The MAX Phases: Unique New Carbide and Nitride Materials

Ternary ceramics turn out to be surprisingly soft and machinable, yet also heat-tolerant, strong and lightweight

Michel W. Barsoum and Tamer El-Raghy

f one could increase the average engine temperature of the worlds jets by one degree Celsius, the fuel savings alone would be worth around $1 billion per year. Using a similar strategy to increase the efficiency of our vehicle fleet by 3 miles per gallon would save roughly a million barrels of oil a day. These stunning figures reflect a simple fact of thermodynamics: The efficiency of any fuel-burning engine is directly proportional to its operating temperature. A jet engine made from a material 50 percent lighter in weight and able to run 200 to 300 degrees hotter could have a staggering economic impact. Todays jet engines are not running hotter for a simple reason: No material exists that can take that kind of heat while spinning furiously. The same goes for the internal-combustion engine; if an automobile engine could be built with a temperature-tolerant material, its radiator, water pump and cooling water could be thrown away. Such an effi-

Michel W. Barsoum obtained his Ph.D. in materials science from the Massachusetts Institute of Technology in 1985, at which time he joined the Department of Materials Engineering at Drexel University, where he is currently a Distinguished Professor. In 2000 he was awarded a HumboldtMax Planck Research Award and is spending a sabbatical year at the Max-Planck Institut fr Metallforschung in Stuttgart, Germany. Tamer El-Raghy obtained his Ph.D. from the Department of Materials Engineering at Drexel University in 1997. He is currently president of the company 3-ONE-2, which he cofounded with Barsoum to develop the materials described in the article for use in jet engines and other applications. Address for Barsoum: Department of Materials Engineering, Drexel University, Philadelphia, PA 19104. Internet: barsoumw@drexel.edu 334 American Scientist, Volume 89

cient, lighter and higher-temperature engine would squeeze more miles from every gallon of fuel. Roughly three decades ago, most materials scientists appreciated that above 1,000 degrees Celsius even the best metal alloys turn into taffy and become useless for load-bearing applications. Building hotter engines would require employing another class of materials, namely ceramics. This realization ignited a worldwide research and development race that to date has cost billions of dollars. And although there has been undeniable progress, the wide use of ceramics as structural materials in the aerospace, automotive and chemical industries remains elusive. It is fair to say that had ceramics not been so hard or brittle, they would have been more useful. The glibness of this statement becomes apparent, however, when it is appreciated that properties come in bundles: Hardness, brittleness and poor machinability are inexorably linked to good high-temperature properties. One cannot get one without the other, or so it was believed. So it sounded too good to be true five years ago when we discovered a material that was stiff, lightweight, machinable, made from relatively inexpensive raw materials, resistant to oxidation and thermal shock, and capable of remaining strong up to temperatures in excess of 1,300 degrees C in air. Disparaging references to snake oil were overheard once or twice. But not only did we discover one such material, we also identified more than 50 closely related compounds. Since then, we have shown that these compounds behave like no others before them. As we will explain, we call them Mn+1AXn

or MAX phases because of their composition. They constitute an exciting new class of materials that is more revolutionary than evolutionary. Not Your Fathers Carbide Late in 1995, with funding from the National Science Foundation, we were busy exploiting a processing method invented by one of us (Barsoum) for fabricating dense, bulk, ultrarefractory materials that could not otherwise be made. The recipe involves heating the starting materials in a sealed glass container under pressure to simultaneously compress them and initiate a reaction. At the time we were fabricating some very hard and refractory borides and carbides. A major drawback of these solids, however, was their poor oxidation resistance, a deficiency that could in principle be remedied by the substitution of silicon for boron. So we turned our attention to the titaniumcarbon-silicon system and learned of the existence of titanium silicon carbide, Ti3SiC2. While carrying out a literature search, we decided to synthesize this compound. Wolfgang Jeitschko and Hans Nowotny first synthesized this phase in 1967 at the University of Vienna and determined its structure. Initial hints that Ti3SiC2 was not a typical carbide came as early as 1972, when a German group working on chemically vapor deposited films showed that it was anomalously soft for a carbide. The fabrication of single-phase, bulk samples proved more challenging; several groups had tried and failed. A group headed by Roman Pampuch in Poland had come closest; their best samples were about 85 percent pure by volume. Using these

Sigma Xi, The Scientific Research Society. Reproduction with permission only. Contact perms@amsci.org.

