Precipitation hardening, also called age hardening or particle hardening, is a heat treatment technique used to increase the yield strength of malleable materials, including most structural alloys of aluminium, magnesium, nickel, titanium, and some steels, stainless steels, and duplex stainless steel. In superalloys, it is known to cause yield strength anomaly providing excellent high-temperature strength.
Precipitation hardening relies on changes in solid solubility with temperature to produce fine particles of an impurity phase, which impede the movement of dislocations, or defects in a crystal's lattice. Since dislocations are often the dominant carriers of plasticity, this serves to harden the material. The impurities play the same role as the particle substances in particle-reinforced composite materials. Just as the formation of ice in air can produce clouds, snow, or hail, depending upon the thermal history of a given portion of the atmosphere, precipitation in solids can produce many different sizes of particles, which have radically different properties. Unlike ordinary tempering, alloys must be kept at elevated temperature for hours to allow precipitation to take place. This time delay is called "aging". Solution treatment and aging is sometimes abbreviated "STA" in specifications and certificates for metals.
Two different heat treatments involving precipitates can alter the strength of a material: solution heat treating and precipitation heat treating. Solid solution strengthening involves formation of a single-phase solid solution via quenching. Precipitation heat treating involves the addition of impurity particles to increase a material's strength.W.D. Callister. Fundamentals of Materials Science and Engineering, 2nd ed. Wiley & Sons. pp. 252.
Kinetics versus thermodynamics This technique exploits the phenomenon of supersaturation, and involves careful balancing of the driving force for precipitation and the thermal activation energy available for both desirable and undesirable processes. The most commonly accepted theory behind precipitation is classical nucleation theory (CNT).
Nucleation occurs at a relatively high temperature (often just below the solubility limit) so that the kinetic barrier of surface energy can be more easily overcome and the maximum number of precipitate particles can form. These particles are then allowed to grow at lower temperature in a process called ageing. This is carried out under conditions of low solubility so that thermodynamics drive a greater total volume of precipitate formation.
Diffusion's exponential dependence upon temperature makes precipitation strengthening, like all heat treatments, a fairly delicate process. Too little diffusion (under ageing), and the particles will be too small to impede dislocations effectively; too much (over ageing), and they will be too large and dispersed to interact with the majority of dislocations.
Alloy design Precipitation strengthening is possible if the line of solid solubility slopes strongly toward the center of a phase diagram. While a large volume of precipitate particles is desirable, a small enough amount of the alloying element should be added so that it remains easily soluble at some reasonable annealing temperature. Although large volumes are often wanted, they are wanted in small particle sizes as to avoid a decrease in strength as is explained below.
Elements used for precipitation strengthening in typical aluminium and titanium alloys make up about 10% of their composition. While binary alloys are more easily understood as an academic exercise, commercial alloys often use three components for precipitation strengthening, in compositions such as Al(Mg, Cu) and Ti(Al, V). A large number of other constituents may be unintentional, but benign, or may be added for other purposes such as grain refinement or corrosion resistance. An example is the addition of Sc and Zr to aluminum alloys to form FCC L12 structures that help refine grains and strengthen the material. In some cases, such as many aluminium alloys, an increase in strength is achieved at the expense of corrosion resistance. More recent technology is focused on additive manufacturing due to the higher amount of metastable phases that can be obtained due to the fast cooling, whereas traditional casting is more limited to equilibrium phases.
The addition of large amounts of nickel and chromium needed for corrosion resistance in stainless steels means that traditional hardening and tempering methods are not effective. However, precipitates of chromium, copper, or other elements can strengthen the steel by similar amounts in comparison to hardening and tempering. The strength can be tailored by adjusting the annealing process, with lower initial temperatures resulting in higher strengths. The lower initial temperatures increase the driving force of nucleation. More driving force means more nucleation sites, and more sites means more places for dislocations to be disrupted while the finished part is in use.
Many alloy systems allow the ageing temperature to be adjusted. For instance, some aluminium alloys used to make rivets for aircraft construction are kept in dry ice from their initial heat treatment until they are installed in the structure. After this type of rivet is deformed into its final shape, ageing occurs at room temperature and increases its strength, locking the structure together. Higher ageing temperatures would risk over-ageing other parts of the structure, and require expensive post-assembly heat treatment because a high ageing temperature promotes the precipitate to grow too readily.
