Chem 109H Fall08

As you can see, there is no order to the arrangement of the atoms. We call materials like this amorphous. This is the glass that is used for telescope lenses and such things. It has very good optical properties, but it's brittle. For everyday uses, we need something tougher. Most glass is made from sand, and when we melt down the sand, we usually add some sodium carbonate. This gives us a tougher glass with a structure that looks like this:

So is this a polymer or not? Usually it isn't considered as such. Why? Some may say it's inorganic, and polymers are usually organic. But there are many inorganic polymers out there. For example, what about polysiloxanes? These linear, and yes, inorganic materials have a structure very similar to glass, and they're considered polymers. Take a look at a polysiloxane:

So glass could be considered a highly crosslinked polysiloxane. But we usually don't think of it that way. Why not? Probably because even in a highly crosslinked system, you could still trace a polymer chain and see where the crosslinks are. But with glass, it'd be tough to do that.

Other examples of thermoplastics are: Polyethylene: packaging, electrical insulation, milk and water bottles, packaging film, house wrap, agricultural film Polypropylene: carpet fibers, automotive bumpers, microwave containers, external prostheses Polyvinyl chloride (PVC): sheathing for electrical cables, floor and wall coverings, siding, credit cards, automobile instrument panels

These monomers are then chemically bonded into chains called polymers.

The resulting resins may be molded or formed to produce several different kinds of plastic products with application in many major markets. The variability of resin permits a compound to be tailored to a specific design or performance requirement.

Polymers are created by the chemical bonding of many identical or related basic units and those produced from a single monomer type are called homopolymers. These polymers are specifically made of small units bonded into long chains. Carbon makes up the backbone of the molecule and hydrogen atoms are bonded along the carbon backbone.

In order to achieve a commercial product, the plastic is subject to further treatment and the inclusion of additives which are selected to give it specified properties

Additives are incorporated into polymers to alter and improve their basic mechanical, physical or chemical properties. Additives are also used to protect the polymer from the degrading effects of light, heat, or bacteria; to change such polymer properties as flow; to provide product color; and to provide special characteristics such as improved surface appearance or reduced friction.

Types of Additives:     antioxidants: for outside application,      colorants: for colored plastic parts, foaming agents: for Styrofoam cups,      plasticizers: used in toys and food processing equipment

A Thermoset is a polymer that solidifies or "sets" irreversibly when heated. Similar to the relationship between a raw and a cooked egg, once heated, a thermoset polymer can't be softened again and once cooked, the egg cannot revert back to its original form.

A Thermoplastic is a polymer in which the molecules are held together by weak secondary bonding forces that soften when exposed to heat and return to its original condition when cooled back down to room temperature. When a thermoplastic is softened by heat, it can then be shaped by extrusion, molding or pressing. Ice cubes are a common household item which exemplify the thermoplastic principle. Ice will melt when heated but readily solidifies when cooled.

In this method, a separate molding and cooling station on the equipment allows the parison to be continuously formed.  This technique is used mainly for small thin-walled parts ranging up to containers with five gallon capacities.  Parison programming can be used to vary the wall thickness.  Continuous extrusion also allows the use of heat-sensitive materials due to streamlined flow areas and die designs.

This technique is performed in three basic ways --reciprocating, ram accumulator, and accumulator head systems.  All three vary in machine design and the flow of molten resin through the die for parison forming.  However, each system is designed to produce larger, heavier, and thicker parts than continuous extrusion.

Blow moldable grades of material are initially injection molded into preform shapes.  These preforms are then thermally conditioned and then stretched (utilizing pneumatically operated stretch rods) low pressure air, followed by high pressure air up to 40 bar to form axially oriented parts with molded in necks.  The process is used to manufacture PET bottles.