Figure 1. Micrographs of a new class of carbide and nitride materialsthe MAX phasesare both colorful and revealing (top). The patches of different hues indicate distinct crystal domains or grains, each made up of thousands of nanolayers of titanium silicon carbide. (Image shows a region 0.7 by 0.5 micrometer.) In this micrograph, the large orange grains of Ti3SiC2 are growing by consuming the much smaller grains in the foreground. The large grains were pre-oriented by a hot forging process. Such aligned microstructures are ductile even at room temperature. These properties would be ideal in future high-performance applications such as jet engines for aircraft. Current engine technology (such as the 100-inch-diameter PW4000 at right, developed in the early 1990s and used in Airbus A330 wide-bodied twinjets) is limited by materials failure at high temperatures. Lighter materials and engines that could operate at higher temperatures would provide immense benefits in cost savings and fuel efficiency. (Micrograph by Patricia Lyons; engine photograph courtesy of Pratt & Whitney )

Sigma Xi, The Scientific Research Society. Reproduction with permission only. Contact perms@amsci.org.

2001

JulyAugust

335

temperature (degrees Celsius) at which oxidation penetrates 2.5 millimeters in 10,000 hours

with silicidation Ti 3 SiC 2 1,000 stainless steels cobalt superalloys chromium-12 steel 500 aluminum alloys

nickel superalloys

molybdenum alloys

tungsten alloys

carbon steel chromalloy steel 0 0 500 1,000 1,500 temperature (degrees Celsius) at which material ruptures after 140 megapascals of stress for 10,000 hours

Figure 2. Materials in demanding applications not only must retain their strength, but also need to resist oxidation. The chart shows how some of the most important high-performance alloys stack up against titanium silicon carbide, Ti3SiC2. Materials toward the right resist breakage under stress at high temperatures; materials toward the top can reach high temperatures before oxidation attacks the material surface. Titanium silicon carbide exceeds all current materials for oxidation resistance and approaches the nickel superalloys in strength. IA IIA

samples, they were the first to show that Ti3SiC2 was quite a stiff material, almost three times as stiff as titanium metal (with the same density). With our processing technique, we succeeded in making bulk, predominantly single-phase samples and looked forward to characterizing them. Our enthusiasm was short-lived, however, because we discovered a paper by a French group that had worked hard to fabricate almost pure samples of Ti3SiC2. Not only did it appear that they had scooped us, but, to our dismay, they also claimed the product was neither oxidation-resistant nor, even worse, thermally stable above 1,400 degrees. Other papers claimed the same; in retrospect, it is ironic that had we carried out a thorough literature search before embarking on this work, we probably would have abandoned the quest. Despite the bad news and its being late on a Friday evening, we pursued our oxidation study anyway. On Monday morning we discovered that the sample we had left in the furnace over the weekend at 1,000 deIIIA IVA VA VIA VII VIIIA

H
Li Na K Rb Cs Fr Be Mg Ca Sr Ba Ra Sc Y Lu Lr Ti Zr Hf V Nb Ta Cr Mo W Mn Tc Re Fe Ru Os Co Rh Ir Ni Pd Pt Cu Ag Au Zn Cd Hg
M early transition metal A group A element X C and/or N

He B Al Ga In Tl C Si Ge Sn Pb N P As Sb Bi O S Se Te Po F Cl Br I At Ne Ar Kr Xe Rn

Unq Unp Unh Uns Uno Une

Figure 3. The MAX phases are made up of an early transition metal M (red) in the periodic table, an element from the A groups, usually IIIA and IVA (dark blue), and a third element, X, which is either nitrogen or carbon (black), in the composition Mn+1AXn, where n is 1, 2 or 3. The classes of materials characterized to date naturally form into three groups, based on the number of atoms of the M, A and X elements in each molecule; these groups are known as 211, 312 and 413 materials. Author Barsoums group has synthesized materials (asterisks) from the base elements marked with yellow, green or pink squares, representing the three classes of materials. 336 American Scientist, Volume 89

211

Ti2AIC* Nb2AIC* Ti2GeC* Zr2SnC* Hf2SnC* Ti2SnC* Nb2SnC* Zr2PbC*

Ti2AIN* (Nb,Ti)2AIC* Cr2AlC Ta2AlC V2AlC V2PC Nb2PC Ti2PbC*

Hf2PbC* Ti2AIN0.5C0.5* Zr2SC Ti2SC Nb2SC Hf2SC Ti2GaC V2GaC

Cr2GaC Nb2GaC Mo2GaC Ta2GaC* Ti2GaN Cr2GaN V2GaN V2GeC

V2AsC Nb2AsC Ti2CdC Sc2InC Ti2InC Zr2InC Nb2InC Hf2InC

Ti2InN Zr2InN Hf2InN Hf2SnN Ti2TlC Zr2TlC Hf2TlC Zr2TlN

312

Ti3AIC2* Ti3SiC2*

Ti3GeC2*

413

Ti4AIN3*

Sigma Xi, The Scientific Research Society. Reproduction with permission only. Contact perms@amsci.org.

