|Density||965 kg m−3|
|Melting point||N/A (vitrifies)|
|Boiling point||N/A (vitrifies)|
|Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)|
|(what is: / ?)|
Polydimethylsiloxane (PDMS) belongs to a group of polymeric organosilicon compounds that are commonly referred to as silicones. PDMS is the most widely used silicon-based organic polymer, and is particularly known for its unusual rheological (or flow) properties. PDMS is optically clear, and, in general, inert, non-toxic, and non-flammable. It is also called dimethicone and is one of several types of silicone oil (polymerized siloxane). Its applications range from contact lenses and medical devices to elastomers; it is also present in shampoos (as dimethicone makes hair shiny and slippery), food (antifoaming agent), caulking, lubricating oils, and heat-resistant tiles.
- 1 Structure
- 2 Mechanical properties
- 3 Chemical compatibility
- 4 Applications
- 5 Safety and environmental considerations
- 6 See also
- 7 References
- 8 External links
The chemical formula for PDMS is CH3[Si(CH3)2O]nSi(CH3)3, where n is the number of repeating monomer [SiO(CH3)2] units. Industrial synthesis can begin from dimethyldichlorosilane and water by the following net reaction:
- n Si(CH3)2Cl2 + n+1 H2O → HO[-Si(CH3)2O-]n H + 2n HCl
The polymerization reaction evolves hydrogen chloride. For medical and domestic applications, a process was developed in which the chlorine atoms in the silane precursor were replaced with acetate groups. In this case, the polymerization produces acetic acid, which is less chemically aggressive than HCl. As a side-effect, the curing process is also much slower in this case. The acetate is used in consumer applications, such as silicone caulk and adhesives.
Branching and capping
- 2 Si(CH3)3Cl + [Si(CH3)2O]n-2[Si(CH3)2OH]2 → [Si(CH3)2O]n-2[Si(CH3)2O Si(CH3)3]2 + 2 HCl
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. Under ideal conditions, each molecule of such a compound becomes a branch point. This can be used to produce hard silicone resins. In a similar manner, 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.
Well-defined PDMS with a low polydispersity index and high homogeneity is produced by controlled anionic ring-opening polymerization of hexamethylcyclotrisiloxane. Using this methodology it is possible to synthesize linear block copolymers, heteroarm star-shaped block copolymers and many other macromolecular architectures.
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' unusually high level of viscoelasticity.
PDMS is viscoelastic, meaning that at long flow times (or high temperatures), it 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 some PDMS is left on a surface overnight (long flow time), it will flow to cover the surface and mold to any surface imperfections. However, if the same PDMS is rolled into a sphere and thrown 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 method requires determination of 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 as a calibration fluid for this type of experiment.
After polymerization and cross-linking, solid PDMS samples will present an external hydrophobic surface. This surface will appear metallic and shiny, although the substrate is clear. This surface chemistry makes it difficult for polar solvents (such as water) to wet the PDMS surface, and may lead to adsorption of hydrophobic contaminants. Plasma oxidation can be used to alter the surface chemistry, adding silanol (SiOH) groups to the surface. Atmospheric air plasma & argon plasma will work for this application. This treatment renders the PDMS surface hydrophilic, allowing water to wet it. This is frequently required for water-based microfluidics. The oxidized surface resists adsorption of hydrophobic and negatively charged species. The oxidized surface can be further functionalized by reaction with trichlorosilanes. After a certain amount of time, recovery of the surface's hydrophobicity is inevitable, regardless of whether the surrounding medium is vacuum, air, or water; the oxidized surface is stable in air for about 30 minutes.
Solid PDMS samples (whether surface oxidized or not) will not allow aqueous solvents to infiltrate and swell the material. Thus PDMS structures can be used in combination with water and alcohol solvents without material deformation. However most organic solvents will diffuse into the material and cause it to swell, making them incompatible with PDMS devices. Despite this, some organic solvents lead to sufficiently small swelling that they can be used with PDMS, for instance within the channels of PDMS microfluidic devices. The swelling ratio is roughly inversely related to the solubility parameter of the solvent. Diisopropylamine swells PDMS to the greatest extent; solvents such as chloroform, ether, and THF swell the material to a large extent. Solvents such as acetone, 1-propanol, and pyridine swell the material to a small extent. Alcohols and polar solvents such as methanol, glycerol and water do not swell the material appreciably.
Surfactants and antifoaming agents
PDMS is a common surfactant and is a component of defoamers, which are used to suppress the formation of foams. PDMS in a modified form is used as an herbicidal penetrant and is a critical ingredient in water-repelling coatings, such as Rain-X.
Dimethicone is also the active silicone fluid in automotive viscous limited slip differentials and couplings. This is usually a non-serviceable OEM component but can be replaced with mixed performance results due to variances in effectiveness caused by refill weights or non-standard pressurizations.
