Manufacturing: Materials and Processing

Materials as a field are most commonly represented by ceramics, metals, and polymers. While
noted improvements have taken place in the area of ceramics and metals, it is the field of
polymers that has experienced an explosion in progress. Polymers have gone from being cheap
substitutes for natural products to providing high-quality options for a wide variety of
applications. Further advances and breakthroughs supporting the economy can be expected in the
coming years.

Polymers are derived from petroleum, and their low cost has its roots in the abundance of the
feedstock, in the ingenuity of the chemical engineers who devised the processes of manufacture,
and in the economies of scale that have come with increased usage. Less than 5 percent of the
petroleum barrel is used for polymers, and thus petroleum is likely to remain as the principal raw
material for the indefinite future. Polymers constitute a high-value-added part of the petroleum
customer base and have led to increasing international competition in the manufacture of
commodity materials as well as engineering thermoplastics and specialty polymers.

The unique and valuable properties of polymers have their origins in the molecular composition
of their long chains and in the processing that is performed in producing products. Both
composition (including chemical makeup, molecular size, branching and cross-linking) and
processing (affected by flow and orientation) are critical to the estimated properties of the final
product.

MATERIALS

Structural Polymers

The familiar categories of materials called plastics, fibers, rubbers, and adhesives consist of a
diverse array of synthetic and natural polymers. It is useful to consider these types of materials
together under the general rubric of structural polymers because macroscopic mechanical
behavior is at least a part of their function. Compared with classical structural materials like
metals, the present usage represents a considerable broadening of the term.

These materials have many different chemical and physical forms, such as cross-linked
versus non-cross-linked, crystalline versus amorphous, and rubbery versus glassy. More recently,
structural polymers having liquid crystalline order have become important. Structural polymers
are rarely used in the pure form but often contain additives in small quantities, such as
antioxidants, stabilizers, lubricants, processing aids, nucleating agents, colorants, and antistatic
agents or, in larger quantities, plasticizers or fillers.

There is rapid growth in the areas of blends and composites. In composites, a material of fixed
shape, such as particles (filler) or fibers, is dispersed in a polymer matrix. The filler or fiber may
be an inorganic material or another organic polymer. Blends (or alloys) on the other hand consist
of two or more polymers mixed together and differ from composites in that the geometry of the
phases is not predetermined prior to processing. Some polymers are used for many different
purposes. A good example is poly (ethylene terephthalate), or PET, which was originally
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developed as a textile fiber. It is now used in film and tape (virtually all magnetic recording tape
is based on PET), as a molding material, and as the matrix for glass-filled composites. One of its
largest uses is for making bottles, especially for soft drinks. PET is also used in blends with other
polymers, such as polycarbonate.

Plastics

The word "plastic" is frequently used loosely as a synonym for "polymer," but the meaning of
"polymer'' is based on molecular size while "plastic" is defined in terms of deformability. Plastics
are polymeric materials that are formed into a variety of three-dimensional shapes, often by
molding or melt extrusion processes. They retain their shape when the deforming forces are
removed, unlike some other polymers such as the elastomers, which return to their original
shape. Plastics are usually categorized as thermoplastics or thermosets, depending on their
thermal processing behavior.

Thermoplastics

Thermoplastics are polymers that soften and flow upon heating and become hard again when
cooled. This cycle can be repeated many times, which makes reprocessing during manufacturing
or recycling after consumer use possible using heat fabrication techniques such as extrusion or
molding. The polymer chains in thermoplastics are linear or branched and do not become cross-
linked as in the case of thermosets. Example Polystyrene, Polypropylene, LDPE, HDPE, PVC

Thermosets

Thermosetting polymers
• This polymer is hard and infusible on heating.
• These are not soft on heating under pressure and they are not re-moluded.
• These polymers are cross linked or heavily branched molecules
These polymers we cannot reuse or recycle. Example, Some common examples are Bakelite,
urea-formaldehyde resins, etc

Elastomers
These are rubber – like solids with elastic properties. In these elastomeric polymers, the polymer
chains are held together by the weakest intermolecular forces. These weak binding forces permit
the polymer to be stretched. A few ‘crosslinks’ are introduced in between the chains, which help
the polymer to retract to its original position after the force is released as in vulcanised rubber.
The examples are buna-S, buna-N, neoprene, etc.