grees had gained less than 1 percent in weight. This was a dramatic sign: Not only did Ti3SiC2 resist oxidation, but also, and more important, our samples were unlike any made before. Our next step was to find out how the samples fared under thermal shock. Small bars of the material were heated to high temperature and quenched in a bucket of water. The higher the temperature from which a brittle material is quenched, the higher the probability that it will shatter. In 1995, few ceramics, if any, could survive a thermal shock of much more than 500 degrees Celsius, so we decided to start at 750 degrees and work our way down in temperature. Surprisingly, the bars survived the first test, so we upped the ante to 1,200 degrees, and again they remained intact. Finally, the bars were quenched from 1,400 degreesimagine dropping a white-hot ceramic bar in a pail of waterand again they survived. But this time their strength actually increased slightly after the quench. We knew this was something out of the ordinary. We also knew from previous work that this material had a layered structure, so we had a hunch it might be machinable. We asked our machinist to drill a hole through a sample. Knowing that we worked with ceramics, he was reluctant, and he demanded to know what the material was. We urged him to trust us, moved a few steps back and watched as the carbide drill bit was dulled, resharpened and dulled again. On the third try, the drill bithaving broken through a hard crustsimply disappeared into the sample. The noise changed from one of harsh grinding to a soft, almost whirring sounda transformation that left us speechless. Ti 3SiC 2 turned out to be nearly as machinable as graphite. And this in a carbide, the material of choice for making cutting tools and drill bits. We soon began looking for similar compounds, but nature was stingy; we identified only two, Ti3GeC 2 and Ti3AlC2 (where a single germanium or aluminum atom substitutes for the silicon), which we synthesized and found to behave like Ti3SiC2. Because of their atomic composition, we refer to these materials as 312 compounds. A perusal of the literature, however, quickly established that the 312s had roughly 50 first cousins with a 211 chemistry. The structures of the vast majority of these compounds were determined in the

1960s by Nowotny and his coworkers, but for reasons that are not entirely clear had been almost totally neglected since. Very recently we identified Ti4AlN3, a nitride with a 413 molecular composition, as another scion of the same family. In other words, we are dealing with a family of ternary layered compounds

with the general formula of Mn+1AXn, where n is 1, 2 or 3, M is an early transition metal (the metals appearing on the left-hand side of the center section of the periodic table), A is an A-group element (appearing generally in sections IIIA or IVA of the periodic table), and X is carbon or nitrogen, or both.

211

312

413

Ti Si

Figure 4. In the crystal structures of all the MAX phases (top), transition metal carbide or nitride layers (red and black atoms) are interleaved with layers of pure A-group element (blue atoms). Every third layer in the 211 compounds (left) is A-group; in the 312 (middle), every fourth layer is A-group; in the 413 class (right), every fifth layer is A-group. At bottom, a high-resolution transmission-electron micrograph provides a cross section of the structure of titanium silicon carbide (the small carbon atoms are not visible in the micrograph), diagrammed on the right. (Micrograph courtesy of Leonid Farber and Igor Levin, National Institute of Standards and Technology.) 2001 JulyAugust 337

Sigma Xi, The Scientific Research Society. Reproduction with permission only. Contact perms@amsci.org.

Figure 5. Although very stiff and capable of resisting intense thermal shock, the MAX carbides can easily be sliced with a hacksaw. In the authors synthesis process, high temperature and high pressure are simultaneously applied in a device called a hot isostatic press. The starting materials react under pressure in a sealed cell to produce the MAX phases. The result is a carbide of almost unimaginable machinability. (Photograph courtesy of the authors.)

Mechanical Wonder The most striking facet of the mechanical response of titanium silicon carbide, and by extension the other phases, is its almost schizoid nature; it is not quite sure whether it wants to be a metal or a ceramic. Like a metal it is

Figure 6. If a Ti3SiC2 sample is fractured, bundles of ligaments form in the spreading crack, as shown in this micrograph. These ligaments are crucial in endowing the material with its high fracture toughness. The same pattern of ligament formation can be seen in cracked wood, a process of delamination and crack bridging that makes freshly cut wood very tough. 338 American Scientist, Volume 89

machinable, thermally and electrically conductive, resistant to thermal shock and plastic at elevated temperatures. Like a ceramic it is refractory (its decomposition temperature is greater than 2,000 degrees Celsius), oxidationresistant, quite stiff and relatively light (4.5 grams per cubic centimeter). Its thermal expansion is also closer to that of typical ceramics than to that of metals; it is, in other words, relatively low. To understand how this can be, we need to look at how crystalline solids deform. The defect that allows metals to deform plastically is called a dislocation. It is only by the generation and movement of millions upon millions of these dislocations that permanent macroscopic deformation is achieved. For Ti3SiC2, dislocations permit plasticity only at temperatures around 1,200 degrees, where deformations in excess of 20 percent are possible in tension, compression and bending. Randomly oriented polycrystalline samples of the compound, on the other hand, are brittle at room temperature. However, if during the processing the grains are highly oriented, then the samples are ductile even at room temperature. The main reason for this state of affairs is Ti3SiC2s ability to deform by forming kink bands.