This process utilizes various thermoplastic materials in a solid pelletized state and converts these materials by way of heat, pressure and compressed air into a finished good stat.The pellitized raw material is conveyed to the feed section of a plasticating extruder by way of a vacuum loader or auger screw.  The raw material is then conveyed forward through the extruder and is plastisized to a molten state of between 350 degrees and 500 degrees F. by way of a feed screw and external heating elements.The material in a melt state is then reshaped into a round hollow geometry termed a parison.  This parison is then extruded vertically from the head section of the machine through a round die at various outside and inside diameters.After extrusion of the parison between the two halves of a mold the press section closes encapsulating the parison inside the mold halves.  Upon mold close compressed air is entered into the parison by way of a centrally located air pipe or by piercing air needles.The molds are chilled with cooled water which transfers the hear form the now formed part inside the mold.  Upon complete part cooling the press section opens and the finished product is removed.  The material which is pinched off outside the mold cavity, or the flash, is then fed into a granulator which cops the flash into a granule size which can be fed back to the feed section of the extruder.

Apparently, it's difficult to use these nanoclays. So the researchers turned to "high-powered ultrasonics — high-frequency sound waves too high for human hearing – to separate and disperse the platelets."

Number 6 goes on polystyrene (Styrofoam) items such as coffee cups, disposable cutlery, meat trays, packing “peanuts” and insulation. It is widely accepted because it can be reprocessed into many items, including cassette tapes and rigid foam insulation.

Usually imprinted with a number 7 or nothing at all, these plastics are the most difficult to recycle and, as such, are seldom collected or recycled.

Since only a fraction of certain types of plastic could realistically be captured by a curbside program, the net impact of initiating curbside collection could be an increase in the amount of plastic landfilled. The Berkeley pilot program showed no reduction of plastic being sent to the landfill in the areas where the curbside collection was in operation.

A chasing arrows symbol means a plastic container is recyclable. The arrows are meaningless. Every plastic container is marked with the chasing arrows symbol. The only information in the symbol is the number inside the arrows, which indicates the general class of resin used to make the container.

Packaging resins are made from petroleum refineries’ waste. Plastic resins are made from non-renewable natural resources that could be used for a variety of other applications or conserved. Most packaging plastics are made from the same natural gas used in homes to heat water and cook.

Using plastic containers conserves energy. When the equation includes the energy used to synthesize the plastic resin, making plastic containers uses as much energy as making glass containers from virgin materials, and much more than making glass containers from recycled materials. Using refillables is the most energy conservative.

Our choice is limited to recycling or wasting. Source reduction is preferable for many types of plastic and isn’t difficult. Opportunities include using refillable containers, buying in bulk, buying things that don’t need much packaging, and buying things in recyclable and recycled packages

Plastic packaging has economic, health, and environmental costs and benefits.

Plastic container producers do not use any recycled plastic in their packaging. Recycled content laws could reduce the use of virgin resin for packaging. Unfortunately, the virgin&endash;plastics industry has resisted such cooperation by strongly opposing recycled -content legislation, and has defeated or weakened consumer efforts to institute stronger laws.

Processing used plastics often costs more than virgin plastic. As plastic producers increase production and reduce prices on virgin plastics, the markets for used plastic are diminishing. PET recyclers cannot compete with the virgin resin flooding the market.

1. Reduce the useSource reduction Retailers and consumers can select products that use little or no packaging. Select packaging materials that are recycled into new packaging - such as glass and paper.

2. Reuse containersSince refillable plastic containers can be reused about 25 times, container reuse can lead to a substantial reduction in the demand for disposable plastic, and reduced use of materials and energy

3. Require producers to take back resins

Make reprocessing easier by limiting the number of container types and shapes, using only one type of resin in each container, making collapsible containers, eliminating pigments, using water-dispersible adhesives for labels, and phasing out associated metals such as aluminum seals.

4. Legislatively require recycled content Requiring that all containers be composed of a percentage of post-consumer material reduces the amount of virgin material consumed.

5. Standardize labeling and inform the public The chasing arrows symbol on plastics is an example of an ambiguous and misleading label. Significantly different standardized labels for "recycled," "recyclable," and "made of plastic type X" must be developed.

