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A holistic perspective of coatings technology.



Organic coatings are functional materials, working substances. They are used in a wide variety of applications for a great number of reasons. Many of the functions that coatings provide meet essential societal needs. Their advancement has been and will continue to be important to the advancement of technology and society. Holism holism

In the philosophy of the social sciences, the view that denies that all large-scale social events and conditions are ultimately explicable in terms of the individuals who participated in, enjoyed, or suffered them.
 is the concept that whole entities have an existence other than the mere sum of their parts and that a broader perspective will yield better understanding and results. A coating is not just a polymer or pigments; a coating system is not just a primer and topcoat acting independently; an end product (i.e., the product to be coated) would not be as valuable without a properly functioning coating system. A coating is a complex material that is often a component of a coating system, which inturn provides added value Added value in financial analysis of shares is to be distinguished from value added. Used as a measure of shareholder value, calculated using the formula:

Added Value = Sales - Purchases - Labour Costs - Capital Costs
 to a final product. Coatings technology spans a wide spectrum, from the complex interactions and effects of individual paint ingredients, to the design of coating systems to perform specific functions, to the design and manufacture of end products. The focus of this paper is to suggest a holistic perspective of coatings technology, to illustrate that diversity of knowledge, thought, and approach in designing these coatings, coating systems, and final products will yield better science, better coatings and better final products.

Keywords: Gas chromatography gas chromatography (GC)

Type of chromatography with a gas mixture as the mobile phase. In a packed column, the packing or solid support (held in a tube) serves as the stationary phase (vapour-phase chromatography, or VPC) or is coated with a liquid stationary phase
, corrosion, corrosion protection, accelerated testing, service life prediction, surface chemistry, coating-substrate interface

**********

In the broadest sense, nearly everything we see, touch, and use is coated in some fashion. Some of these applications have obvious major consequences on our lives, while others are nearly invisible yet still affect almost everything that we do. Consider that for most of our society, two of the largest investments we make are in our homes and automobiles. Coatings are a primary contributing factor to the attractiveness, protection, and longevity of these investments. The proper design, selection, and application of coatings for these applications are critical to their successful long-term attractiveness and performance. We experience many other uses of coatings on nearly a minute-to-minute basis, often without even noticing the benefit or importance. Would you enjoy playing cards playing cards, parts of a set or deck, used in playing various games of chance or skill. The origin of playing cards is unknown, and almost as many theories exist as there are historians of the subject.  without their durable coatings that have low coefficient of friction coefficient of friction
n. pl. coefficients of friction
The ratio of the force that maintains contact between an object and a surface and the frictional force that resists the motion of the object.
 and abrasion abrasion /abra·sion/ (ah-bra´zhun)
1. a rubbing or scraping off through unusual or abnormal action; see also planing.

2. a rubbed or scraped area on skin or mucous membrane.
 resistance? Would your golf and tennis be as enjoyable without the bright and attractive coatings on balls, clubs, and racquets racquets, game played by two or four persons on a court 60 by 30 ft (18.3 m by 9.1 m); it is surrounded by three walls 30 ft (9.1 m) high and a backwall 15 ft (4.6 m) high. The ball, 1 in. (2.54 cm) in diameter, is made of polyethylene with an adhesive tape cover. ? Would you be safe driving without the reflective coatings on roadways and traffic signs? Would your electronic equipment work and have a long lifetime without protective coatings on the components? These examples illustrate the myriad of applications we demand of coatings. Other examples of the use of coatings may be even less obvious but can have even greater consequences.

In July 1967, the USS USS
abbr.
1. United States Senate

2. United States ship

USS abbr (= United States Ship) → Namensteil von Schiffen der Kriegsmarine
 Forrestal, a U.S. Navy aircraft carrier, was sailing off the coast of Vietnam. She had just received a full load of missiles and bombs, and the crew was preparing for aircraft flight operations. Without notice, a missile accidentally launched from one of the aircraft parked on the carrier's deck, exploding into another aircraft. A tremendous fire ensued, with hundreds of active bombs and missiles, dozens of freshly fueled aircraft, and just below the flight deck, a liquid oxygen plant. Within 90 seconds the fire caused a bomb to explode. The ensuing en·sue  
intr.v. en·sued, en·su·ing, en·sues
1. To follow as a consequence or result. See Synonyms at follow.

2. To take place subsequently.
 explosions and fire raged for four and a half days, killing 134 men and wounding hundreds more. One suspected cause for the accidental firing of the missile was electromagnetic interference See EMI.  (EMI (ElectroMagnetic Interference) An electrical disturbance in a system due to natural phenomena, low-frequency waves from electromechanical devices or high-frequency waves (RFI) from chips and other electronic devices. Allowable limits are governed by the FCC. ), which activated the firing mechanism. Coatings may have prevented this tragedy. Coatings that provide EMI shielding and current grounding are now used extensively on avionics avionics (ā'vēŏn`ĭks), electronic instruments used in air or space flight; also the design and production of such instruments. Early planes had few instruments, but as aviation and aircraft became more complex, so did instrumentation.  equipment, such as housings and cable connectors to minimize these types of risks. The extremely short time between the release of the first missile and the first bomb explosion, about 90 seconds, was because the missiles and bombs had only an aesthetic coating on their exterior, which provided no thermal insulation The term thermal insulation can refer to materials used to reduce the rate of heat transfer, or the methods and processes used to reduce heat transfer.