Kink bands are common in nature and are familiar to most people. They typically form when layered materials are loaded parallel to the layers. To form a kink band, stand a deck of cards on end and carefully add weight on top. For small loads, the cards will buckle elastically (that is, if the load is removed, the cards snap back to their original shape). However, at a maximal load the cards will buckle irreversibly, forming one or more kink bands where the layers bend sharply and remain bent. Kink bands have been invoked to explain deformation in wood, polymer fibers, polymer composites, phone books and geologic formations, among others. In crystalline solids, kink bands are formed by creating edge dislocations in the center of what eventually becomes the kink band. These dislocations then move in opposite directions and eventually arrange themselves in walls, which define the kink boundaries. In most cases, the formation of kink bands in a material results in a decrease in mechanical integrity. The fundamental and crucial difference between the kink bands that form in the MAX phases and those in other materials is that even after the initiation of damage, the ternary phases can still carry substantial loads. This so-called damage tolerance was initially quite puzzling and highly unusual. For most materials, once damage is initiated, the point of damage becomes weaker, resulting in further damage, which leads to further weakening and rapid failure. For example, when a graphite-reinforced tennis racquet or ski develops a crack, it is time to replace it. Working with Igor Levin of the National Institute of Standards and Technology, and the transmission-electronmicroscopy expert in our group, Leonid Farber, we were able to shed some light on the problem. Simple geometry dictates that for a kink band to form, part of the crystal that is forming the kink band must be able to glide relative to the part that is not. Furthermore, the layers of the two parts must detach from each other. Going back to the carddeck analogy: For the deck to kink, the cards have to simultaneously be able to slide relative to each other and to delaminate. Had the cards been glued together, or clamped normal to the applied load, they would not have kinked. Containing the Damage This analysis explains how the kink bands form, but it does not totally ex-

Sigma Xi, The Scientific Research Society. Reproduction with permission only. Contact perms@amsci.org.

plain why the MAX phases are so extraordinarily damage-tolerant. The transmission electron micrographs have helped reveal the answer. For a delamination crack to extend in one direction, it has to move all the dislocations in the kink boundary ahead of itan energetically very expensive proposition. Extension in the other direction, however, is easier, since there are no dislocations in its path. The end result is that the crack is not only asymmetrical, but, more important, it also is stopped by the kink boundaries. We like to think of the kink boundaries as containers or reflectors of damage. After the damage is initiated, the damaged area locally hardens, rather than weakens, and the damage migrates to another region. The power and elegance of this unique and fortuitous state of affairs is that the atomic mechanisms responsible for deformation are the same mechanisms ultimately responsible for damage containment. In other words, damage tolerance is built into the structure at the atomic level. And although this is not a self-healing material, it is the next best thing: a damage-tolerant one. For real-world applications, the importance of damage tolerance cannot be overemphasized. The nightmare of every design engineer, and one of the main reasons ceramics have not been used more often in load-bearing applications, is the possibility that sometime during manufacturing or use a small scratch or nick might develop on the surface that seriously compromises the strength of a part. (Glass cutters will attest that all it takes to slice a pane of glass is a shallow surface scratch.) The compound Ti3SiC2 is quite insensitive to such flaws even at room temperatureswhich implies, for example, that a turbine blade made of this material will not shatter every time a small rock is sucked into a jet engine. Recently, in collaboration with Christopher Gilbert, Don Bloyer and Robert Ritchie at Lawrence Berkeley National Laboratory, we have shown that Ti3SiC2 was fatigue-resistant and also exhibited the highest resistance by almost a factor of twoto the extension of cracks of any single-phase ceramic that does not undergo a hardening phase transformation. The main reason is that ligaments made of titanium-carbon-silicon bonded sheets form in the crack wake. These ligaments are extremely tenacious and hold the

crack surfaces together, dramatically enhancing the resistance to crack propagation. Interestingly enough, these ligaments look just like the structures a woodcutter would encounter when chopping wood. It is exactly this combination of delamination and crack bridging that makes wood, especially freshly cut wood, so tough. These materials blend two powerful ideas that have emerged in materials science. The first is that of nanoengineered solids, in which reducing the scale of the microstructure is believed to result in unusual and unexpected benefits. In the past, nanolayered materials were typically fabricated by laying those layers down one at a time, using the very expensive technique known as molecular beam epitaxy. In addition to being quite costly, layers formed in this way had another major disadvantage in that they could not be used at elevated temperatures, since that resulted in their intermixing. The MAX phases benefit from the special

