Sintering or frittage is the process of compacting and forming a solid mass of material by pressure or heat without melting it to the point of liquefaction. Sintering happens as part of a manufacturing process used with metals, ceramics, plastics, and other materials. The atoms/molecules in the sintered material diffuse across the boundaries of the particles, fusing the particles together and creating a solid piece.
Since the sintering temperature does not have to reach the melting point of the material, sintering is often chosen as the shaping process for materials with extremely high melting points, such as tungsten and molybdenum. The study of sintering in metallurgical powder-related processes is known as powder metallurgy.
An example of sintering can be observed when ice cubes in a glass of water adhere to each other, which is driven by the temperature difference between the water and the ice. Examples of pressure-driven sintering are the compacting of snowfall to a glacier, and the formation of a hard snowball by pressing loose snow together.
The material produced by sintering is called sinter. The word sinter comes from the Middle High German , a cognate of English cinder.
General sintering
In manufacturing, sintering is generally considered successful when the process reduces porosity and enhances properties such as strength, electrical conductivity, translucency and thermal conductivity. In some special cases, sintering is carefully applied to enhance the strength of a material while preserving porosity (like in filters or catalysts, where gas adsorption is a priority). During the sintering process, atomic diffusion drives powder surface elimination in different stages, starting at the formation of necks between powders to final elimination of small pores at the end of the process.
The driving force for densification is the change in free energy from the decrease in surface area and lowering of the surface free energy by the replacement of solid-vapor interfaces. It forms new but lower-energy solid-solid interfaces with a net decrease in total free energy. On a microscopic scale, material transfer is affected by the change in pressure and differences in free energy across the curved surface. If the size of the particle is small (and its curvature is high), these effects become very large in magnitude. The change in energy is much higher when the radius of curvature is less than a few micrometers, which is one of the main reasons why much ceramic technology is based on the use of fine-particle materials.
The ratio of bond area to particle size is a determining factor for properties such as strength and electrical conductivity. To yield the desired bond area, temperature and initial grain size are precisely controlled over the sintering process. At steady state, the particle radius and the vapor pressure are proportional to (p0)2/3 and to (p0)1/3, respectively.
The source of power for solid-state processes is the change in free or chemical potential energy between the neck and the surface of the particle. This energy creates a transfer of material through the fastest means possible; if transfer were to take place from the particle volume or the grain boundary between particles, particle count would decrease and pores would be destroyed. Pore elimination is fastest in samples with many pores of uniform size because the boundary diffusion distance is smallest. During the latter portions of the process, boundary and lattice diffusion from the boundary become important.
Control of temperature is very important to the sintering process, since grain-boundary diffusion and volume diffusion rely heavily upon temperature, particle size, particle distribution, material composition, and often other properties of the sintering environment itself.
Ceramic sintering
Sintering is part of the firing process used in the manufacture of pottery and other ceramic objects. Sintering and vitrification (which requires higher temperatures) are the two main mechanisms behind the strength and stability of ceramics. Sintered ceramic objects are made from substances such as glass, alumina, zirconia, silica, magnesia, lime, beryllium oxide, and ferric oxide. Some ceramic raw materials have a lower affinity for water and a lower plasticity index than clay, requiring organic additives in the stages before sintering.
Sintering begins when sufficient temperatures have been reached to mobilize the active elements in the ceramic material, which can start below their melting point (typically at 50–80% of their melting point), e.g. as premelting. When sufficient sintering has taken place, the ceramic body will no longer break down in water; additional sintering can reduce the porosity of the ceramic, increase the bond area between ceramic particles, and increase the material strength.
Industrial procedures to create ceramic objects via sintering of powders generally include:
mixing water, binder, deflocculant, and unfired ceramic powder to form a slurry spray-drying the slurry putting the spray dried powder into a mold and pressing it to form a green body (an unsintered ceramic item) heating the green body at low temperature to burn off the binder sintering at a high temperature to fuse the ceramic particles together.
All the characteristic temperatures associated with phase transformation, glass transitions, and melting points, occurring during a sinterisation cycle of a particular ceramic's formulation (i.e., tails and frits) can be easily obtained by observing the expansion-temperature curves during optical dilatometer thermal analysis. In fact, sinterisation is associated with a remarkable shrinkage of the material because glass phases flow once their transition temperature is reached, and start consolidating the powdery structure and considerably reducing the porosity of the material.
