12.9: Contemporary Materials

Learning Objective

1. To become familiar with the properties of some contemporary materials.

In addition to polymers, other materials, such as ceramics, high-strength alloys, and composites, play a major role in almost every aspect of our lives. Until relatively recently, steel was used for any application that required an especially strong and durable material, such as bridges, automobiles, airplanes, golf clubs, and tennis rackets. In the last 15 to 20 years, however, graphite or boron fiber golf clubs and tennis rackets have made wood and steel obsolete for these items. Likewise, a modern jet engine now is largely composed of Ti and Ni by weight rather than steel (Table 12.8 "The Approximate Elemental Composition of a Modern Jet Engine"). The percentage of iron in wings and fuselages is similarly low, which indicates the extent to which other materials have supplanted steel. The Chevrolet Corvette introduced in 1953 was considered unusual because its body was constructed of fiberglass, a composite material, rather than steel; by 1992, Jaguar fabricated an all-aluminum limited-edition vehicle. In fact, the current models of many automobiles have engines that are made mostly of aluminum rather than steel. In this section, we describe some of the chemistry behind three classes of contemporary materials: ceramics, superalloys, and composites.

Table 12.8 The Approximate Elemental Composition of a Modern Jet Engine

Element	Percentage by Mass
titanium	38
nickel	37
chromium	12
cobalt	6
aluminum	3
niobium	1
tantalum	0.025

Ceramics

A ceramic is any nonmetallic, inorganic solid that is strong enough for use in structural applications. Traditional ceramics, which are based on metal silicates or aluminosilicates, are the materials used to make pottery, china, bricks, and concrete. Modern ceramics contain a much wider range of components and can be classified as either ceramic oxides, which are based on metal oxides such as alumina (Al₂O₃), zirconia (ZrO₂), and beryllia (BeO), or nonoxide ceramics, which are based on metal carbides such as silicon carbide (carborundum, SiC) and tungsten carbide (WC), or nitrides like silicon nitride (Si₃N₄) and boron nitride (BN).

All modern ceramics are hard, lightweight, and stable at very high temperatures. Unfortunately, however, they are also rather brittle, tending to crack or break under stresses that would cause metals to bend or dent. Thus a major challenge for materials scientists is to take advantage of the desirable properties of ceramics, such as their thermal and oxidative stability, chemical inertness, and toughness, while finding ways to decrease their brittleness to use them in new applications. Few metals can be used in jet engines, for example, because most lose mechanical strength and react with oxygen at the very high operating temperatures inside the engines (approximately 2000°C). In contrast, ceramic oxides such as Al₂O₃ cannot react with oxygen regardless of the temperature because aluminum is already in its highest possible oxidation state (Al³⁺). Even nonoxide ceramics such as silicon and boron nitrides and silicon carbide are essentially unreactive in air up to about 1500°C. Producing a high-strength ceramic for service use involves a process called sintering, which fuses the grains into a dense and strong material (Figure 12.33).

Figure 12.33 Sintering. These photos show the effects of sintering magnesium oxide grains: (a) the microstructure before sintering; (b) the microstructure of the ceramic after sintering for two hours at 1250°C; and (c) the microstructure after sintering for two hours at 1450°C. During the sintering process, the grains fuse, forming a dense and strong material.

Note the Pattern

Ceramics are hard, lightweight, and able to withstand high temperatures, but they are also brittle.

One of the most widely used raw materials for making ceramics is clay. Clay minerals consist of hydrated alumina (Al₂O₃) and silica (SiO₂) that have a broad range of impurities, including barium, calcium, sodium, potassium, and iron. Although the structures of clay minerals are complicated, they all contain layers of metal atoms linked by oxygen atoms. Water molecules fit between the layers to form a thin film of water. When hydrated, clays can be easily molded, but during high-temperature heat treatment, called firing, a dense and strong ceramic is produced.

Because ceramics are so hard, they are easily contaminated by the material used to grind them. In fact, the ceramic often grinds the metal surface of the mill almost as fast as the mill grinds the ceramic! The sol-gel process was developed to address this problem. In this process, a water-soluble precursor species, usually a metal or semimetal alkoxide [M(OR)_n] undergoes a hydrolysis reaction to form a cloudy aqueous dispersion called a sol. The sol contains particles of the metal or semimetal hydroxide [M(OH)_n], which are typically 1–100 nm in diameter. As the reaction proceeds, molecules of water are eliminated from between the M(OH)_n units in a condensation reaction, and the particles fuse together, producing oxide bridges, M–O–M. Eventually, the particles become linked in a three-dimensional network that causes the solution to form a gel, similar to a gelatin dessert. Heating the gel to 200°C–500°C causes more water to be eliminated, thus forming small particles of metal oxide that can be amazingly uniform in size. This chemistry starts with highly pure \(SiCl_4\) and proceeds via the following reactions:

• Alkoxide Formation

\[ SiCl_4 (s) + 4 CH_3CH_2OH (l) + 4 NH_3 (g) \rightarrow Si(OCH_2CH_3)_4 (s) + 4 NH_4 Cl (s) \tag{12.4}\]

• Hydroylysis of the alkoxide (sol)

\[Si(OCH_2CH_3)_4 (s) + 4 H_2O (l) \rightarrow (HO)_3Si - OH (s) + 4 CH_3CH_2OH (aq) \tag{12.5}\]

• Condensation

\[ (HO)_3 Si - OH (s) + n HO - Si(OH)_3 (s) \rightarrow (HO)_3 Si(-O-Si(OH)_3)_n (s) + n H_2O (l) \tag{12.6}\]

Nature uses the same process to create opal gemstones.

Superalloys

Superalloys are high-strength alloys, often with a complex composition, that are used in systems requiring mechanical strength, high surface stability (minimal flaking or pitting), and resistance to high temperatures. The aerospace industry, for example, requires materials that have high strength-to-weight ratios to improve the fuel efficiency of advanced propulsion systems, and these systems must operate safely at temperatures greater than 1000°C.

Although most superalloys are based on nickel, cobalt, or iron, other metals are used as well. Pure nickel or cobalt is relatively easily oxidized, but adding small amounts of other metals (Al, Co, Cr, Mo, Nb, Ti, and W) results in an alloy that has superior properties. Consequently, most of the internal parts of modern gas turbine jet engines are now made of superalloys based on either nickel (used in blades and disks) or cobalt (used in vanes, combustion chamber liners, and afterburners). The cobalt-based superalloys are not as strong as the nickel-based ones, but they have excellent corrosion resistance at high temperatures.

Other alloys, such as aluminum–lithium and alloys based on titanium, also have applications in the aerospace industry. Because aluminum–lithium alloys are lighter, stiffer, and more resistant to fatigue at high temperatures than aluminum itself, they are used in engine parts and in the metal “skins” that cover wings and bodies. Titanium’s high strength, corrosion resistance, and lightweight properties are equally desirable for applications where minimizing weight is important (as in airplanes). Unfortunately, however, metallic titanium reacts rapidly with air at high temperatures to form TiN and TiO₂. The welding of titanium or any similar processes must therefore be carried out in an argon or inert gas atmosphere, which adds significantly to the cost. Initially, titanium and its alloys were primarily used in military applications, but more recently, they have been used as components of the airframes of commercial planes, in ship structures, and in biological implants.

Composite Materials

Composite materials have at least two distinct components: the matrix (which constitutes the bulk of the material) and fibers or granules that are embedded within the matrix and limit the growth of cracks by pinning defects in the bulk material (Figure 12.34). The resulting material is stronger, tougher, stiffer, and more resistant to corrosion than either component alone. Composites are thus the nanometer-scale equivalent of reinforced concrete, in which steel rods greatly increase the mechanical strength of the cement matrix, and are extensively used in the aircraft industry, among others. For example, the Boeing 777 is 9% composites by weight, whereas the newly developed Boeing 787 is 50% composites by weight. Not only does the use of composite materials reduce the weight of the aircraft, and therefore its fuel consumption, but it also allows new design concepts because composites can be molded. Moreover, by using composites in the Boeing 787 multiple functions can be integrated into a single system, such as acoustic damping, thermal regulation, and the electrical system.

Three distinct types of composite material are generally recognized, distinguished by the nature of the matrix. These are polymer-matrix composites, metal-matrix composites, and ceramic-matrix composites.

Figure 12.34 Some Possible Arrangements of Fibers in Fiber-Reinforced Composite Materials. The arrangements shown range from discontinuous and randomly oriented to continuous and aligned. The fibers limit the growth of cracks by pinning defects within the matrix.

