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1, MARCH 2001

Conductive Materials for ESD Applications: An Overview

Robert B. Rosner
Invited Paper

AbstractPolymer resins, because of their low cost, versatility, and ease of use, are the principle component in many static-control items. These items include containers and packages used to store and transport sensitive electronics. This paper seeks to explain how polymers are used for these demanding applications by providing a basic tutorial in polymer science as well as a brief description of the commercial polymers used in static-control products. This paper also contains a review of the various ways of imparting electrical conductivity on plastic resins through the use of antistatic agents, conductive fillers, and intrinsically conductive polymers. Index TermsAntistatic, conducting materials, plastics, staticcontrol.

Fig. 1.

Styrene monomer and polystyrene.





ROM simple milk cartons to super-clean temperature-resistant electronic processing equipment, polymer materials are seen in a greater range of applications than perhaps any other class of material. The success of polymer materials is derived from two important advantages: the exceptionally wide range of properties exhibited by polymers and their almost limitless flexibility in processing. For example, some polymer resins are clear and flexible, ideal for low-cost packaging, while others exhibit outstanding strength and temperature properties for use in more exotic engineering applications. Polymers can be stretched, squeezed, extruded, molded, and made into almost any shape or size. In addition, polymers often hold the edge when cost and weight concerns are paramount. Static-control applications for electronics represent a special challenge for polymer engineers. The protection of sensitive electronic devices requires an environment in which wayward electrical charges, voltages, and electric fields are minimized. In order to safely drain these charges and protect the devices, polymers used in the packaging, transportation, and storage of electronic devices must be able to conduct electricity. However, in their natural state, almost all commercial polymers are electrical insulators. In order to render them conductive, polymers must undergo special modifications either through chemical treatment or the addition of conductive agents during processing. The level of conductivity required in the polymer depends on its
Manuscript received December 26, 2000; revised February 13, 2001. The author is with the 3M Electronic Handling and Protection Division, Austin, TX 78726 USA (e-mail: Publisher Item Identifier S 1530-4388(01)04122-1.

end use. For example, high-conductivity (low-resistance) plastics are needed for protective containers and totes. Typically, such a plastic should have a resistance no greater than 10 , whereas plastics used in flooring and work surfaces should exhibit resistances in the range of 10 10 . Several publications and standards are readily available which describe these important requirements [1]. The goal of this paper is to explain how and why polymers are used for static-control applications and is divided into three sections. The first section explains how polymers differ from other materials by reviewing important aspects of polymer science from first principals. The second section uses these principals to understand the properties of commercial polymer resins commonly used in static-control applications. The third section describes ways in which these polymer resins can be modified to achieve the level of electrical conductivity needed for static control. II. POLYMER PRINCIPLES Polymers, as a class of material, are unique because of their molecular size and chemistry. A polymer is a giant molecule made up of many smaller units called monomers. The monomers are chemically bonded to each other. The easiest way to envision this is to imagine a polymer molecule as a long string of beads; each single bead representing a monomer that is chemically bonded to its neighbors. An example of the relationship between the monomer and polymer is shown in Fig. 1 for the case of polystyrene. Many of the special properties of polymers can be explained in terms of their size and chemistry. Looking again at our bead analogy, imagine that instead of just a single beaded chain, we have thousands of long beaded chains mixed together in a bowl. Try to remove one chain and what happens? The beads are

15304388/01$10.00 2001 IEEE



Fig. 2.

Polymer chains in amorphous and crystalline regions.

Fig. 3.

Processing temperatures of polyethylene.