Types of hardening There are several ways by which a matrix can be hardened by precipitates, which could also be different for deforming precipitates and non-deforming precipitates.Thosmas H. Courtney. Mechanical Behavior of Materials, 2nd ed. Waveland Press, Inc.. pp. 198-205.
Deforming particles (weak precipitates):
Coherency hardening occurs when the interface between the particles and the matrix is coherent, which depends on parameters like particle size and the way that particles are introduced. Coherency is where the lattice of the precipitate and that of the matrix are continuous across the interface. Small particles precipitated from supersaturated solid solution usually have coherent interfaces with the matrix. Coherency hardening originates from the atomic volume difference between precipitate and the matrix, which results in a coherency strain. If the atomic volume of the precipitate is smaller, there will be tension because the lattice atoms are located closer than their normal conditions while when the atomic volume of the precipitate is larger, there will be compression of the lattice atoms, as they are further apart than their normal position. Regardless of whether the lattice is under compression or tension, the associated stress field interacts with dislocations leading to decreased dislocation motion either by repulsion or attraction of the dislocations, leading to an increase in yield strength, similar to the size effect in solid solution strengthening. What differentiates this mechanism from solid solution strengthening is the fact that the precipitate has a definite size, not an atom, and therefore a stronger interaction with dislocations.
Modulus hardening results from the different shear modulus of the precipitate and the matrix, which leads to an energy change of dislocation line tension when the dislocation line cuts the precipitate. Also, the dislocation line could bend when entering the precipitate, increasing the affected length of the dislocation line. Again, the strengthening arises in a way similar to that of solid solution strengthening, where there is a mismatch in the lattice that interacts with the dislocations, impeding their motion. Of course, the severity of the interaction is different than that of solid solution and coherency strengthening.
Chemical strengthening is associated with the surface energy of the newly introduced precipitate-matrix interface when the particle is sheared by dislocations. Because it takes energy to make the surface, some of the stress that is causing dislocation motion is accommodated by the additional surfaces. Like modulus hardening, the analysis of interfacial area can be complicated by dislocation line distortion.
Order strengthening occurs when the precipitate is an ordered structure such that bond energy before and after shearing is different. For example, in an ordered cubic crystal with composition AB, the bond energy of A-A and B-B after shearing is higher than that of the A-B bond before. The associated energy increase per unit area is anti-phase boundary energy and accumulates gradually as the dislocation passes through the particle. However, a second dislocation could remove the anti-phase domain left by the first dislocation when traverses the particle. The attraction of the particle and the repulsion of the first dislocation maintains a balanced distance between two dislocations, which makes order strengthening more complicated. Except for when there are very fine particles, this mechanism is generally not as effective as others to strengthen. Another way to consider this mechanism is that when a dislocation shears a particle, the stacking sequence between the new surface made and the matrix is broken, and the bonding is not stable. To get the sequence back into this interface, another dislocation, is needed to shift the stacking. The first and second dislocation are often called a superdislocation. Because superdislocations are required to shear these particles, there is strengthening because of the decreased dislocation motion.
Non-deforming particles (strong precipitate):
In non-deforming particles, where the spacing is small enough or the precipitate-matrix interface is disordered, dislocation bows instead of shears. The strengthening is related to the effective spacing between particles considering finite particle size, but not particle strength, because once the particle is strong enough for the dislocations to bow rather than cut, further increase of the dislocation penetration resistance won't affect strengthening. The main mechanism therefore is Orowan strengthening, where the strong particles do not allow for dislocations to move past. Therefore bowing must occur and in this bowing can cause dislocation loops to build up, which decreases the space available for additional dislocation to bow between. If the dislocations cannot shear particles and cannot move past them, then dislocation motion is successfully impeded.
Theory
The primary species of precipitation strengthening are second phase particles. These particles impede the movement of dislocations throughout the lattice. You can determine whether or not second phase particles will precipitate into solution from the solidus line on the phase diagram for the particles. Physically, this strengthening effect can be attributed both to size and modulus effects, and to interfacial or surface energy.