Figure 7. A simple card trick illustrates the microscopic phenomenon that gives MAX materials their sturdinessthe kink band. Take a deck of cards and stand them upright. When the deck is put under pressure from above, it bends as each card folds slightly, and then returns to its previous shape when the load is removed. But when the deck is put under substantial stress, each card bends irreversibly to form a kink and the cards separate (delaminate).

k kin d n a b

delamination cracks

edge dislocation wall undeformed region

Figure 8. Kink bands form in a crystalline solid when dislocations form and move in opposite directions (small T symbols in the diagram), settling into a configuration with well-defined kink boundaries. Any cracks that start to separate the layers bump into the kink boundaries and are stopped. The two sets of layers can still slide past each other to provide ductility as the kink boundaries maintain mechanical integrity. Optical micrograph shows a typical macroscopic kink band (top right), whereas the transmission electron microscope image shows a microscopic kink band and its boundaries (bottom right). Note that the cracks extend only into the area defined by the kink boundaries and not beyond them. 2001 JulyAugust 339

Sigma Xi, The Scientific Research Society. Reproduction with permission only. Contact perms@amsci.org.

Figure 9. MAX phase materials are nanolaminates, assemblages of microscopic layers analogous to the flaky phyllo dough in some pastries layers that are revealed when an object is run across the surface of a Ti3SiC2 sample (left). Additional damage mechanisms are observed when the nanolaminates are intentionally damaged by a mechanical indenter, including the popping out of entire laminated crystalline grains (middle) and buckling of the grains (right). (Images courtesy of the authors.)

properties arising from nanolayering but do not have this disadvantage. The second idea is that of biomimetics, the attempt to capture the properties of the splendid designs that have evolved over millions of years in nature. A good material for engineers to mimic is the abalone shell, which is mainly composed of a brittle calcium

Figure 10. Natures designs for strength and toughness are surprisingly similar to the structures found in the MAX phases. A micrograph of a Ti3SiC2 sample that has been deformed at high temperature clearly shows layered features and kinked grains responsible for the materials unusual properties (top). The cracked shell of an abalone also exhibits a layered structure of calcium carbonate and protein, which gives this natural material a fracture toughness 3,000 times greater than that of the crystals alone (bottom). (MAX micrograph courtesy of the authors; abalone micrograph courtesy of Daniel E. Morse, University of California, Santa Barbara.] 340 American Scientist, Volume 89

carbonate and yet is quite tough. This toughness arises from a submicron polymer film that lies between the layers of the calcium carbonate. The polymer essentially behaves like the crackstopping ligaments mentioned above. The microstructural similarities between the fractured surfaces of an abalone shell and some of the micrographs we obtained in Ti3SiC2 are noteworthy. The layering in abalone, however, is at a coarser scale than the layered compounds discussed herein. Another crucial distinction is that the properties of abalone are optimized for normal temperatures at the earths surface. Heating an abalone shell to a few hundred degrees destroys the polymer and concomitant toughness. Most recently, and based in part on the work of Miladin Radovic and Peter Finkel of Drexel University, we have shown that despite vast differences in their physical, electrical, thermal and chemical properties, Ti3SiC2 and ordinary water ice also behave very similarly when their mechanical properties are compared. It is difficult to conceive of two more dissimilar solids: one is transparent, insulating and soft and melts at 0 degrees; the other is metallic, conductive and at least 30 times stiffer, and dissociates at temperatures greater than 2,300 degrees). This discovery is quite surprisingalmost as surprising as discovering high-temperature superconductivity in oxides or conductive polymers. One simply does not associate carbides with ice, especially when considering their mechanical response. On the other hand, since both solids deform by a similar microscopic mechanism, their response to the rate at which they are stressed is strikingly similar. If loaded rapidly, both fail in a brittle manner; if loaded slowly, they flow. (It is this

