the generation of intense magnetic fields. Realization of these new technologies requires development of specifically designed superconducting alloys and composite conductors. An alloy of niobium and titanium (NbTi) has a great number of applications in superconductivity; it becomes superconducting at 9.5 K (critical superconducting temperature, Tc). This alloy is preferred because of its ductility and its ability to carry large amounts of current at high magnetic fields, represented by Jc(H) (where Jc is the critical current and H is a given magnetic field), and still retain its superconducting properties. Brittle compounds with intrinsically superior superconducting properties are also being developed for magnet applications. The most promising of these are compounds of niobium and strontium (Nb3Sn), vanadium and gallium (V3Ga), niobium and germanium (Nb3Ge), and niobium and aluminum (Nb3Al), which have higher Tc (15 to 23 K) and higher Jc (H) than NbTi.
Superconducting materials possess other unique properties such as magnetic flux quantization and magnetic-field-modulated super-current flow between two slightly separated superconductors.
These properties form the basis for electronic applications of superconductivity such as high-speed computers or ultrasensitive magnetometers. Development of these applications began using lead or niobium (Tc of 7 and 9 K) in bulk form, but the emphasis then was transferred to materials deposited in thin-film form. PbIn and PbAu alloys are more desirable than pure lead films, as they are more stable. Improved vacuum deposition systems eventually led to the use of pure niobium films as they, in turn, were more stable than lead alloy films. Advances in thin-film synthesis techniques led to the use of the refractory compound niobium nitride (NbN) in electronic applications. This compound is very stable and possesses a higher Tc (15 K) than either lead or niobium.
Novel high-temperature superconducting materials have revolutionary impact on superconductivity and its applications. These materials are ceramic, copper-oxide-based materials that contain at least four and as many as six elements. Typical examples are yttrium-barium-copper-oxygen (Tc 93 K), bismuth-strontium-calcium-copper-oxygen (Tc 110K), and thallium-barium-calcium-copper (Tc 125 K). These materials become superconducting at such high temperatures that refrigeration is simpler, more dependable, and less expensive. Much research and development has been done to improve the technologically important properties such as Jc(H), chemical and mechanical stability, and device-compatible processing procedures. It is anticipated that the new compounds will have a significant impact in the growing field of superconductivity.