These methods recover some of the value from the plastic. Recycling recovers the raw material, which can then be used to make new plastic products. Incineration recovers the chemical energy, which can be used to produce steam and electricity. Landfilling plastics does neither of these things. The value of landfilled plastic is buried forever.

A recycling plant uses seven steps to turn plastic trash into recycled plastic:

1. Inspection  Workers inspect the plastic trash for contaminants like rock and glass, and for plastics that the plant cannot recycle.  2. Chopping and Washing  The plastic is washed and chopped into flakes. 3. Flotation Tank  If mixed plastics are being recycled, they are sorted in a flotation tank, where some types of plastic sink and others float. 4. Drying  The plastic flakes are dried in a tumble dryer. 5. Melting  The dried flakes are fed into an extruder, where heat and pressure melt the plastic. Different types of plastics melt at different temperatures. 6. Filtering  The molten plastic is forced through a fine screen to remove any contaminants that slipped through the washing process. The molten plastic is then formed into strands. 7. Pelletizing  The strands are cooled in water, then chopped into uniform pellets. Manufacturing companies buy the plastic pellets from recyclers to make new products. Recycled plastics also can be made into flowerpots, lumber, and carpeting.  

Because plastics are made from fossil fuels, you can think of them as another form of stored energy. Pound for pound, plastics contain as much energy as petroleum or natural gas, and much more energy than other types of garbage. This makes plastic an ideal fuel for waste-to-energy plants.

So, should we burn plastics or recycle them? It depends. Sometimes it takes more energy to make a product from recycled plastics than it does to make it from all-new materials. If that’s the case, it makes more sense to burn the plastics at a waste-to-energy plant than to recycle them. Burning plastics can supply an abundant amount of energy, while reducing the cost of waste disposal and saving landfill space.  

A study by Canadian scientist Martin Hocking shows that making a paper cup uses as much petroleum or natural gas as a polystyrene cup. Plus, the paper cup uses wood pulp. The Canadian study said, “The paper cup consumes 12 times as much steam, 36 times as much electricity, and twice as much cooling water as the plastic cup.” And because the paper cup uses more raw materials and energy, it also costs 2.5 times more than the plastic cup.

scientists have figured out two ways to make plastics degrade: biodegradation and photodegradation.

Photodegradable plastics are a different matter. They use no organic additives. They are made with a special type of plastic that breaks down and becomes brittle in the presence of sunlight. Of course, that means photodegradable plastics do not break down when they are covered by leaves or snow, or when they are buried in a landfill. 

Example 1:A carboxylic acid monomer and an amine monomer can join in an amide linkage. As before, a water molecule is removed, and an amide linkage is formed. Notice that an acid group remains on one end of the chain, which can react with another amine monomer. Similarly, an amine group remains on the other end of the chain, which can react with another acid monomer. Thus, monomers can continue to join by amide linkages to form a long chain. Because of the type of bond that links the monomers, this polymer is called a polyamide.

Example 2:A carboxylic acid monomer and an alcohol monomer can join in an ester linkage. A water molecule is removed as the ester linkage is formed. Notice the acid and the alcohol groups that are still available for bonding.

Because the monomers above are all joined by ester linkages, the polymer chain is a polyester. This one is called PET, which stands for poly(ethylene terephthalate). (PET is used to make soft-drink bottles, magnetic tape, and many other plastic products.)

The two types of polymer configurations are cis and trans. These structures can not be changed by physical means (e.g. rotation). The cis configuration arises when substituent groups are on the same side of a carbon-carbon double bond. Trans refers to the substituents on opposite sides of the double bond.

Three distinct structures can be obtained. Isotactic is an arrangement where all substituents are on the same side of the polymer chain. A syndiotactic polymer chain is composed of alternating groups and atactic is a random combination of the groups. The following diagram shows two of the three stereoisomers of polymer chain.