PDMS is commonly used as a stamp resin in the procedure of soft lithography, making it one of the most common materials used for flow delivery in microfluidics chips. The process of soft lithography consists of creating an elastic stamp, which enables the transfer of patterns of only a few nanometers in size onto glass, silicon or polymer surfaces. With this type of technique, it is possible to produce devices that can be used in the areas of optic telecommunications or biomedical research. The stamp is produced from the normal techniques of photolithography or electron-beam lithography. The resolution depends on the mask used and can reach 6 nm.
In biomedical (or biological) microelectromechanical systems (bio-MEMS), soft lithography is used extensively for microfluidics in both organic and inorganic contexts. Silicon wafers are used to design channels, and PDMS is then poured over these wafers and left to harden. When removed, even the smallest of details is left imprinted in the PDMS. With this particular PDMS block, hydrophilic surface modification is conducted using plasma etching techniques. Once surface bonds are disrupted, usually a piece of glass slide is placed on the activated side of the PDMS (the side with imprints). Once the bonds relax to their normal state, the glass is permanently sealed to the PDMS, thus creating a waterproof channel. With these devices, researchers can utilize various surface chemistry techniques for different functions creating unique lab-on-a-chip devices for rapid parallel testing. PDMS can be cross-linked into networks and is a commonly used system for studying the elasticity of polymer networks. PDMS can be directly patterned by surface-charge lithography.
Medicine and cosmetics
PDMS is used variously in the cosmetic and consumer product industry as well. For example, PDMS can be used in the treatment of head lice on the scalp and dimethicone is used widely in skin-moisturizing lotions where it is listed as an active ingredient whose purpose is "skin protection." Some cosmetic formulations use dimethicone and related siloxane polymers in concentrations of use up to 15%. The Cosmetic Ingredient Review's (CIR) Expert Panel, has concluded that dimethicone and related polymers are "safe as used in cosmetic formulations."
PDMS compounds such as amodimethicone, are effective conditioners when formulated to consist of small particles and be soluble in water or alcohol/act as surfactants (especially for damaged hair), and are even more conditioning to the hair than common Dimethicone and/or Dimethicone copolyols.
Domestic and niche uses
Many people are indirectly familiar with PDMS because it is an important 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, mold release agents, damping fluids, heat transfer fluids, polishes, cosmetics, hair conditioners and other applications. PDMS has also been used as a filler fluid in breast implants.
Safety and environmental considerations
According to Ullmann's Encyclopedia, no "marked harmful effects on organisms in the environment" have been noted for siloxanes. PDMS is nonbiodegradable, but is absorbed in waste water treatment facilities. Its degradation is catalyzed by various clays.
- Siloxanes and other organosilicon compounds
- Polymethylhydrosiloxane (PMHS)
- Silicone rubber
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- Conditioning Agents for Hair and Skin, by Randy Schueller and Perry Romanowski, page 273, retrieved on 11 Nov 2014. Amodimethicone is recognized for its extremely robust conditioning and for its ability to form clear products when used in high-surfactant shampoos. Amodimethicone is a useful ingredient in conditioners, gels, mousses, and permanents, but its use in shampoos has proved troublesome due to interactions between the cationic and the anionic surfactants, which can result in compatibility problems. However, the amodimethicone emulsion can be made compatible in high-surfactant-level shampoos
- Principles of Polymer Science and Technology in Cosmetics and Personal Care, by E. Desmond Goddard & James V. Gruber, page 299, retrieved on 11 Nov 2014. Amodimethicone is typically an emulsion-polymerized polymer; however, utilizing linear processing technology amodimethicone fluids may be prepared as neat fluids, and then emulsified by a mechanical process as desired. The most widely utilized amodimethicone emulsions contain as the surfactant pair either (1) tallowtrimonium chloride (and) nonoxy- nol-10, or (2) cetrimonium chloride (and) trideceth-10 or -12. These "uncapped" amino- functional silicone compounds may be characterized by a linear or branched structure. In either case, amodimethicone polymers will undergo a condensation cure reaction during drying to form a somewhat durable elastomeric film on the hair, providing wet- and dry- combing benefits, lowering triboelectric charging effects, and increasing softness of the dry hair. They are excellent conditioning agents, often found in conditioners, mousses, setting lotions, and less frequently in 2-in-l shampoos
- Ingredients and Production of Cosmetics: Technology of Skin- and Hair-Care Products in Japan, Hiroshi Iwata and Kunio Shimada, Springer Science & Business Media, page 144, retrieved on 11 Nov 2014. Amodimethicone is the most widely used amino-modified silicone. It has an aminopropyl group attached to the methyl group of Dimethicone. Amodimethicone of various degrees of amino modification are available as well as those that have POP, POE, or an alkyl group attached. Amino-modified silicones are cationic and affinitive to hair keratin. They are particularly highly affinitive to damaged hair, which is anionic due to the presence of cysteic acid
- Handbook of Cosmetic Science and Technology, Fourth Edition, André O. Barel, Marc Paye, Howard I. Maibach, page 567, retrieved on 11 Nov 2014. ...and amodimethicone, which is an amino-substituted silicone and silicone quats, which contain permanently quaternized ammonium groups. In general, amodimethicones and silicone quats condition better than dimethicones, which condition better than dimethicone copolyols
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