Bonding fluoropolymers

Table 7.3. Peel Strength of Adhesive Bonded Fluoropolymers ...

Fig. 2.10. Chemical state images obtained with the Escascope in Fig. 2.9, from a contaminated fluoropolymer [2.29]. (A) image in contribution to C Is from C-F bonding, (B) image in contribution to C Is from C-C bonding.

While polymeric surfaces with relatively high surface energies (e.g. polyimides, ABS, polycarbonate, polyamides) can be adhered to readily without surface treatment, low surface energy polymers such as olefins, silicones, and fluoropolymers require surface treatments to increase the surface energy. Various oxidation techniques (such as flame, corona, plasma treatment, or chromic acid etching) allow strong bonds to be obtained to such polymers. 

Curiously, fluorine incorporation can result in property shifts to opposite ends of a performance spectrum. Certainly with reactivity, fluorine compounds occupy two extreme positions, and this is true of some physical properties of fluoropolymers as well. One example depends on the combination of the low electronic polarizability and high dipole moment of the carbon-fluorine bond. At one extreme, some fluoropolymers have the lowest dielectric constants known. At the other, closely related materials are highly capacitive and even piezoelectric. 

Thus, the strong C—F bond, the special arrangement of atoms in macromolecule, and low surface energy impart some unique physical properties to PTFE and other fluoropolymers high chemical and thermal resistance, nonstick character, low friction coefficient, and low wettability. This combination of properties... 

Teflon is the brand name for the chemical compound called polytetrafluoroethylene (PTFE). One molecule of PTFE contains two carbon atoms bonded to four fluorine atoms. Many molecules of PTEE can form polymer chains known as fluoropolymers. 

Carbon-fluorine bonds also have unusual electrooptical properties. Fluoropolymers are often used to provide favorable electrical properties such as low dielectric constants. The low dielectric constants are another consequence of the relatively low polarizability of C—F bonds. Polarizability a is related to index of refraction n through the following equation ... 

Arguments similar to those stated above can be used to explain the relative chemical inertness of fluoropolymers. Consider the reactivity of alkanes vs. perfluoroalkanes as shown in Table 4.2 (abstracted from Sheppard and Sharts Statistically, FA based materials will have many more types of bonds, in addition to C—F, than fluoropolymers. These bonds will be subject to the same chemical fate during assault by aggressive reagents as bonds in their hydrocarbon counterparts. Similar reasoning can be used to explain the relative thermal stability of FAs compared to fluoropolymers. Thus, incorporation of perfluoroalkyl groups will not make the modified material less stable than the native one. 

Electrooptical properties will be covered only briefly. Fluorocarbons find widespread utility in altering electrooptical properties of coatings. These properties are to be considered as derived from bulk properties of the fluorocarbon. In that regard, fluoropolymers are the most often selected. It is known from Eq. (2) that the electrooptical properties of fluorocarbons can be linked directly to the nature of the C—F bond (a oc n and e <=< n ). It is instructive to consider some relevant values. The dielectric constants e of PTFE, PE, and nylon-6,6 have been determined to be 2.1 (60 Hz-2 GHz), 2.2-2.3 (1 kHz), and 3.6-3.0 (100 Hz-1 GHz), respectively. The dielectric constants for PE and PTFE are comparable. The explanation can be found by comparing segmental polarizabilities a for groups with C—F bonds versus those with C—H bonds, as shown in Table 4.1. They are nearly identical. As e is related to a, it is not surprising that PE and PTFE have similar dielectric constants. The value of e for nylon-6,6 is included above for comparison. 

All of the unique properties imparted by fluorocarbons can be traced back to a single origin the nature of the C—F bond. These properties include low surface tension, excellent thermal and chemical stability, low coefficient of friction, and low dielectric constant. However, not all of these properties are possessed by the entire inventory of available fluorocarbons. The fluorocarbons can be assigned to two major categories (1) fluoropolymers, which are materials that are comprised mainly of C—F bonds and include such examples as PTFE, and (2) fluorochemicals (FA) based on the perfluoroalkyl group, which are materials that generally have fewer C—F bonds and often exist as derivatives of other classes of molecules (e.g., acrylates, alcohols, esters). In addition, the properties that dictate the uses of fluorocarbons can be classified into (1) bulk properties (e.g., thermal and chemical stability, dielectric constant) and (2) surface properties (e.g., low surface tension, low coefficient of friction). The types of materials available and properties imparted are not exclusive and overlap substantially. From this array of fluorocarbons and attributes, a large variety of unique materials can be constructed. 

---