Report on

Teflon

To Doctor

Moustafa Salem

By

George Alfred Aiad

469

1-Inroduction

2-Discussion A-Phyzical & Chemical Properties B- Synthesis of

Teflon

C- Properties of Teflon D- Applications of Teflon E- Emulsion polymerization

F- Toxicity

G- Recycling

3-Conclusion

1-Inroduction

Polytetrafluoroethylene (PTFE) was discovered on April 6, 1938 by Roy Plunkett, a research chemist at DuPont.

What seems to have happened is this. Plunkett and his technician assistant, Jack Rebok, were testing the chemical reactions of the refrigerant gas tetrafluoroethylene (TFE). One pressurized cylinder of the gas, which they themselves had filled earlier, failed to discharge when its valve was opened. They set the cylinder aside, but Rebok later noticed it was too heavy to be empty, and suggested they cut it open to see what had gone wrong. Plunkett agreed, despite the risk of an explosion; and they discovered that the gas inside the cylinder had inexplicably solidified into a white powder. Intrigued, Plunkett put his scheduled work aside and began to test the properties of this substance. It was much more lubricant than other slippery solids, like graphite; and in addition, it proved inert to virtually all other chemicals and had an extremely high melting point

In time, Plunkett found that the gas had polymerized (that is, its molecules had bonded), becoming polytetrafluoroethylene (PTFE) resin. Its unique properties were caused by an impenetrable shield of fluorine atoms which lock onto and protect the compound's essential string of carbon atoms. More importantly, Plunkett invented a way to reproduce the TFE-to-PTFE polymerization in the lab

2-Discussion

A-Phyzical & Chemical Properties

Nonpolarity: The carbon backbone of the linear polymer is completely sheathed by the electron cloud of fluorine atoms, much like a wire core is protected by insulation coating. This ensheathment, and the angles at which the carbon-fluorine bonds are disposed, causes the centers of electronegativity and electropositivity to be perfectly balanced across the polymer chain cross section. As a result, no net charge difference prevails. This Nonpolarity of the polymer is partly responsible for its lack of chemical reactivity. Low interchain forces: The bond forces between two adjacent polymer chains are significantly lower than the forces within one chain. PFA PTFE linear polymer chains are otherwise restrained. However, in PFA FEP and PFA, interpolymer chain entanglement of the pendant structure precludes the shifting of polymer chains to relieve the implied load. The "creep" normally associated with PFA PTFE is mostly avoided with PFA FEP and even more so with PFA. High C-F and C-C bond strengths are among the strongest in single bond organic chemistry. The polymer must absorb considerable energy to disrupt these bonds. Chemical reactions represent a kinetic and thermodynamic resolution of bond-making and bond-breaking in favor of the most stable system. These bond strengths are hard to overcome. Crystallinity: The high degree of crystallinity in these semicrystalline polymers results in high melting points, mechanical properties, and an integral barrier to migrating, small, nonpolar molecules. Under certain conditions, these molecules penetrate the plastics. High degree of polymerization: The unbranched nature of the polymers and their low interpolymer chain attraction requires very long chain lengths in PFA PTFE and entanglement in PFA FEP and PFA to provide load-bearing mechanical properties. The chain length also has an impact on flow and crystallinity of the polymers. These unique properties lead to the following benefits: High melting points (327C [621F] for PFA PTFE; 260C [500F] for PFA FEP, and 305C [582F] for PFA PFA). The melting point of PFA PTFE is one of the highest in organic polymer chemistry. Other materials can attain higher temperatures, but they degrade rather than melt. Compared to PFA PTFE, the lower melting temperature of PFA FEP results from lower of polymerization and crystallinity. In PFA PFA, a higher degree of polymerization, enhanced entanglement of the pendant structure and lower comonomer content combine to provide a melting point closer to that of PFA PTFE. High thermal stability: Due to the strength of the carbon-fluorine and carbon-carbon single bonds, appreciable thermal energy must be absorbed by the polymers before thermal degradation. The rate of decomposition of a part of PFA depends on the particular resin, temperature, and heat exposure time; and to a lesser extent, pressure and nature of the environment. At maximum continuous service temperatures, thermal degradation of the resins is minimal. For example, at 400C, PFA FEP is measured at 4/100,000 of 1 percent, and PFA PTFE at 1/100,000 of 1 percent. At high processing temperatures, adequate ventilation is recommended. High upper service temperature (260C [500F] for PFA PTFE, 204C [400F] for PFA FEP and 260C [500F] for PFA). The polymers' high melting points and morphological features allow components made from the resin to be used continuously at the stated temperatures. Above this temperature, the component's