attribute of ice that allows icebreakers to break ice and glaciers to flow). Well-Behaved Materials A metals machinability is inextricably and inversely linked to its performance at higher temperature. The same mechanisms that render metals useful at higher temperatures (namely, obstacles in the way of the dislocations) are the ones that make them difficult to machine. Superalloys, difficult and expensive to machine, are a case in point. Ceramics are even more difficult to machine because they are harder and more brittle. One of the joys of working with these new ternary compounds is their ease of machinability. Regular high-speed tool bits can be used with no lubrication or cooling. They are the only carbides or nitrides that can be sliced or diced with a manual hacksaw. It is interesting that they do not machine by plastic deformation, as in the case of metals, but rather by the breaking off of tiny microscopic flakes. A good analogy here is that of scooping ice cream versus shaving ice; the former is like machining metals, the latter like working with the MAX compounds. The fact that these solids machine readily is of technological importance for three reasons. First, easy machinability allows for the fabrication of relatively cheap prototypes, which in turn means it will be possible to test the materials for a variety of applications. The second reason has to do with tight tolerances. In many applications, such as engines, the tolerances required are more stringent than can be fabricated, and a postfabrication machining step is typically required. The third has to do with joining. Joining ceramics to other materials is a nontrivial exercise fraught with pit-

Sigma Xi, The Scientific Research Society. Reproduction with permission only. Contact perms@amsci.org.

falls. Machinability allows for alternative solutions. For example, the tubes used by the petrochemical and chemical industries can be quite long (about 12 meters) and pose a serious processing challenge to any traditional ceramic material that currently exists. Machinability greatly simplifies the problem: 1- or 2meter lengths of tubes can be extruded and their ends threaded and screwed together, end to end, to any desired length. Oxidation resistance is a necessary requirement of any material that is to operate in air at elevated temperatures. The only naturally oxidation-resistant materials are the oxides, but they are not useful high-temperature structural materials because they are brittle and susceptible to thermal shock. The design of oxidation-resistant materials depends on the presence of an element that, on exposure to oxygen, will oxidize and form a thin, adherent and protective oxide layer. Few elements form oxides that are protective enough to be useful oxidation barriers at temperatures greater than 1,000 degrees. Most notable of these are the oxides of silicon, aluminum and chromium. The superalloys used today in jet engines are nickel-based but contain enough chromium to render them oxidation-resistant. In the presence of oxygen they become covered with a thin chromium oxide (Cr2O3) layer that is both tenacious and protective, but only up to about 1,000 degrees. (Incidentally, it is also by adding chromium to steel that the latter becomes stainless.) Above 1,200 degrees, the oxide of choice is silicon dioxide, SiO2, because it is almost impermeable by oxygen, even at temperatures as high as 1,700 degrees. Of all the MAX compounds, the only one that contains silicon is Ti3SiC2. Unfortunately, the concentration of silicon in a 312 material is insufficient to form a layer of pure SiO2; a duplex layer of SiO2 and TiO2 forms instead. At 1,000 degrees, this layer is as protective as chromium oxide, but as the temperature climbs to 1,400 degrees, the oxidation rate becomes troubling. To enhance the oxidation resistance of Ti3SiC2 at temperatures as high as 1,500, we patented a process by which its surface is reacted with silicon to form TiSi2 and SiC. Once this surface layer is formed, the oxidation resistance is enhanced by about five orders of magnitude, because the protective oxide that now forms is SiO2. Having TiSi2 and SiC on the surface also enSigma Xi, The Scientific

How Materials Deform

a 1 2 3 4 5 6 7 8 9 10 1112

eforming a perfect crystal is as hard as moving a huge carpet by lifting one edge and pulling on it. There is another, albeit slower, way to move the carpet that requires very little forceintroduce a small crease in the carpet, and move the crease. The atomic equivalent of a crease in a solid is a defect called a dislocation. How a material responds to molding and shapingits ductilityis directly related to the flow and movement of these tiny shifts in the crystalline order. A particular kind of dislocation is the edge dislocation, visible in transmission electron micrographs of the MAX materials (above). The dark lines labeled with numbers are columns of atoms; whereas most columns continue from top to bottom without a break, one of them (7) is broken by the rightward shift of the displaced columns to the left. These dislocations are analogous to the crease that might form in a carpet being pushed across a floor (a). The carpet deforms slightly, just as the crystal lattice breaks and reforms (b). The fold in the carpet can now be pushed along; in a crystal, the bonds snap and reform to move the dislocation along the lattice (c and d). Eventually the dislocation reaches the end of the material and the entire row of atoms has been moved one lattice unit (e). Each dislocation only represents an atomic shift, so billions upon billions of these dislocations have to move before any macroscopic deformation is observed. Moving dislocations consumes energy, which is ultimately responsible for the toughness of materials.