pulled up together in one mass. This is because the chains are randomly (amorphously) distributed and so entangled that they behave as a single unit. Polymer molecules behave in the same way. They can be wrapped and twisted around each other. But the bead analogy fails in two important ways. First, polymer chains are not static; they are constantly in motion, bumping, rubbing, and sliding against each other. They behave more like a bowl of snakes than a bowl of chains. And second, they are not always randomly distributed or amorphous. Polymer molecules can align themselves into organized crystalline units. Some polymers are completely amorphous; others are a mix of amorphous and crystalline regions. Still others, such as polyethylene, are largely crystalline and only 5% amorphous. This is demonstrated in Fig. 2. Both the amorphous and crystalline regions undergo a thermodynamic transition at a particular temperature. The amorphous regions undergo what is called the glass transition. Below the glass-transition temperature , polymer chains do not have the thermal energy to move and slide against each other. Molecular motion slows down and the polymer resin becomes brittle and glassy. Above the , the polymer chains are mobile and the polymer is ductile, soft, and plastic. of the The second transition is the melting temperature crystalline regions. These crystalline regions are important to the resin because they impart strength, heat stability, and chem, the polymer resin is ical resistance to the resin. Above the fluid and putty-like. A good example of the importance of these two temperais 80 C and whose is tures is polyethylene, whose 110 C. Below the glass-transition temperature, polyethylene is glassy and brittle, not well suited for commercial use. Above the melting point, the polymer is fluid and putty-like. This is the temperature at which processing (injection molding, extrusion, etc.) occurs. The interim temperatures (between 80 C and 110 C) is the region where polyethylene is tough and plastic, yet strong. This region, where most of the resins applications occur, is shown diagrammatically in Fig. 3. Another important property that is often used in comparing resins is the strength of the resin. While there are many ways to determine strength, the most common is to measure the tensile strength and modulus. Tensile strength is the force (per crosssectional area) required to pull apart a rectangular sample when it is gripped at both ends. The modulus is the same force but normalized (divided) by the length the sample is stretched. Both are reported in terms of force per unit area.

Fig. 4.

Polyolefin structures.

III. COMMON POLYMERS Manmade polymers first appeared in the middle of the 19th century as replacements for natural products. In 1870, responding to a severe shortage of ivory used in making billiard balls, John and Isaiah Hyatt patented a process for making a horn-like material using celluloid [2] . Many of the resins that we are familiar with today, such as polyethylene and polystyrene, first saw commercial development in the 1930s and 1940s. Further developments, particularly in the area of synthetic rubber research, occurred as a result of the raw materials shortages during the Second World War. Since that time, the plastics industry has enjoyed significant growth as more and more resins were developed to fit increasing numbers of commercial and industrial applications. This section discusses the physical and chemical properties of some of the resins commonly found in static-control applications. A. Polyolefins Polyolefins (also known as hydrocarbon polymers) are the most common polymer resins in use today and include polyethylene and polypropylene. Domestic production of polyethylene alone reached nearly 28 billion pounds in 1998 [3]. The general structure for polyolefins is given in Fig. 4. Polyethylene is so common that the resin is further subdivided into several classes of polymer based on its density. The best known of these is low-density polyethylene (LDPE), with densities ranging from 0.91 to 0.94 g/cm , and high-density polyethylene (HDPE), with densities between 0.95 and 0.97 g/cm . Low-density polyethylene is among the cheapest resins available. Physically, it is considered a low-strength low-melting resin (see Table I for physical properties). LDPE however, also shows good chemical resistance and good electrical properties. It finds its widest applications in food packaging and wire insulation. For static-control applications, it is most often




Fig. 5.

PTFE structure and bond energies.

rendered conductive by loading with carbon and then used in static-control bags and liners. High-density polyethylene molecules are very linear and flexible. They are easily folded into crystal structures and, as a consequence, exhibit crystallinities of 90% or more. This high level of crystallinity provides the resin with higher strength than LDPE and chemical resistance that is second only to Teflon. However, a melting point of only 130 C limits the use of the resin to low-temperature applications. HDPE is commonly found in juice and food containers and in larger structures like kayaks or buoys. Static-control applications would include carbon-loaded resins for bags and injection-molded articles like static-control containers and totes. Polypropylene is of the same family as polyethylene, but a ) careful look at Fig. 4 shows that there is an extra methyl ( group on one side of each monomer. Going back to our analogy of the polymer chain as a string of beads, where polyethylene is a string of plain beads, polypropylene is a string of beads with an extra piece hanging off each bead. Two important changes occur as a result of this extra methyl group. First, the chains do not slide past each other as readily. This means that more thermal energy is needed to move these and big polymer chains. The result of this is seen in higher values. As noted in Table I, polypropylenes glass transition occurs at around 30 C and its melting point occurs around 165 C. The second effect is that the more complex polypropylene chains are difficult to organize into ordered regimes and therefore exhibit a lower degree of crystallinity. The higher processing temperatures mean somewhat broader applications for polypropylene, which is stronger, stiffer, and more brittle than polyethylene. For example, this resin has a high enough thermal tolerance to withstand sterilization and is used in molded parts for the health industry. Owing to its easy processability and glossy surface, polypropylene is also used in nonstructural molding applications for appliances and automobiles and in filament rope. It should be noted that commercial polypropylene resins are often modified with rubber to improve their poor impact resistance. For static-control applications, this resin is most often used as a carbon-filled conductive material for injection-molded containers and totes. B. Polystyrene Polystyrene is itself a commercially important resin as well as a modifier for other resins. Unmodified polystyrene is clear,