physical properties may begin to decrease. The polymer itself, however, will be unaffected if the temperature is insufficient for thermal degradation. Insolubility: There is no known solvent for PFA fluorocarbon resins under ordinary conditions. Inertness to chemical attack: The intrapolymer-chain bond strengths preclude reaction with most chemicals. Under relatively unusual circumstances the polymer can be made to react. Examples of unusual reagents include: - Sodium, in a suitable media, etches the fluorocarbon polymer. - Finely divided metals often interact with the polymer. - Interhalogen compounds often induce halogen interchange with the fluorine. - Ionized oxygen in oxygen plasma is often sufficiently energetic to react with the polymer chain. - Electron bombardment at the megarad level can sever the polymer chain. Low coefficient of friction: The low coefficient of friction of PFA results from low interfacial forces between its surface and another material and the comparatively low force to deform. Low dielectric constant and dissipation factor: PFA provides low, if not the lowest, values for these parameters. These low values arise from the polymer's Nonpolarity as well as the tight electron hold in the ultrapolymer bonds. Low water absorptivity: For PFA to absorb water, the surface must remain wet for a long enough time for water to become physico-chemically associated with the polymer chains, and then it must become included in the polymer bulk structure. Water is a very high energy material and PFA has a very low surface energy. Therefore, these events are energetically incompatible and only occur under special circumstances and to a small extent. Excellent weatherability: Weather includes light of various wavelengths (IR, visible, UV), water (liquid or gas), other gases, and normal temperatures and pressure. The physical and chemical makeup of PFA makes it inert to these influences. Flame resistant: PFA will burn when exposed to flame, but will not continue to burn when the flame is removed. Excellent toughness: Some mechanical properties of PFA resins are shown in Table 1. Toughness characteristics are high and differ somewhat between resin types.

Unique properties associated with fluoropolymers :

High temperature stability (300 to 350 deg C) This is sometimes called "thermal resistance" chemical resistance These properties result from the great stability of the C-F bond, and also the small size of the fluorine, which makes it possible for the fluorine atoms to pack tightly about the polymer backbone. self-lubricating

B- Synthesis of

Teflon

F F | | C=C | | F F

The monomer of PTFE ( [C2F4]n ), as stated above is tetrafluoroethylene (C2F4). It is comprised of a double bonded two carbon backbone and four fluorine molecules. Fluoropolymers have significantly different behaviors than hydrocarbon chains. Fluorine is a highly reactive element. It the most electronegative of all elements, has unshared electron pairs, and is more easily converted to F- than H is to H-. Bond strength is higher for C-F bonds over C-H bonds (116 kcal/mole vs. 99.5 kcal/mole). F is larger than H, and the C-F bond is more highly polarized than a C-H bond in hydrocarbons. The synthesis of PTFE can be accomplished through emulsion polymerization under pressure, using freeradical catalysts (i.e. peroxides or persulfates) under pressure with oxygen, peroxides, or peroxydisulfates. Polymerization of tetrafluoroethylene is highly exothermic and generates 41.12 kcal/mole heat. PTFE does not branch due to the polarity and strength of the C-F bonds. It does form a helical conformation which helps minimize the steric repulsion of the large fluorine atoms. At temperatures of up to up to 19 C the polymer rotates 180 in the length of 13 carbons. Above 19 C it rotates 180 around in 15 carbons. It is inert to chemicals and solvents up to 300C. In fact, the only things that react with it above that temperature are molten alkali metals, chlorine trifluoride, and gaseous fluorine. The size of the fluorine atom and the C-F bond length are such that the carbon back bone is blanketed with fluorine atoms which render the C-F bond impervious to attack. It has an initial melting point of 342 +- 10 degrees Celsius and a secondary melting point of 327 +- 10 degrees Celsius. PTFE also can temporarily withstand temperatures of 260 degrees Celsius and still have the same chemical properties. PTFE retains its chemical properties in cryogenic temperatures of -240 degrees Celsius. It is very stable in its normal temperature range. Fluoropolymers do not ignite easily and do not sustain flame. To get PTFE to burn on its own you have to provide it with an atmosphere of over 95% oxygen. PTFE has the lowest coefficient of friction of any polymer (Dynamic coefficient of Friction is 0.04)

1-Synthesis of tetrafluoroethylene from chloroform via an exchange process:

H | Cl - C - Cl | Cl H | Cl - C - F | F F F | | C = C | | F F

HF -----> SbF 5

--->

From the notes it appears that the step where HCl is eliminated is achieved by mixing the chlorodifluoromethane with steam at 950 deg C, but that temperature seems excessively high, sufficient to cause combustion, so this needs to be checked: Scrub gases are employed to remove the HCl, then the tetrafluoroethylene is distilled.