Figure 11. Machinability is a big advantage with the MAX materials and will be necessary if they are to be adopted commercially. Prototype tubes for high-temperature chemical industrial processes (one is pictured in Figure 5) are being developed, as well as everyday components such as the bolt shown here. (Image courtesy of the authors.)

hances the hardness and presumably the wear resistance. For obvious reasons, Ti3SiC2 is not as hard and wear-resistant as other ceramics. However, the astute reader will have noted that during our first attempt to machine the ternary carbide we had to break through a hard crust. This intrigued us, and on closer inspection we discovered that the hard, wearresistant crust was titanium carbide, TiC, one of the hardest carbides known. This crust formed as a result of a reaction with the graphite foil used as a mold release in our hot press. A Material of Many Talents The technological impact of these ternary compounds will not derive from any single extraordinary property but rather because they achieve a unique combination of properties. The fact that the raw materials to make some of these are abundant and inexpensive (the cost of Ti3SiC2 is roughly equal to that of titanium powder, between $20 and $40 per kilogram), together with their machinability, will accelerate their use in a wide range of applications. Today, just five years after the discovery of the Mn+1AXn phases, kilogram batches of Ti3SiC2 powder are being produced commercially. Probably the greatest potential impact these materials will have will be on the transportation sector. The severe problems associated with dwindling fossil fuels and rising greenhouse gases, together with the reluctance of people to give up their cars, mandate a technical solution: We must increase the efficiency of our cars and airplanes. Ti3SiC2 is roughly half the density of the alloys used in todays jet engines and maintains its strength to temperatures that would render the best nickel-based superalloys on the market today unusable. To pursue this objective, we have re342 American Scientist, Volume 89

cently founded a company that will be commercializing Ti3SiC2 and the other MAX phases. We are working with others, including Ted Exely of Teledyne, with funding from the U.S. Department of Energy, to fabricate Ti3SiC2 components to test in jet engines. We can envision an entire automobile engine made of Ti3SiC2. Such an engine would not only operate at substantially higher temperatures than todays engines, but would do so without requiring cooling, with the obvious benefits of simpler design, reduced vehicle weight and higher fuel efficiency. Perhaps these engines could be machined out of solid blocks rapidly and economically. Once machined to the tolerances required, the surfaces that would tend to wear, such as cylinder walls, would be increased in carbon content to greatly enhance their wear resistance. Other surfaces subjected to oxidizing atmospheres would have their silicon content raised to enhance their oxidation and wear resistances. The low cost of raw materials, ease of machinability and high-temperature capabilities together with corrosion resistance render titanium silicon carbide a potential substitute for superalloys currently used in the chemical and petrochemical industries. We are working closely with Mats Sundberg of Kanthal, Sweden, on developing Ti3SiC2 tubes and other components for the chemical and petrochemical industries. Tubes up to one meter long have already been extruded in Sweden. It is worth noting here, that a colleague of ours at Drexel University, Richard Knight, has shown that Ti3SiC2 can be thermally sprayed, either by high-velocity oxy-fuel in air or plasma in vacuum, onto metallic substrates, including steel, with relative ease. The sprayed coatings are resistant to corrosion by most acids; thus a potential application for Ti3SiC2 could be thermally sprayed corrosion coatings. Investigators in Australia and England, using our samples and based on our earlier reports that Ti3SiC2 possesses self-lubricating properties, have shown that some cleavage planes in the material have some of the lowest friction coefficients of any material known to date, including graphite. They also reported that the low friction coefficients were maintained even after exposure to air for six months. Unfortunately we have shown that the low friction does not translate to polycrystalline surfaces. Nevertheless, the compounds potential advantages over

graphite in applications where rotating electrical contacts are required, such as commutating brushes for direct-current motors, are obvious; Ti3SiC2 is roughly three orders of magnitude more conductive, and significantly harder and thus more wear-resistant than graphite. The latter may actually be a problem, since it may be too hard for some applications. The combination of good electrical conductivity, stiffness at high temperatures and oxidation resistance, together with the potential for self-lubricity, is also noteworthy. Some of these compounds could potentially be ideal materials for applications, such as bearings, that demand lubricity at elevated temperatures in air or other oxidizing environments such as steam. Just Getting Started The characteristics we have reported to date are zero-generation properties; we are just developing the first usable samples. The first generation of a new material is very seldom, if ever, the one used. There is little doubt that the properties exhibited by titanium silicon carbide are superior to those of any other high-temperature structural material ever developed, when compared at a comparable stage of development. That is not to say that Ti3SiC2 does not already exhibit drawbacks. Brittleness at room temperature is a major problem, but one that, in principle, could be solved by fabricating microstructures with oriented grains. The fact that Ti 3SiC 2 is damage-tolerant at room temperature is also a plus. Three future directions are clear. The first, which we have begun to explore, is understanding the role of microstructure on material properties. The second, which we have also started, is studying the effect of solid solutions on the properties. Third is the addition of reinforcing phases, such as silicon nitride, silicon carbide and others, to enhance the properties that we are seeking. We are now convinced that new inorganic materials with exotic and unusual properties are to be found in ternary and higher phases. It is, after all, the synergistic combination of more than two elements that creates the unique combination of properties of the MAX phases. Binary compounds of titanium, silicon and carbon all yield hard, brittle solids; and yet the combination of all three elements yields a relatively soft, machinable solid. Like many other dis-