The ability of an atom to rotate this way relative to the atoms which it joins is known as an adjustment of the torsional angle. If the two atoms have other atoms or groups attached to them then configurations which vary in torsional angle are known as conformations.

different conformation may represent different potential energies of the molecule. There several possible generalized conformations: Anti (Trans), Eclipsed (Cis), and Gauche (+ or -). The following animation illustrates the differences between them.

The geometric arrangement of the bonds is not the only way the structure of a polymer can vary. A branched polymer is formed when there are "side chains" attached to a main chain. A simple example of a branched polymer is shown in the following diagram.

One of these types is called "star-branching". Star branching results when a polymerization starts with a single monomer and has branches radially outward from this point. Polymers with a high degree of branching are called dendrimers Often in these molecules, branches themselves have branches.

A separate kind of chain structure arises when more that one type of monomer is involved in the synthesis reaction. These polymers that incorporate more than one kind of monomer into their chain are called copolymers. There are three important types of copolymers. A random copolymer contains a random arrangement of the multiple monomers. A block copolymer contains blocks of monomers of the same type. Finally, a graft copolymer contains a main chain polymer consisting of one type of monomer with branches made up of other monomers. The following diagram displays the different types of copolymers.

In addition to the bonds which hold monomers together in a polymer chain, many polymers form bonds between neighboring chains. These bonds can be formed directly between the neighboring chains, or two chains may bond to a third common molecule.

Polymers with a high enough degree of cross-linking have "memory." When the polymer is stretched, the cross-links prevent the individual chains from sliding past each other. The chains may straighten out, but once the stress is removed they return to their original position and the object returns to its original shape.

In vulcanization, a series of cross-links are introduced into an elastomer to give it strength. This technique is commonly used to strengthen rubber.

Elastomers,or rubbery materials, have a loose cross-linked structure. This type of chain structure causes elastomers to possess memory. Typically, about 1 in 100 molecules are cross-linked

Natural and synthetic rubbers are both common examples of elastomers. Plastics are polymers which, under appropriate conditions of temperature and pressure, can be molded or shaped (such as blowing to form a film). In contrast to elastomers, plastics have a greater stiffness and lack reversible elasticity.

Thermoset materials are generally stronger than thermoplastic materials, and are also better suited to high-temperature applications. They do not lend themselves to recycling like thermoplastics, which can be melted and re-molded.

Examples Natural Rubber Bakelite, a Phenol Formaldehyde Resin (used in electrical insulators and plastic wear) Duroplast Urea-Formaldehyde Foam (used in plywood, particleboard and medium-density fibreboard) Melamine (used on worktop surfaces) Polyester Resin (used in glass-reinforced plastics/Fibreglass (GRP)) Epoxy Resin (used as an adhesive and in fibre reinforced plastics such as glass reinforced plastic and graphite-reinforced plastic)

Take a piece of copper wiring," says Meddick. "It is encased in plastic - a kind of hydrocarbon material. We release all the hydrocarbons, which strips the casing off the wire." Not only does the process produce fuel in the form of oil and gas, it also makes it easier to extract the copper wire for recycling.

Autofluff is the stuff that is left over after a car has been shredded and the steel extracted. It contains plastics, rubber, wood, paper, fabrics, glass, sand, dirt, and various bits of metal. GRC says its Hawk-10 can extract enough oil and gas from the left-over fluff to run the Hawk-10 itself and a number of other machines used by Gershow.

Because it makes extracting reusable metal more efficient and evaporates water from autofluff, the Hawk-10 should also reduce the amount of end material that needs to be deposited in landfill sites.

One such molecule is the ethylene monomer, the starting point for a variety of plastics. Ethylene is a small hydrocarbon consisting of four hydrogen atoms and two carbon atoms.

Polymerization is often started by combining the monomers through the use of a catalyst - a substance that aids a chemical reaction without undergoing any permanent chemical change itself. During the chemical reaction, hundreds or thousands of monomers combine to form a polymer chain, and millions of polymer chains are formed at the same time. The mass of polymers that results is known as a resin.

Polyethylene is made from just ethylene monomers - but it's also possible to create polymers from two or more different monomers. You can make hundreds of different polymers depending on which monomers and catalysts you use.