2-Synthesis of teflon- Poly(tetrafluoroethylene) (teflon) is prepared via suspension polymerization.

F F | | C = C | | F F F F | | -[- C - C -]| | F F

--->

The conventional suspension polymerization techniques produce a granula product suitable for moulding and extrusion. CF2 = CF2 is polymerized under pressure in stainless steel autoclaves with free radical initiators such as ammonium persulfate. The reaction is rapid and exothermic and requires careful temperature control. the product is a high molecular weight polymer. Conditions can be modified to give a dispersion of polymer of a much finer particle size and a lower molecular weight.

C- Properties of Teflon

Teflon is a white opaque solid with a waxy appearance and feel. It is a tough flexible material of moderate tensile strength with a tendency to under creep under compression (this is an inference to "cold flow.") Teflon has outstanding electrical insulating properties, and of course, Its "non-stick" properties are excellent. Teflon has a high crystallinity, and a chemical resistance to everything except molten alkali metals and fluorine. It is insoluble in everything except fluorocarbon oils at very high temperatures (temperature must be as high as the crystalline melting point temperature.) It has good thermal stability and Good weather resistance. Teflon is self lubricating And its nonstick properties correspond to its very low coefficient of friction. The relatively stiff coil makes Teflon slippery. Teflon has a low glass transition temperature. You can't plasticize Teflon because the plasticizer will leach out.

D- Applications of Teflon

wire coatings gaskets holders and spacers pump parts lab equipment non-stick coverings in kitchen utensils low friction linings for hoppers diaphragms for low temperature equipment

E- Emulsion polymerization

Emulsion polymerization is when a liquid monomer is submerged in an insoluble liquid This causes emulsion, the suspension of small micelles of liquid in another liquid because together they are unable to form a solution. Most emulsion polymerizations require an emulsifier, which is a surfactant that helps promote emulsion of the non dissolving liquid. PTFE has the advantage of having no known solvent, making it ideal for emulsion polymerization. The TFE monomer can be dissolved in an inert solvent with the rest of the polymerization system. After polymerization, the PTFE precipitates out of the solution, making it easy to collect.

F- Toxicity

The monomer TFE is a confirmed animal carcinogen with unknown relevance to humans. The finished polymer in solid form is inert under ordinary conditions. There is some indication that the powdered forms of PTFE may be carcinogenic if inhaled

Monomer Health Effects Causes acute effects when inhaled, including irritation of upper respiratory tract and eyes, mild depression of central nervous system, nausea and vomiting, and dry cough. Massive inhalation produces cardiac arrhythmia, cardiac arrest, and death. A study by National Toxicology Program has reported kidney and liver tumors in rats and mice, which had exposed to lifetime inhalation of TFE. Relationship to human response has not been established. An exposure limit of 5ppm has been established by fluoropolymer producers. The monomer TFE is a confirmed animal carcinogen with unknown relevance to humans.

G- Recycling

It is easy to recycle since no chemical reaction is necessary. Only the extruded forms are recycled (not the resin or powerdered forms) it is separated from impurities and heated to a working temperature. It is then extruded in a long strand which can then be cut down to pellets and shipped to manufacturing companies that use the recycled material. Alternately it is simply ground up to form powders.

The incentive to recycle fluoroplastic scrap has a strong economic component due to the high value of these plastics. In reforming the product, the molecular weight is lowered, Lowering of molecular weight adversely affects a number of properties of parts made from recycled fluoroplastics. Because the molecular weight distribution in PTFE is usually not controlled, the uses of recycled PTFE are restricted. It is typically ground up into fine powders and used as additives in such products as inks, paints, and cosmetics

References:

http://web.mit.edu/invent/iow/plunkett.html http://www.omega.com/techref/fluoro.html http://web.mst.edu/~wlf/chem381/chap26.html