glassy, and easily processed, but is limited by its low resistance to heat and easy attack by common solvents such as gasoline and acetone. A study of polystyrenes chemical structure (shown in Fig. 1) and a brief return to our beaded chain analogy will help explain these features. Polystyrenes structure is similar to polypropylene in that each individual monomer unit or bead has an extra chemical feature attached at the side. This pendant unit greatly influences the resins properties. In the case of polypropylene, ) group. In the case of polythe pendant unit is a methyl ( styrene, the pendant unit is the much larger phenyl ring (the hexagonal ring seen in Fig. 1). We know that bulky side groups make molecular motion and organization more difficult, thereby raising the transition temperatures and decreasing the degree of crystallinity. This effect is greatly magnified in polystyrene, which has a glass-transition temperature of 105 C and no crysvalue would explain the brittle natalline regions. The high ture of the resin, and the lack of protective crystalline regions explains the susceptibility to chemical attack. Polystyrene applications tend to be limited to low-end injection-molded parts. Many of the resins limitations can be overcome by forming two and three component mixtures. Perhaps the best-known such alloy is the mixture of acrylonitrile, butadiene, and styrene to form ABS. Here, the acrylonitrile content enhances chemical resistance while the butadiene rubber improves impact strength. Similarly, high-impact polystyrene (HIPS) has a rubber component. ABS resins, while still limited by low heat resistance, have found many applications in appliance housings, automotive parts, and childrens toys. Static-control applications include trays and carriers. C. Fluorinated Resins Polytetrafluoroethylene (PTFE), also known commercially as Teflon, is famous for its extreme properties. This material is almost completely immune to chemical attack (except from concentrated alkali metals) and is thermally stable to more than 250 C. On the other hand, it is very difficult to process and has poor mechanical properties. A simple look at the beaded chain model will not explain these unusual properties, because they are inherent in the chemical makeup of the polymer. This chemical structure is shown in Fig. 5. The actual structure of PTFE is the same as polyethylene, except that the hydrogen atoms are completely replaced with fluorine atoms. This swapping of atoms greatly improves the chemical stability of the chains, because it takes much more energy to break the carbonfluorine bond found in PTFE than the carbonhydrogen bond in polyethylene [4]. After all, that is what chemical and thermal stability are all about: resistance to breaking bonds. Stronger bonds in the polymer chain



Fig. 6.

Polyethylene terephthalate. Fig. 7. Polyetheretherketone (PEEK) and polycarbonate.

mean better chemical resistance and greater thermal stability. These strengths are further helped by PTFEs high level of crystallinity, which, like HDPE, ranges from 93% to 98%. In addition to its chemical and thermal inertness, PTFE has excellent electrical properties and high lubricity. This resin finds applications in a wide arena of products, including insulation for wires, cables, and high-frequency electronics, as well as situations involving chemical or food processing. For electronics applications, PTFE is often used in areas requiring cleanliness such as wafer processing and in cleanrooms. PTFE is highly triboelectric and often creates static-control problems by generating static charges during handling. While PTFE itself is not found in conductive forms, other fluorinated polymers are available with conductive fillers. D. Polyesters Polyester is a generic name for a wide class of polymers that share a common trait: they contain an ester group on the chain. The most common and widely used polyester resin is polyethylene terephthalate (PET). The structure of PET is shown in Fig. 6, where the ester linkage is highlighted. Physical properties are given in Table I. Polyesters, particularly PET, are like polystyrene in that they contain bulky groups and exhibit high thermal transition temperof PET are well above room temperature atures. The and at 70 C and 265 C, respectively. But unlike polystyrene, which is brittle under these conditions, PET shows great flexibility, toughness, and impact strength. How is this possible? Unfortunately, the answer goes beyond the beaded chain analogy that has served so well up to this time. The answer involves molecular motion. Where polystyrene has little or no molecular motion below its and is brittle, PET still has a significant amount of polymer chain motion. As we mentioned before, it is the motion of the chains, moving and sliding against one another, which imparts toughness and flexibility to the polymer. Looking again at Fig. 6, we can see that there are two different parts to the PET chain: a long slender portion that contains the oxygen and , and the larger slow-moving phenyl ring. The molecular motion responsible for toughness is found in the flexible ethy) segment. In a sense, this short section lene oxide ( of the chain behaves in the same way as the butadiene segments of ABS by providing a rubbery element to the polymer. PET and its derivatives, such as PETG, are also easily drawn into fibers for fabrics and easily molded. PET resins show excellent chemical and moisture barrier properties and are nontoxic, making it a preferred plastic for food and pharmaceutical applications. Similarly, in the electronics industry, PET resins are