Cellulose, the basic component of plant cell walls is a polymer, and so are all the proteins produced in your body and the proteins you eat. Another famous example of a polymer is DNA - the long molecule in the nuclei of your cells that carries all the genetic information about you.

lastics are classified into two categories according to what happens to them when they're heated to high temperatures. Thermoplastics keep their plastic properties: They melt when heated, then harden again when cooled. Thermosets, on the other hand, are permanently "set" once they're initially formed and can't be melted. If they're exposed to enough heat, they'll crack or become charred.

Thermoplastics have long, linear polymer chains that are only weakly chemically bonded, or connected, to each other. When a thermoplastic object is heated, these bonds are easily broken, which makes the polymers able to glide past each other like strands of freshly cooked spaghetti. That's why thermoplastics can readily be remolded. The weak bonds between the polymers reform when the plastic object is cooled, which enable it to keep its new shape.

The linear chains are crosslinked - strongly chemically bonded. This prevents a thermoplastic object from being melted and reformed.

The most common method for making plastics is molding. To make a thermoplastic object, plastic granules known as resin are forced into a mold under high heat and pressure. When the material has cooled down, the mold is opened and the plastic object is complete. When making plastic fibers, the molten resin is sprayed through a strainer with tiny holes.

Thermosets are produced in two steps: 1. Linear polymers are formed. 2. The linear polymers are forced into a mold where "curing" takes place. This may involve heating, pressure, and the addition of catalysts. During this process, a cross-linked or networked structure forms, creating a permanently hard object that is no longer meltable or moldable.

For most applications, the ideal polymer is a long, straight chain with a highly regular molecular structure. Early synthetic polymers, however, often exhibited odd little branches and other irregularities. In the 1950s, German chemist Karl Ziegler (1898–1973) discovered that an entirely different type of catalyst - a combination of aluminum compounds with other metallic compounds - could solve some of these annoying problems and increase the length of a polymer chain, producing superior plastics.

olymers often have short side chains, which can occur on either side of the main chain. If side branches occur randomly to the left or right, the polymer has an irregular structure. Italian chemist Giulio Natta (1903–1979) discovered that some Ziegler catalysts led to a uniform structure in which all the side branches are on the same side.

Firstly, there is an environmental impact from plastics production; however the plastics industry has worked hard to reduce energy and water use, as well as waste generation during the manufacturing processes.

Secondly, during their lives, plastic products can save energy and reduce carbon dioxide emissions in a variety of ways. For example, they're lightweight, so transporting them is energy efficient. And plastic parts in cars and airplanes reduce the weight of those vehicles and therefore less energy is needed to operate them and lower emissions are created.

Biopolymer Natural Source What is it? Lactic Acid Beets, corn, potatoes, and others Produced through fermentation of sugar feedstocks, such as beets, and by converting starch in corn, potatoes, or other starch sources. It is polymerized to produce polylactic acid -- a polymer that is used to produce plastic. Triglycerides Vegetable oils These form a large part of the storage lipids found in plant and animal cells. Vegetable oils are one possible source of triglycerides that can be polymerized into plastics.

Using Fermentation to Produce Plastics Fermentation, used for hundreds of years by humans, is even more powerful when coupled with new biotechnology techniques.

Today, fermentation can be carried out with genetically engineered microorganisms, specially designed for the conditions under which fermentation takes place,

Fermentation, in fact, is the process by which bacteria can be used to create polyesters. Bacteria called Ralstonia eutropha are used to do this. The bacteria use the sugar of harvested plants, such as corn, to fuel their cellular processes. The by-product of these cellular processes is the polymer.

Lactic acid is fermented from sugar, much like the process used to directly manufacture polymers by bacteria. However, in this fermentation process, the final product of fermentation is lactic acid, rather than a polymer. After the lactic acid is produced, it is converted to polylactic acid using traditional polymerization processes.