Heat is transferred from one material to another by conduction, convection and/or radiation.
 from the fire. Coatings could have greatly minimized the explosions and the extent of the fire. Now intumescent coatings are applied which delay up to 10 minutes before a bomb or missile will reach its detonation "cook off" temperature during a fire, allowing more time to fight the fire and move the explosives. The USS Forrestal was severely damaged but was saved due to the heroic efforts of her crew. (1)

[FIGURE 1 OMITTED]

On September 11, 2001, the World Trade Center South Tower collapsed just 54 minutes after being struck by an aircraft; the North Tower fell one hour and 54 minutes after the aircraft impact. One major cause for the collapse was the fire that ensued, which weakened the load-bearing steel structure. Coatings designed to provide thermal insulation during a fire were applied to these structures; these coatings can be effective at temperatures well above 1500[degrees]F. However, the thermal insulating coatings used on the towers were not designed to withstand the mechanical forces resulting from the aircraft collision. Upon impact, the coatings flew off of the structures, leaving them unprotected from the fire, which further weakened the structure. If the coatings remained intact, the buildings may not have collapsed. (2)

What Are Paints and Coatings?

By the simplest definition, paints are "any pigmented pigmented /pig·ment·ed/ (pig-ment´id) colored by deposit of pigment.

pig·ment·ed
adj.
Colored as the result of a deposit of pigment.
 liquid, liquifiable Adj. 1. liquifiable - capable of being liquefied
liquefiable

liquid - existing as or having characteristics of a liquid; especially tending to flow; "water and milk and blood are liquid substances"
, or mastic mastic, resin obtained from the small mastic tree Pistacia lentiscus (of the sumac family), found chiefly in Mediterranean countries. When the bark of the tree is injured, the resin exudes in drops. It is transparent and pale yellow to green in color.  composition designed for application to a substrate as a thin layer which is converted to an opaque solid film after application." (3) On a more detailed and fundamental level, coatings and paints are complex materials. Organic coatings usually consist of polymers, pigments, organic solvents and/or water, and numerous additives. A mature coating formulation may contain up to 20 different ingredients, all required to perform in the wet and dry state of a coating (and the transition from one state to the other--film formation). These ingredients do not exist or perform independently; they interact both physically and chemically. These interactions are complex and have been the subject of many studies. From another perspective, coatings are almost always applied in systems. Some coatings systems may consist of a primer and topcoat, while others have four to six coatings (e.g., automotive coating systems). Again, these coating layers do not perform independently. Coating systems are applied for a reason; each coating has functions to perform, and those functions are affected by the other coatings in the system. Interactions between coatings and coating system performance are complicated even further by the various interfaces, which include interfaces between coatings and at the substrate and surface. Finally, coatings are applied to products: cars, houses, cans, ships, airplanes, appliances, etc. The "appeal" and "performance" of these final products, which includes appearance, is very much dependent upon these coatings. So, coatings can and should be considered from a number of perspectives: as complex materials, in the coating systems they form, and for the role they play on the final end product. Of course this discussion has not begun to address other broader coating types, such as inorganic inorganic /in·or·gan·ic/ (in?or-gan´ik)
1. having no organs.

2. not of organic origin.


in·or·gan·ic
n.
1.
, metallic, and ceramic coatings ceramic coating,
n a thin layer of ceramic material, commonly hydroxyapatite, used to cover dental implants. This typically increases the hardness of the implant and can also make the implant bond more readily with bone.
. These also perform critical functions but will not be considered in this presentation due to the breadth of those technologies and the narrower scope of this paper.

Various Narrow Views of Coatings Technology

Coatings technology involves many disciplines, from the basics of chemistry and physics, to more advanced and specialized areas such as organic, polymer, and surface chemistry, to the applied fields of materials science and engineering Materials science and engineering

A multidisciplinary field concerned with the generation and application of knowledge relating to the composition, structure, and processing of materials to their properties and uses.
, to real-world knowledge of how materials behave, how they work, and how they fail. With these disciplines as a basis, along with the demands of career positions, technologists within the coatings industry take many specialized forms, each of us having our own perspective of coatings. The chemist at a raw material supplier of resins or additives may have expertise in polymer, organic, or surface chemistry, but may not be familiar with how to most effectively combine these ingredients (i.e., formulate) to obtain desired properties and performance of the applied coating. The paint chemist for a coatings manufacturer has the goal of formulating ingredients to develop a coating for production and sale, but may not have in-depth knowledge about polymer chemistry Polymer chemistry or macromolecular chemistry is a multidisciplinary science that deals with the chemical synthesis and chemical properties of polymers or macromolecules. , mechanical properties, or failure mechanisms. Engineers, designers, and specifiers have the responsibility of selecting coatings and coating systems for various end-use applications but may not be familiar with how coatings are developed, how they perform, and how they may or may not succeed in their end-use application. Similar statements may be made about coating applicators and end-users.