most often found in packaging applications where the resin is modified to be static dissipative or electrically conductive. Perhaps its weakest link as a commercial resin is its chemical and thermal resistance. PET is highly susceptible to degradation when heated above 150 C in the presence of moisture. For this reason, PET must be thoroughly dried prior to processing and cannot be exposed to elevated temperatures [5] . E. Engineering Resins The commercial resins so far investigated have shown wide variety of properties, including chemical inertness and great toughness. However, most of these resins are limited to temperatures below 125 C, a severe limitation for the automotive and electronics industries. A new generation of polymer materials is being put forth which addresses the need for high temperature resistance and high strength. These resins are grouped together as engineering resins. They include polyetheretherketone (PEEK), polycarbonate (PC), polyphenylene sulfide (PPS), polyphenylene oxide (PPO), and polyether sulfone (PES) among others. The structure of PEEK and PC are given in Fig. 7. The success of these resins is due in part to the absence of weaker thermally intolerant segments. For example, methyl are (when not crystallized) very susceptible groups to chemical and oxidative attack. While this chemical unit is found in virtually all the common low-temperature resins, it is not found in any of the engineering resins [6]. The second prong of this strategy is to bulk up the polymer chain with stable thermally tolerant chemical segments. The hexagonal phenyl ring is a highly stable chemical entity and plays a prominent role in the structure of these engineering resins. It appears several times in the monomer units of both PEEK and PC, not as a side group (like polystyrene), but as part of the main chain. These and other strategies have been used to increase the useful working temperature of PEEK, for example, to 240 C and higher [7]. In order to maximize the usefulness of these resins, they are often available as reinforced composites. Again, looking at PEEK as an example, carbon-fiber reinforcement increases the heat distortion temperature from 150 C to 300 C and in the tensile modulus from 0.5 to 1.9 Mpsi. Use of these resins is limited by cost and processing concerns. The resins can cost considerably more than standard commercial resins. Furthermore, their high processing temperature may not be suitable for all plastics processing equipment.



Still, their high purity, good wear, low flammability, and outstanding physical properties have made engineering resins important components for automatic transmission and engine parts as well as cleanroom products. In static-control applications, these resins are often made conductive by the addition of carbon fibers and used in equipment and carriers for wafer processing. IV. METHODS OF ENHANCING CONDUCTIVITY A considerable amount of time and energy has been spent in developing ways of rendering polymers to be either static dissipative or electrically conductive. The remainder of this paper deals with some of the most common methods. These are divided into three categories: chemical additives, conductive fillers, and inherently dissipative and conductive polymers. A. Chemical Additives Resins can often be brought into the dissipative range (10 to 10 ) [8] by incorporating a chemical additive such as an antistatic agent (antistat) to the mix. Antistatic agents can be either topical or internal. A topical agent is simply sprayed or coated onto the surface of the finished article. These antistatic agents are transient at best, since they are easily wiped or rubbed off. Internal antistats, on the other hand, are dissolved into the molten plastic during processing and represent a more permanent fix to the problem. Internal antistats are partially soluble in the polymer resin. After the plastic is solidified, the antistatic agent slowly blooms or migrates to the surface, where it becomes electrically active. Over time, rubbing and washing may remove some of the internal antistatic agent. However, unlike topical additives, internal antistats constantly replenish themselves by migrating from the interior to the surface [9]. A closer look at the chemical structure of a typical antistatic agent will help explain its behavior. Most antistatic agents have two halves of opposite chemical nature: a hydrophilic or water-loving head and a hydrophobic or water-hating tail (see Fig. 8). Both segments play a critical role in the operation of the antistatic agent. The hydrophobic tail is often a short-chain hydrocarbon, almost like a short section of polyethylene. It avoids water but interacts very well with polymers. This interaction explains why antistatic agents are at least partially soluble in the bulk plastic. On the other hand, the hydrophilic head is usually a very polar chemical, sometimes even ionic (electrically charged). This means that the head interacts very poorly with most plastics, but very well with water, salts, and other ionic chemicals. This represents the electrically conducting part of the antistatic agent. A generalized way of looking at the action of an antistatic agent is that the polymer-loving tail group buries itself in the body of the plastic, while the polymer-hating polar head group stays just above the surface. Like a buoy in the water, the antistatic agent remains half submerged and half exposed. The polar head group attracts water, ions, and salts from the environment onto the plastic surface to form a thin layer of conductive soup. This is the conductive layer that allows electric charge to flow over the surface and renders the plastic electrically dissipative [10] . The action of an antistatic agent is shown in Fig. 8.

