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Polydimethylsiloxane (PDMS) is the most widely used silicon-based organic polymer, and is particularly known for its unusual rheological (or flow) properties. It is optically clear, and is generally considered to be inert, non-toxic and non-flammable. PDMS has been assigned CAS number 63148-62-9, and is occasionally called dimethicone. It is one of several types of silicone oil.
The chemical formula for PDMS is (CH3)3SiO[SiO(CH3)2]nSi(CH3)3, where n is the number of repeating monomer [SiO(CH3)2] units. Industrial synthesis can begin from dimethylchlorosilane and water by the following net reaction:
n[Si(CH3)2Cl2] + n[H2O] → [SiO(CH3)2]n + 2n[HCl]
This also produces hydrochloric acid, which is generally released as a gas. For medical uses, a process was developed where the chlorine atoms in the silane precursor were replaced with acetate groups, so that the reaction product of the final curing process is nontoxic acetic acid (vinegar). As a side effect, the curing process is also much slower in this case. This is the chemistry used in consumer applications, such as silicone caulk and adhesives.
Silane precursors with more acid-forming groups and fewer methyl groups, such as methyltrichlorosilane, can be used to introduce branches or cross-links in the polymer chain. Ideally, each molecule of such a compound becomes a branch point. This can be used to produce hard silicone resins. Similarly, precursors with three methyl groups can be used to limit molecular weight, since each such molecule has only one reactive site and so forms the end of a siloxane chain.
The polymer is manufactured in multiple viscosities, ranging from a thin pourable liquid (when n is very low), to a thick rubbery semi-solid (when n is very high). PDMS molecules have quite flexible polymer backbones (or chains) due to their siloxane linkages, which are analogous to the ether linkages used to impart rubberiness to polyurethanes. Such flexible chains become loosely entangled when molecular weight is high, which results in PDMS having an unusually high level of viscoelasticity.
Viscoelasticity means that at long flow times (or high temperatures), PDMS acts like a viscous liquid, similar to honey. However at short flow times (or low temperatures) it acts like an elastic solid, similar to rubber. In other words, if you leave some PDMS on a surface overnight (long flow time), it will flow to cover the surface and mold to any surface imperfections. However if you roll the same PDMS into a sphere and throw it onto the same surface (short flow time), it will bounce like a rubber ball.
Although the viscoelastic properties of PDMS can be intuitively observed using the simple experiment described above, they can be more accurately measured using dynamic mechanical analysis. This involves using a specialized instrument to determine the material's flow characteristics over a wide range of temperatures, flow rates, and deformations. Because of PDMS's chemical stability, it is often used a calibration fluid for this type of experiment.
Many people are indirectly familiar with PDMS because it is the primary component in Silly Putty, to which PDMS imparts its characteristic viscoelastic properties. The rubbery, vinegary-smelling silicone caulks, adhesives, and aquarium sealants are also well-known. PDMS is also used as a component in silicone grease and other silicone based lubricants, as well as in defoaming agents, damping fluids, heat transfer fluids, cosmetics and other applications. PDMS has also been used as a filler fluid in breast implants, although this practice has decreased somewhat, due to safety concerns. It continues to be used in knuckle replacement implants, with good results.
Activated dimethicone, a mixture of polydimethylsiloxanes and silicon dioxide (sometimes called simethicone), is used in over-the-counter preparations as an anti-foaming agent and carminative.
As a food additive, it has the E number E900 and is used as an anti-foaming agent and an anti-caking agent.