Sintering is performed at high temperature. Additionally, a second and/or third external force (such as pressure, electric current) could be used. A commonly used second external force is pressure. Sintering performed by only heating is generally termed "pressureless sintering", which is possible with graded metal-ceramic composites, utilising a nanoparticle sintering aid and bulk molding technology. A variant used for 3D shapes is called hot isostatic pressing.
To allow efficient stacking of product in the furnace during sintering and to prevent parts sticking together, many manufacturers separate ware using ceramic powder separator sheets. These sheets are available in various materials such as alumina, zirconia and magnesia. They are additionally categorized by fine, medium and coarse particle sizes. By matching the material and particle size to the ware being sintered, surface damage and contamination can be reduced while maximizing furnace loading.
Sintering of metallic powders
Most metals can be sintered, although some with greater difficulty (i.e., aluminium alloy and titanium alloysGerman, R. M. (2020). Titanium sintering science: A review of atomic events during densification. International Journal of Refractory Metals and Hard Materials, 89, 105214. https://doi.org/10.1016/j.ijrmhm.2020.105214). This applies especially to pure metals produced in vacuum which suffer no surface contamination. Sintering under atmospheric pressure requires the use of a protective gas, quite often endothermic gas. Sintering, with subsequent reworking, can produce a great range of material properties. Changes in density, alloying, and heat treatments can alter the physical characteristics of various products. For instance, the Young's modulus En of sintered iron powders remains somewhat insensitive to sintering time, alloying, or particle size in the original powder for lower sintering temperatures, but depends upon the density of the final product:
where D is the density, E is Young's modulus and d is the maximum density of iron.
Sintering is static when a metal powder under certain external conditions may exhibit coalescence, and yet reverts to its normal behavior when such conditions are removed. In most cases, the density of a collection of grains increases as material flows into voids, causing a decrease in overall volume. Mass movements that occur during sintering consist of the reduction of total porosity by repacking, followed by material transport due to evaporation and condensation from diffusion. In the final stages, metal atoms move along crystal boundaries to the walls of internal pores, redistributing mass from the internal bulk of the object and smoothing pore walls. Surface tension is the driving force for this movement.
A special form of sintering (which is still considered part of powder metallurgy) is liquid-state sintering in which at least one but not all elements are in a liquid state. Liquid-state sintering is required for making cemented carbide and tungsten carbide.
Sintered bronze in particular is frequently used as a material for bearings, since its porosity allows lubricants to flow through it or remain captured within it. Sintered copper may be used as a wicking structure in certain types of heat pipe construction, where the porosity allows a liquid agent to move through the porous material via capillary action. For materials that have high melting points such as molybdenum, tungsten, rhenium, tantalum, osmium and carbon, sintering is one of the few viable manufacturing processes. In these cases, very low porosity is desirable and can often be achieved.
Sintered metal powder is used to make frangible shotgun shells called breaching rounds, as used by military and SWAT teams to quickly force entry into a locked room. These shotgun shells are designed to destroy door deadbolts, locks and hinges without risking lives by ricocheting or by flying on at lethal speed through the door. They work by destroying the object they hit and then dispersing into a relatively harmless powder.
Sintered bronze and stainless steel are used as filter materials in applications requiring high temperature resistance while retaining the ability to regenerate the filter element. For example, sintered stainless steel elements are employed for filtering steam in food and pharmaceutical applications, and sintered bronze in aircraft hydraulic systems.
Sintering of powders containing precious metals such as silver and gold is used to make small jewelry items. Evaporative self-assembly of colloidal silver nanocubes into supercrystals has been shown to allow the sintering of electrical joints at temperatures lower than 200 °C.
Advantages Particular advantages of the powder technology include:
Very high levels of purity and uniformity in starting materials Preservation of purity, due to the simpler subsequent fabrication process (fewer steps) that it makes possible Stabilization of the details of repetitive operations, by control of grain size during the input stages Absence of binding contact between segregated powder particles – or "inclusions" (called stringering) – as often occurs in melting processes No deformation needed to produce directional elongation of grains Capability to produce materials of controlled, uniform porosity. Capability to produce nearly net-shaped objects. Capability to produce materials which cannot be produced by any other technology. Capability to fabricate high-strength material like turbine blades. After sintering the mechanical strength to handling becomes higher.
The literature contains many references on sintering dissimilar materials to produce solid/solid-phase compounds or solid/melt mixtures at the processing stage. Almost any substance can be obtained in powder form, through either chemical, mechanical or physical processes, so basically any material can be obtained through sintering. When pure elements are sintered, the leftover powder is still pure, so it can be recycled.
Plastics sintering