Plants are becoming factories for the production of plastics. Researchers created a Arabidopis thaliana plant through genetic engineering. The plant contains the enzymes used by bacteria to create plastics. Bacteria create the plastic through the conversion of sunlight into energy. The researchers have transferred the gene that codes for this enzyme into the plant, as a result the plant produces plastic through its cellular processes. The plant is harvested and the plastic is extracted from it using a solvent. The liquid resulting from this process is distilled to separate the solvent from the plastic.

Currently, fossil fuel is still used as an energy source during the production process. This has raised questions by some regarding how much fossil fuel is actually saved by manufacturing bioplastics. Only a few processes have emerged that actually use less energy in the production process.

Energy use is not the only concern when it comes to biopolymers and bioplastics. There are also concerns about how to balance the need to grow plants for food, and the need to grow plants for use as raw materials. Agricultural space needs to be shared. Researchers are looking into creating a plant that can be used for food, but also as feedstock for plastic production.

Biopolymers and bioplastics are the main components in creating a sustainable plastics industry. These products reduce the dependence on non-renewable fossil fuels, and are easily biodegradable. Together, this greatly limits the environmental impacts of plastic use and manufacture. Also, characteristics such as being biodegradable make plastics more acceptable for long term use by society. It is likely that in the long term, these products will mean plastics will remain affordable, even as fossil fuel reserves diminish.

In contrast to amylopectin, which comprises 70 to 90 percent of natural starch, α-amylose is a branching polysaccharide.

Branches occur at every twelve to thirty residues along a chain of α (1→4) linked glucoses. As a result, amylopectin has one reducing end and many nonreducing ends.

Amylopectin and α-amylose are broken down by the enzyme amylase. In animals, salivary α-amylase begins the digestion process in the mouth. Pancreatic α-amylase continues the process in the intestine.

Glycogen is the energy storage carbohydrate in animals. Glycogen is found mainly in the liver (where it is responsible for up to 10 percent of liver mass) and skeletal muscle (1 to 2 percent of skeletal muscle mass)

However, glycogen branches more abundantly than amylopectin, with branches at every eight to twelve residues. As a result, it has many more nonreducing ends. Glycogen is broken down at these nonreducing ends by the enzyme glycogen phosphorylase to release glucose for energy.

The primary structural homopolysaccharides are cellulose and chitin. Cellulose, a major component of plant cell walls, is the most abundant natural polymer on Earth.

Like α-amylose, cellulose is a linear polysaccharide composed entirely of glucose. However, in cellulose the glucose residues occur in β(1→4) linkage rather than α (1→4) (see Figure 1).

In addition, individual cellulose strands can form hydrogen bonds with one another to provide additional strength. Most animals, including humans, lack the enzymes necessary to dissolve α(1→4) linkages and so cannot digest cellulose

The animals that can (such as ruminants) do so via a symbiosis with bacteria that secrete cellulose-degrading enzymes.

The second most abundant polymer on Earth is chitin. Chitin comprises much of the exoskeletons of crustaceans, insects, and spiders, as well as the cell walls of fungi. Structurally, chitin is very similar to cellulose, except that its basic monosaccharide is N-acetylglucosamine

To form polypeptides and proteins, amino acids are joined together by peptide bonds (def), in which the amino or NH2 of one amino acid bonds to the carboxyl (acid) or COOH group of another amino acid as shown in (see Fig. 2). Animation showing the formation of a peptide bond.

The actual order of the amino acids in the protein is called its primary structure (def) (see Fig. 3) and is determined by DNA.

it is commonly said that the order of deoxyribonucleotide bases (def) in a gene determines the amino acid sequence of a particular protein. Since certain amino acids can interact with other amino acids in the same protein, this primary structure ultimately determines the final shape and therefore the chemical and physical properties of the protein.

In globular proteins such as enzymes, the long chain of amino acids becomes folded into a three-dimensional functional shape or tertiary structure (def).

In some cases, such as with antibody molecules and hemoglobin, several polypeptides may bond together to form a quaternary structure (def) (see Fig 6).