Fig. 8. Antistatic agent structure and properties.

Antistatic agents are widely used because they are cheap and efficient. However, they are limited in several important ways. They provide limited conductivity in articles by operating in the dissipative region only. Furthermore, owing to the need of an antistat to absorb atmospheric moisture and salts, the conductivity can vary significantly with humidity. They tend to impart a greasy feel to the surface and are not suitable for cleanroom applications due to the potential for ionic and chemical contamination. They are most often employed in commodity static-control applications such as vinyl and rubber work surfaces, polyethylene bags, and polypropylene containers and trays. B. Conductive Fillers Perhaps the earliest and best known method of making a polymer electrically conductive is to load the resin with a conductive filler to make a composite. Many conductive fillers are available, such as metal particles, metal-coated glass, and carbon fibers. Most common to static-control applications is carbon powder, also known as carbon black, which has been in use since the 1950s [11]. Numerous factors can affect the properties of a conductive filler/polymer composite. It is up to the polymer engineer to make the choices among filler type, loading level, process conditions, surface treatments, etc., in order to achieve the desired level of conductivity. For the purposes of this article, we will explore three of the most basic factors: particle conductivity, loading level, and particle shape.



Fig. 10.

Approaching the percolation threshold.

Fig. 9. Resistivity as a function of filler volume. Fig. 11. Resistivity of high- and low-structure carbon black composites.

As might be expected, the resistivity of the composite is closely related to the resistivity of the filler. For example, carbon black, which in pure powder form has a volume resistance of cm, can produce polymer composites approximately 0.1 cm. However, silver powder with resistivities down to 1.0 cm can be used to with a resistance of only make polymer composites with volume resistances as low as cm [11]. This difference becomes important when 10 considering EMI shielding. Metal coatings and fillers may be used for EMI shielding applications, whereas carbon-black composites cannot. The effect of filler loading on the composite resistivity follows a nearly universal pattern regardless of which fillers are chosen. At low filler loadings, the composite properties remain almost undisturbed. As the filler loading reaches a critical point, the resistivity will suddenly and precipitously drop. This point is called the percolation threshold and represents the moment at which there is enough conductive filler present to make a continuous network within the composite. This phenomenon is illustrated in Fig. 9, which shows the resistance of a polymer/silver composite as a function of the volume of silver spheres. As seen in this graph, network formation occurs over a slight increase in filler volume and yet results in a tremendous change in the electrical resistance. Fig. 10 gives a simplified view of this percolation transition. At low filler loadings, the filler particles act like conductive islands in a sea of electrically insulating polymer resin. Little or no change in resistance will occur because electrons moving through the composite will still encounter the insulating polymer. As more particles are introduced (filler volume increases), the conductive particles become more crowded and are more likely to come into contact with each other. Finally, at the percolation threshold, a majority of filler particles are in