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Fibers

A fiber may be defined as a structure whose length is much greater than its cross-sectional
dimension. The diameter of fibers is characterized in, a unit of linear density corresponding to
the weight in grams of a 10,000-meter length of the fiber (the same units are used to describe
individual filaments and multifilament yarns). Typical filament values run from 1 to 10. One
gram of a filament is over 5 miles in length. Fibres are the thread forming solids which possess
high tensile strength and high modulus. These characteristics can be attributed to the strong
intermolecular forces like hydrogen bonding. These strong forces also lead to close packing of
chains and thus impart crystalline nature used in textile industries The examples are polyamides
(nylon 6, 6), polyesters (terylene), etc.

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Adhesives

An adhesive is a material that, by means of surface attachment, can hold together solid materials.
Adhesives have been used for most of recorded history. The physical strength of an assembly
made by the use of adhesives, known as an adhesive joint, is due partly to the forces of adhesion,
but primarily to the cohesive strength of the polymeric materials used to formulate the adhesive.
Thus, the range of strengths available in adhesive joints is limited to the strengths of the
polymers useful in the formulation of adhesives.

Adhesives are typically classified by their use or application. Thus structural adhesives are those
materials used to join engineering materials such as metals, wood, and composites.

Hot melt adhesives are those adhesives that are applied from the melt and whose properties are
attained when the adhesive solidifies.

Pressure-sensitive adhesives provide adherence and strength with only finger pressure during
application. Adhesive tapes are manufactured by applying a pressure-sensitive adhesive to a
backing.

Rubber-based adhesives are, as the name implies, based on elastomers and are usually applied as
a mastic or spray applied from solvent or water. Pressure-sensitive adhesives can be considered
to be a subset of rubber-based adhesives.

Each of the major classes of adhesives described above can be further classified by its chemistry.
Thus, the majority of structural adhesives are based on one or more of the following chemistries:
phenolic, epoxy, acrylic, bismaleimide, imide, and protein (derived from blood, soybean, casein,
and so on). Adhesives have several advantages over other joining technologies. The major
limitations to the broader use of adhesives in industry are the extreme sensitivity of adhesive
bonding to surface conditions and the lack of a nondestructive quality control method.

Blends and Alloys

There are several driving forces for blending two or more existing polymers. Quite often, the
goal is to achieve a material having a combination of the properties unique to each of the
components, such as chemical resistance and toughness. Another issue is cost reduction; a high-
performance material can be blended with a lower-cost polymer to expand market opportunities.
A third driving force for blending polymers of different types is addition of elastomeric materials
to rigid and brittle polymers for the purpose of toughening. Such blends were the first
commercial example of polymer blend technology and, even today, probably account for the
largest volume of manufacturing of multicomponent polymer systems.

One of the earliest blend products was a miscible mixture of poly (phenylene oxide) and
polystyrene. The former is relatively expensive and rather difficult to process. The addition of
polystyrene lowers the cost and makes processing easier. Numerous other commercial products
are now based on miscible or partially miscible polymer pairs, including polycarbonate-polyester
blends and high-performance ABS materials. A wide variety of compatibilized polymer alloys

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have been commercialized, and the area is experiencing a high rate of growth. A product based
on poly (phenylene oxide), a polyamide, and an elastomer has been introduced for use in forming
injection-molded automobile. The polyamide confers toughness and chemical resistance, the
poly (phenylene oxide) contributes resistance to the harsh thermal environment of automotive
paint ovens, while the elastomer provides toughening.

Another automotive application is the formation of plastic bumpers by injection molding of

Structural Composites

Polymer composites can provide the greatest strength-to-weight and stiffness-to-weight ratios
available in any material, even the lightest, strongest metals. Hence, high-performance and fuel-
economy-driven applications are prime uses of such composites. One of the most important
attributes is the opportunity to design various critical properties to suit the intended application.
Indeed, performance may be controlled by altering the constituents, their geometries and
arrangement, and the interfaces between them in the composite systems. This makes it possible
to "create" materials tailored to applications, the single greatest advantage and future promise of
these material systems. Structural composites are of interest in aerospace applications and in
numerous industrial and consumer uses in which light weight, high strength, long fatigue life,
and enhanced corrosion resistance are critical. Much needs to be done to advance processibility
and durability, to provide a more comprehensive database, and to improve the economics of
these systems. A wide range of future needs encompasses synthesis, characterization, processing,
testing, and modeling of important polymer matrix composite systems.

Liquid Crystalline Polymers

Liquid crystal polymer concepts have been extended to encompass a vast number of
homopolymer and copolymer compositions that exhibit either lyotropic or thermotropic
behavior. Industrially, most of the effort has been focused on the main-chain nematic polymers.
These polymers combine inherently high thermal and mechanical properties with processing ease
and versatility. Processing ease originates from the facile way that molecular rods can slide by
one another, the very high mechanical properties come from the "extended chain" morphology
present in the solid state, and the thermal stability derives from the highly aromatic chain
chemistry. Inherent in this structure is a high level of structural, and hence property, anisotropy
(for example, the axial modulus is 1 to 2 orders of magnitude higher than the transverse
modulus). The direction of molecular chain orientation is coincident with the direction of
covalent bonding in the chain; normal to the orientation direction the bonding is secondary (van
der Waals, hydrogen bonding, and so on). Low orientation in these materials means global but
not local randomness, and properties within "domains" are highly anisotropic.