• Fiberglass is a polymer-matrix composite that consists of glass fibers embedded in a polymer, forming tapes that are then arranged in layers impregnated with epoxy. The result is a strong, stiff, lightweight material that is resistant to chemical degradation. It is not strong enough, however, to resist cracking or puncturing on impact. Stronger, stiffer polymer-matrix composites contain fibers of carbon (graphite), boron, or polyamides such as Kevlar. High-tech tennis rackets and golf clubs as well as the skins of modern military aircraft such as the “stealth” F-117A fighters and B-2 bombers are made from both carbon fiber–epoxy and boron fiber–epoxy composites. Compared with metals, these materials are 25%–50% lighter and thus reduce operating costs. Similarly, the space shuttle payload bay doors and panels are made of a carbon fiber–epoxy composite. The structure of the Boeing 787 has been described as essentially one giant macromolecule, where everything is fastened through cross-linked chemical bonds reinforced with carbon fiber.
• Metal-matrix composites consist of metals or metal alloys reinforced with fibers. They offer significant advantages for high-temperature applications but pose major manufacturing challenges. For example, obtaining a uniform distribution and alignment of the reinforcing fibers can be difficult, and because organic polymers cannot survive the high temperatures of molten metals, only fibers composed of boron, carbon, or ceramic (such as silicon carbide) can be used. Aluminum alloys reinforced with boron fibers are used in the aerospace industry, where their strength and lightweight properties make up for their relatively high cost. The skins of hypersonic aircraft and structural units in the space shuttle are made of metal-matrix composites.
• Ceramic-matrix composites contain ceramic fibers in a ceramic matrix material. A typical example is alumina reinforced with silicon carbide fibers. Combining the two very high-melting-point materials results in a composite that has excellent thermal stability, great strength, and corrosion resistance, while the SiC fibers reduce brittleness and cracking. Consequently, these materials are used in very high-temperature applications, such as the leading edge of wings of hypersonic airplanes and jet engine parts. They are also used in the protective ceramic tiles on the space shuttle, which contain short fibers of pure SiO₂ mixed with fibers of an aluminum–boron–silicate ceramic. These tiles are excellent thermal insulators and extremely light (their density is only about 0.2 g/cm³). Although their surface reaches a temperature of about 1250°C during reentry into Earth’s atmosphere, the temperature of the underlying aluminum alloy skin stays below 200°C.

Example 11

An engineer is tasked with designing a jet ski hull. What material is most suited to this application? Why? Given: design objective Asked for: most suitable material Strategy: Determine under what conditions the design will be used. Then decide what type of material is most appropriate. Solution: A jet ski hull must be lightweight to maximize speed and fuel efficiency. Because of its use in a marine environment, it must also be resistant to impact and corrosion. A ceramic material provides rigidity but is brittle and therefore tends to break or crack under stress, such as when it impacts waves at high speeds. Superalloys provide strength and stability, but a superalloy is probably too heavy for this application. Depending on the selection of metals, it might not be resistant to corrosion in a marine environment either. Composite materials, however, provide strength, stiffness, and corrosion resistance; they are also lightweight materials. This is not a high-temperature application, so we do not need a metal-matrix composite or a ceramic-matrix composite. The best choice of material is a polymer-matrix composite with Kevlar fibers to increase the strength of the composite on impact. Exercise In designing a new generation of space shuttle, National Aeronautics and Space Administration (NASA) engineers are considering thermal-protection devices to protect the skin of the craft. Among the materials being considered are titanium- or nickel-based alloys and silicon-carbide ceramic reinforced with carbon fibers. Why are these materials suitable for this application? Answer: Ti- or Ni-based alloys have a high strength-to-weight ratio, resist corrosion, and are safe at high temperatures. Reinforced ceramic is lightweight; has high thermal and oxidative stability; and is chemically inert, tough, and impact resistant.

Summary

Ceramics are nonmetallic, inorganic solids that are typically strong; they have high melting points but are brittle. The two major classes of modern ceramics are ceramic oxides and nonoxide ceramics, which are composed of nonmetal carbides or nitrides. The production of ceramics generally involves pressing a powder of the material into the desired shape and sintering at a temperature just below its melting point. The necessary fine powders of ceramic oxides with uniformly sized particles can be produced by the sol-gel process. Superalloys are new metal phases based on cobalt, nickel, or iron that exhibit unusually high temperature stability and resistance to oxidation. Composite materials consist of at least two phases: a matrix that constitutes the bulk of the material and fibers or granules that act as a reinforcement. Polymer-matrix composites have reinforcing fibers embedded in a polymer matrix. Metal-matrix composites have a metal matrix and fibers of boron, graphite, or ceramic. Ceramic-matrix composites use reinforcing fibers, usually also ceramic, to make the matrix phase less brittle.

Key Takeaway

Materials that have contemporary applications include ceramics, high-strength alloys, and composites, whose properties can be modified as needed.

Conceptual Problems

1. Can a compound based on titanium oxide qualify as a ceramic material? Explain your answer. 2. What features make ceramic materials attractive for use under extreme conditions? What are some potential drawbacks of ceramics? 3. How do composite materials differ from the other classes of materials discussed in this chapter? What advantages do composites have versus other materials? 4. How does the matrix control the properties of a composite material? What is the role of an additive in determining the properties of a composite material?

Contributors