contact with at least two nearest neighbors, thereby forming a continuous chain or network. Electrical charge can now pass through the composite via this network without encountering the high-resistance polymer resin. Additional filler loading beyond the percolation threshold does not greatly reduce the resistance of the composite [12]. The shape of the particle plays a critical role in where (at what filler volume) percolation occurs. The more structured or elaborately shaped the particle, the more likely it is to contact a nearest neighbor and the easier it is to form a continuous network. Perfectly spherical fillers, which arguably have the least elaborate and least structured shape, can require as much as 40% loading in order to reach the percolation threshold. Carbon-black particles are more irregularly shaped and often have long branches reaching out from the main body of the particle. These moderately structured fillers can require anywhere from 5% to 35% loading to reach the percolation threshold [13] (see Fig. 11). Finally, highly shaped fillers such as carbon or stainless-steel fibers, may be present in as little as a few volume percent in order to achieve low resistance. The great majority of commercial resins are available as conductive composites. Most often, these resins are compounded with 15%30% carbon black to make containers, trays, bags, work surfaces, wrist straps, etc. Polymer/carbon-black composites are versatile, relatively inexpensive, and permanently conductive. But there are several disadvantages as well. Carbon-black composites are not welcome in cleanroom environments because of the possibility of contamination by shedding carbon particles. This is known as sloughing. Also, because of the steepness of the percolation curve (Fig. 9), it is very difficult to precisely control the level of electrical



Fig. 13.

Polyacetylene structures.

Fig. 12.

Inherently dissipative polymer.

resistance for a particular resin or achieve resistivity levels range. Some of these problems have been in the 10 10 overcome using innovative processing techniques and materials [14][16]. High-temperature composites made with engineering resins such as PEEK and polyamide often incorporate carbon fibers instead of particles. The fibers provide excellent levels of resistivity while reinforcing the polymer resin for stronger, more temperature-resistant products. Since carbon fibers are much less likely to slough, these resins are often used for electronics processing and in cleanrooms. C. Inherently Dissipative and Conductive Polymers Inherently dissipative polymers (IDP) and inherently conductive polymers (ICP) represent two new classes of materials finding their way into static-control applications. While their names may sound similar, these two materials have very different chemistries and properties. Inherently dissipative polymers show resistivities more along the lines of an antistatic agent, while inherently conductive polymers have resistivities approaching those of metals and are even referred to as synthetic metals. 1) Inherently Dissipative Polymers: Inherently dissipative resins are most often employed as an additive for more common commercial resins. Typically, an IDP polymer is mixed in with a host resin, say polypropylene, at a level of 10% to 30%. At this level, there is enough IDP present to lower the resistance range, which of the polymer mixture into the 10 10 is about the same level of resistance that would be expected when using an antistatic agent. This is because IDPs act on similar principles as antistatic agents by using the conduction associated with the movement of ions and charged species [17]. Once again, we will look at the structure of IDPs to explain this. Inherently dissipative polymers are really copolymers, that is, they contain two or more polymer species on the same chain. One of those polymer species is polyethylene oxide (PEO), shown in Fig. 12. The only difference in structure between polyethylene oxide and polyethylene (Fig. 4) is the oxygen atom jammed between the methyl groups. But this oxygen atom makes a big difference in the chemistry of the polymer by adding a polar character to the chain. The oxygen atoms attract and interact with both water and ions. Conduction occurs when

ions hop or jump from oxygen to oxygen, thus travelling along the chain length. Another important aspect of the IDPs operation is how they blend in with their host polymers. IDPs are added into the host polymer, such that they form a separate interpenetrating network within the host polymer (see Fig. 12). While antistatic agents must migrate to the surface of the host polymer in order to be effective, IDPs conduct charge while buried within the host resin. Taking all these factors into account, IDPs provide several important advantages over antistatic agents. Because they are large polymer molecules, IDPs are much less likely to migrate or leach out of the system the way antistatic agents do. This also makes IDPs a much cleaner alternative to antistats. Furthermore, because IDPs form a network buried within the host resin, they are largely independent of atmospheric humidity. However, care must also be taken during processing to insure that the IDP network is not broken up during extrusion or injection molding. IDPs can be added to many commercial polymers, including ABS, polycarbonate, polystyrene, and polyolefins, without greatly changing the mechanical properties of the host polymer. Inherently dissipative polymers are finding applications in a number of static-control applications and in cleanroom environments. 2) Inherently Conductive Polymers: Up to this point, the polymers we have looked at have been rendered conductive by adding electrically conductive elements such as metal particles, ions, and salts. The polymers themselves merely provide a supporting role as the matrix or host material for the conductor. This situation changes completely in the case of inherently conductive polymers (ICPs), in which it is the polymer chain that provides the conductive path for the electrons. This comes about because of a dramatic change in the architecture of these polymers. To explain these changes, we have to introduce a few more chemical terms: double bonds, conjugation, and doping. A regular chemical bond occurs when two atoms share a pair of electrons. A single line drawn between the atoms (such as CC) denotes this. It is this sharing of electrons that binds atoms together and keeps molecules from flying apart. A double bond occurs when the atoms share an extra pair of electrons, bringing the total number to four. This is denoted by a double line drawn between the participating atoms (C=C). Keep in mind that extra electrons can be very useful if you want to conduct electricity. Conjugation occurs when a molecule contains both single and double bonds. In particular, the single and double bonds must alternate within the structure. A good example of this is polyacetylene (Fig. 13), which is constructed entirely of alternating single and double bonds. Conjugated systems are special because the extra electrons of the double bonds are free to roam or move throughout the system. In fact, they are so free and move so rapidly that it is impossible to know exactly where they are. We indicate this movement and freedom by simply drawing a dashed line throughout