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 Films, Membranes, and Coatings

Polymers are used in many applications in which their main function is to regulate the migration
of small molecules or ions from one region to another. Examples include containers whose walls
must keep oxygen outside or carbon dioxide and water inside; coatings that protect substrates
from water, oxygen, and salts; packaging films to protect foodstuffs from contamination,
oxidation, or dehydration; so-called "smart packages," which allow vegetables to respire by
balancing both oxygen and carbon dioxide transmission so that they remain fresh for long
storage or shipping times; thin films for controlled delivery of drugs, fertilizers, herbicides, and
so on; and ultrathin membranes for separation of fluid mixtures. These diverse functions can be
achieved partly because the permeability to small molecules via a solution-diffusion mechanism
can be varied over enormous ranges by manipulation of the molecular and physical structure of
the polymer. The polymer that has the lowest known permeability to gases is bone dry poly
(vinyl alcohol), while the recently discovered poly (trimethylsilyl propyne) is the most
permeable polymer known to date. The span between these limits for oxygen gas is a factor of
1010. A variety of factors, including free volume, intermolecular forces, chain stiffness, and
mobility, act together to cause this enormous range of transport behavior. Recent experimental
work has provided a great deal of insight, while attempts to simulate the diffusional process
using molecular mechanics are at a very primitive stage. There is clearly a need for guidance in
molecular design of polymers for each of the types of applications described in more detail
below. In addition, innovations in processing are needed.

Barrier Polymers

As shown earlier, packaging applications currently consume roughly one-third of the production
of thermoplastic polymers for fabrication of a wide array of rigid and flexible package designs.
These packages must have a variety of attributes, but one of the most important is to keep
contaminants, especially oxygen, out, while critical contents such as carbon dioxide, flavors, and
moisture are kept inside. Metals and glass are usually almost perfect barriers, whereas polymers
always have a finite permeability, which can limit the shelf-life of the products they protect. In
spite of this deficiency, the light weight, low cost, ease of fabrication, toughness, and clarity of
polymers have driven producers to convert from metal and glass to polymeric packaging.
Polymers often provide considerable savings in raw materials, fabrication, and transportation, as
well as improved safety for the consumer relative to glass; however, these advantages must be
weighed against complex life-cycle issues now being addressed. The following discussion
illustrates the current state of this technology, its problems, and future opportunities. There are
certain polymer molecular structures that provide good barrier properties; however, these
structural features seem invariably to lead to other problems. For example, the polar structures of
poly(vinyl alcohol), polyacrylonitrile, and poly(vinylidene chloride) make these materials
extremely good barriers to oxygen or carbon dioxide under certain conditions, but each material
is very difficult to melt fabricate for the same reason. The good barrier properties stem from the
strong interchain forces caused by polarity that make diffusional jumps of penetrant molecules
very difficult. To overcome these same forces by heating, so that the polymer chains can move in
relation to one another in a melt, requires temperatures that cause these reactive materials to
degrade chemically by various mechanisms. Thus neither poly (vinyl alcohol) nor
polyacrylonitrile can be melt processed in its pure form. Resorting to solvent processing of these

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materials or using them to make copolymers compromises their value. Poly(vinyl alcohol), by
virtue of its hydrogen bonding capability, is very hygroscopic, to the point of being water
soluble, and this property prevents its use as a barrier material in the pure form even if it could be
melt processed. In general, polarity favors good oxygen barrier properties but leads to poor water
barrier properties. This is true for aliphatic polyamides (nylon). On the other hand, very nonpolar
materials, such as polyethylene and polypropylene, are excellent barriers to water but not
oxygen. This property-processibility trade-off has led to an interest in composite structures. The
''composites" can be at the molecular level (copolymers), micro-level (blends), or macro-level
(multilayers).