Sigma Xi, The Scientific Research Society. Reproduction with permission only. Contact perms@amsci.org.

coveries, this one was totally serendipitous; we set out to fabricate ultra-hard, refractory materials, only to end up with machinable carbides and nitrides. One never knows what new physics or new physical phenomena could be lurking around the corner. To a materials scientist, this is as close to nirvana as one could ever hope to get. Acknowledgments The authors thank the Division of Materials Research, National Science Foundation, and Army Research Office for financial support enabling these developments. Michel Barsoum would also like to thank the Humboldt and Max Planck Foundations for their financial support during his sabbatical leave in Germany. Bibliography
Barsoum, M. W. 2000. The MN+1AXN phases: A new class of solids: Thermodynamically stable nanolaminates. Progress in Solid State Chemistry 28:201281. Barsoum, M. W., M. Ali and T. El-Raghy. 2000. Processing and characterization of Ti2AlC, Ti2AlN and Ti2AlC0.5N0.5. Metallurgical and Materials Transactions 31A:18571865. Barsoum, M. W., and T. El-Raghy. 1996. Synthesis and characterization of a remarkable ceramic: Ti3SiC2. Journal of the American Ceramic Society 79:19531956.

Barsoum, M. W., and T. El-Raghy. 1999. Room temperature ductile carbides. Metallurgical and Materials Transactions 30A:363369. Barsoum, M. W., T. El-Raghy, C. J. Rawn, W. D. Porter, H. Wang, A. Payzant and C. Hubbard. 1999. Thermal properties of Ti3SiC2. Journal of Physics and Chemistry of Solids 60:429439. Barsoum, M. W., L. Farber and T. El-Raghy. 1999. Dislocations, kink bands and room temperature plasticity of Ti3SiC2. Metallurgical and Materials Transactions 30A:17271738. Barsoum, M. W., M. Radovic, P. Finkel and T. El-Raghy. In press. Ti3SiC2 and ice. Applied Physics Letters. El-Raghy, T., and M. W. Barsoum. 1998. Diffusion kinetics of the carburization and silicidation of Ti3SiC2. Journal of Applied Physics 83:112119. Jeitschko, W., and H. Nowotny. 1967. Die Kristallstructur von Ti3SiC2Ein Neuer Komplxcarbid-Typ. Monatschrift fr Chemie 98:329337. Nickl, J. J., K. K. Schweitzer and P. Luxenberg. 1972. Gasphasenabscheidung im Systeme Ti-C-Si. Journal of the Less Common Metals 6:335353. Nowotny, H. 1970. Struktuchemie Einiger Verbindungen der bergangsmetalle mit den elementen C, Si, Ge, Sn. Progress in Solid State Chemistry 2:2762. Pampuch, R., J. Lis, L. Stobierski and M. Tymkiewicz. 1989. Solid combustion synthesis of Ti3SiC2. Journal of the European Ceramic Society 5:283287. Pietzka, M. A., and J. C. Schuster. 1994. Summary of constitution data of the system AlC-Ti. Journal of Phase Equilibria 15:392400.

Procopio, A. T., M. W. Barsoum and T. ElRaghy. 2000. Characterization of Ti4AlN3. Metallurgical and Materials Transactions 31A:333. Radovic, M., M. W. Barsoum, T. El-Raghy, J. Seidensticker and S. Wiederhorn. 2000. Tensile properties of Ti 3 SiC 2 in the 251300C temperature range. Acta Materialia 48:453459. Schuster, J. C., H. Nowotny and C. Vaccaro. 1980. The ternary systems: Cr-Al-C, V-Al-C and Ti-Al-C and the Behavior of the Hphases (M2AlC). Journal of Solid State Chemistry 32:213219. Tzenov, N., and M. W. Barsoum. 2000. Synthesis and characterization of Ti3AlC1.8. Journal of the American Ceramic Society 83:825-832. Yoo, H.-I., M. W. Barsoum and T. El-Raghy. 2000. Ti3SiC2 has negligible thermopower. Nature 407:581582.

Links to Internet resources for The MAX Phases: Unique New Carbide and Nitride Materials are available on the American Scientist Web site: http://www.americanscientist.org/ articles/01articles/barsoum.html

Sigma Xi, The Scientific Research Society. Reproduction with permission only. Contact perms@amsci.org.

2001

JulyAugust

343