Fig. 14. Inherently conductive polymers.

with marginal conductivity. This paper reviews many of the ways in which polymers can be rendered electrically conductive for static-control applications and describes the wide range of properties that are achievable. The popularity of polymers in static-control applications is due in no small part to the wide variety of physical and chemical properties available in commercial polymer resins. This flexibility is further enhanced by a large and steadily increasing number of ways in which polymers can be rendered electrically conductive or dissipative by additives and treatments. ACKNOWLEDGMENT The author wishes to thank D. Swenson, S. Koehn, and C. Miller for their help and suggestions with this paper. He also wishes to thank his wife Leslie for her support. REFERENCES
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the conjugated system. By doing this we are saying, We know the extra electrons are in there somewhere; we just dont know exactly where. Now we have two important elements for conduction: extra electrons and mobility. One could rightfully expect that a polymer chain, like polyacetylene, would conduct electricity throughout its length. Unfortunately, this is not the case. Very long conjugated systems like polyacetylene tend to revert down into shorter conjugated systems of limited length and therefore cannot conduct charge like a metal. In order for a conjugated polymer to conduct electricity, it must first be doped. Doping of a polymer is not the same as doping silicon, where there is a substitution of atoms. Conductive polymers are doped with oxidizing or reducing agents, chemicals which remove electrons from or add electrons to the polymer. Without going into great detail, the oxidation or reduction changes the electronic structure of the polymer so that it can conduct electricity. The degree of conductivity is related to many factors, including the polymer structure, degree of doping, and the type of dopant. From a more practical standpoint, the first generation of intrinsically conductive polymers did not achieve great commercial success. These polymers tended to be insoluble, unprocessable, and extremely sensitive to environmental conditions. For example, iodine-doped polyacetylene has to be stored in an oxygen-free environment in order to prevent degradation of its conductivity. Since that time, several polymers have been developed which exhibit much greater stability and show the promise of commercial success. These include polyaniline, polypyrrole, and polythiophene. These polymers are shown in Fig. 14. Conductivities of ICPs can reach as high as 10 S/cm cm) [18], however, the typical conductivities are (10 in the range of 1100 S/cm. ICPs are still most often used as additives or coatings for static-control applications. ICPs are used for coating materials for films and electronic packaging and can be melt processed with conventional resins such as polyethylene to form static-control articles such as films and trays. These ICP alloys show much greater thermal and chemical stability than their predecessors. ICPs still impart some color (green or blue) to their host polymers, but can be used to make clear films and sheeting. V. SUMMARY Because of the varied and complicated nature of todays electronics manufacturing environment, no individual polymer resin or conductive filler can be considered ideal for all situations. Some applications may demand high-temperature resistance and superior cleanliness while others need low cost

Robert B. Rosner was born in Holyoke, MA, in 1963. He received the B.Sc. degree in chemistry from McGill University, Montreal, ON, Canada, in 1986 and the M.S. and Ph.D. degrees in polymer science from the Massachusetts Institute of Technology, Cambridge, in 1989 and 1992, respectively. Since that time, he has been employed as a Research Scientist in the Electronic Handling and Protection Division of 3M Company, Austin, TX. His research interests include the electrical and electronic properties of polymer composites.