The attractive barrier characteristics of poly (vinyl alcohol) have been captured via copolymers,
and this achievement has led to some important commercial products using clever molecular
engineering and processes that minimize its shortcomings of water uptake and lack of melt
processibility. Copolymers containing units of ethylene and vinyl alcohol are made commercially
by starting with ethylene and vinyl acetate copolymers and then hydrolyzing them. By critically
balancing the structure of these materials, melt processable products that are relatively good
barriers with reduced moisture sensitivity can be achieved. These copolymers are incorporated
into multilayer structures by co-extrusion processes. For example, blow-molded bottles with five
to seven layers in the side wall are in commercial use for marketing very sensitive foodstuffs.
Lightweight, squeezable, fracture-resistant bottles for ketchup are now on the market. Layers of
ethylene/vinyl alcohol copolymer provide the oxygen barrier to prevent spoilage of the sensitive
tomato base, while layers of polypropylene provide the water barrier that prevents dehydration
on storage. Interlayers are often needed to adhere the functional layers to one another when the
two differ greatly in chemical structure. Sometimes a mixed layer is included to accommodate
recycled material from the process. The barrier function can also be provided by metal foil or by
coatings of other polymers or inorganic layers onto containers. Of course, composite structures
are inherently more difficult to recycle. Layers based on halogen-based polymers generate acid
gases upon incineration. Reconciling these issues will be a major preoccupation during the next
decade.

Membranes

Membranes are used to produce potable water from the sea and brackish waters, to treat
industrial effluents, to recover hydrogen from off-gases, to produce nitrogen and oxygen-
enriched air from air, to upgrade fuel gases, and to purify molecular solutions in the chemical
and pharmaceutical industries. They are the key elements in artificial kidneys and controlled
drug delivery systems. Basically, membranes may function in one of two general ways,
depending on the separation to be performed and the structure of the membrane. Some
membranes act as passive filters, albeit usually on a very small scale. These membranes have
pores through which fluid flows, but the pores retain larger particles, colloids, or
macromolecules (e.g., proteins). Depending on the scale of the pores and the solute or particles,
the operations are subdivided into ultrafiltration, microfiltration, and macro-filtration. The
material dictates the manner in which the membrane can be formed and especially the size and
distribution of the pores. Porous polymer-based membranes are made by solution processes,
mechanical stretching, extraction, or ion bombardment processes. The nature of the membrane
material is a key factor in resistance to damage and fouling and in compatibility with the fluid

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phase (e.g., blood). Gas separation is clearly one of the most active and promising areas of
membrane technology for polymer science and engineering.

Inorganic Polymers

The materials described above are made up primarily of polymer molecules based on
covalently bonded chains in which carbon is the principal element. Polyethylene, polystyrene,
poly (methyl methacrylate), and poly (vinyl chloride) are all based on carbon chains with
differing side groups. Nitrogen and oxygen can also be incorporated into polymer chains, as in
polyamides (nylons) and polyesters, but carbon atoms separate the hetero-atoms. Considering the
importance and variety of organic polymers, natural and synthetic, it is remarkable that the
chemistry of carbon is so unique and so dominant. Other polymers exist in which carbon is less
dominant. Polypeptides and proteins have one nitrogen for every two carbons, and the great
variety is derived entirely from differences in groups attached to the alpha carbon atom. All of
these materials are, however, entirely "organic" in character. Polyoxymethylene is a polymer
with alternating oxygen and carbon along the main chain. It is a partially crystalline molding
compound. Poly (ethylene oxide), with two carbons for each oxygen in the chain, has been of
particular interest because of its water solubility.

SILICONES

Silicones are polymers whose backbones are long, flexible chains of alternating silicon and
oxygen atoms. Dangling from the backbone like charms from a bracelet are side chains, usually
small, carbon-based units, and the choice of these side chains gives silicones a remarkable
range of properties. The water-repellent grease has oily, nonpolar side chains such as methyl
groups. The nonpolar side chains and the polar water molecules do not mix, repelling the water
from the silicone. Another application of silicones depends on a careful balance between polar
and nonpolar side chains. Small amounts of silicone foaming agents control the bubble size in
polyurethane foams. A high proportion of polar side chains makes the foam foamier. The
bubbles become bigger, forming open pores and producing the soft foams found in car seats
and furniture cushions. Reduce the number of polar side chains, and the bubbles remain small.
These tiny bubbles do not open up to form pores, and the foam is a much stiffer solid used for
insulation.

Silicones have other, seemingly contradictory properties. A silicone resin coating the bread
pans in a bakery keeps fresh-baked bread from sticking in the pan, and a liquid silicone
polymer on the molds in tire factories does the same thing for newly made tires. But adding a
"tackifying resin" makes the silicone sticky and produces the drug-permeable contact adhesive
used on those skin patches containing nicotine (for smokers who are trying to quit) or
scopolamine (for seasickness sufferers who are trying not to lose it). Silicon and oxygen are the
two most abundant elements on Earth, and they combine naturally to form silicates, including
glass and such minerals as quartz and granite.

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