Considering the areas of concentration within the industry, it seems that very often we take a narrow, specialized view of coatings technology. For example, it is not unusual for a student studying the field of organic coatings to have a number of polymer courses, but no course on basic materials science materials science

Study of the properties of solid materials and how those properties are determined by the material's composition and structure, both macroscopic and microscopic.
. Such a course would provide at least a preliminary understanding of other materials, such as those that are common substrates for coatings. It also may provide a perspective of coatings composition, properties, and performance other than the traditional polymer perspective. Another frequent omission is knowledge of corrosion, which is a primary reason for many coating applications. The message is that all too often we take a narrow view of and approach to coatings technology, only the narrow view that seemingly is needed to complete the immediate task at hand.

[FIGURE 2 OMITTED]

A Holistic Perspective of Coatings Technology

Holism is the concept that whole entities have an existence other than the mere sum of their parts and that a broader perspective will yield better understanding and results. A coating is not just a polymer or pigments; a coating system is not just a primer and topcoat acting independently; an end product (i.e., the product to be coated) would not be as valuable without a properly functioning coating system. A coating is a complex material that is typically a component of a coating system, which provides added value (appearance, protection, etc.) to a final product. Coatings technology spans a wide spectrum, from the complex interactions and effects of individual paint ingredients, to the design of coating systems to perform specific functions, to the design and manufacture of end products. The focus of this paper is to suggest a holistic perspective of coatings technology, to illustrate that diversity of knowledge, thought, and approach in designing these coatings, coating systems, and final products will yield better science, better coatings, and better final products. This diversity can be obtained by individuals who have the ability, desire, and fortitude Fortitude
See also Bravery.

Fratricide (See MURDER.)

Asia

despite torture, refuses to deny Moses. [Islam: Walsh Classical, 35]

Calantha

fulfills wifely and queenly duties despite losses. [Br. Lit.
 to learn and practice multiple disciplines. It also can be displayed by utilizing functional teams of people, with various skills and disciplines, each providing their own perspective and value.

COATINGS AS COMPLEX MATERIALS

One approach to study and understand materials is to view the cause-effect relationships between composition, structure, processing, properties, and performance. (4) In essence, a material's composition, structure, and processing determine its properties and performance. When viewing coatings as materials, this approach can be expanded as illustrated in Figure 1, and could be expanded even further with a greater focus on raw materials. To discuss and understand all of these relationships is well beyond the scope of this paper. In fact, this topic may be beyond the scope of several undergraduate and graduate level courses. These statements reflect one message of this section: coatings are complex materials and if they are to be thoroughly understood, advanced, and utilized, it is essential that we take the time and effort to understand these relationships with a much broader perspective and far beyond a basic level. The following is an introductory view of these contributing factors, followed by an illustration of their complexity and importance.

Composition and Structure

Many have expressed the complexity and uniqueness of coatings in both composition and function. Coating formulations contain many materials with an exceptionally wide variety of chemistries. It is generally agreed that formulations consist of four classes of materials: polymers, pigments, solvents, and additives, each having the potential to provide selective properties. Commercial paint formulations may contain several ingredients within each of these material classes, leading to recipes that can include 20 or more ingredients of different chemistries, each contributing certain facets to final properties and performance (see Table 1 for an example). From a thermodynamic ther·mo·dy·nam·ic
adj.
1. Characteristic of or resulting from the conversion of heat into other forms of energy.

2. Of or relating to thermodynamics.
 perspective it is amazing a·maze  
v. a·mazed, a·maz·ing, a·maz·es

v.tr.
1. To affect with great wonder; astonish. See Synonyms at surprise.

2. Obsolete To bewilder; perplex.

v.intr.
 that this variety of ingredients can be combined to form a stable product (paint) in both the wet and applied (dry) states. On the other hand, thermodynamic interactions between ingredients can have a tremendously positive impact on coating material coating material,
n a biologically acceptable, usually porous nonmetal applied over the surface of a metallic implant with the expectation that tissue ingrowth will occur in the pores. Often a carbon polymer or ceramic substance.
 properties. For the most part, compositional effects of established ingredients used in coatings are fairly well understood and have been well documented. From a practical standpoint of coating formulation development, we certainly have learned how to "put raw materials together" to obtain some desired properties. However, it is not clear that we have taken full advantage of more intricate ingredient interactions and effects to obtain the best performance.

What do we mean by "structure" in a coating? The structure of a material describes the arrangement of its internal components. The structure of coating ingredients and applied coatings is multi-faceted and spans orders of magnitude, much more than many other materials.

Some facets of material structure within coatings include:

* Subatomic subatomic /sub·atom·ic/ (-ah-tom´ik) of or pertaining to the constituent parts of an atom.

sub·a·tom·ic
adj.
1. Of or relating to the constituents of the atom.

2.
 structure; e.g., electrons within atoms interacting with nuclei nuclei /nu·clei/ (noo´kle-i) [L.] plural of nucleus.

nu·cle·i
n.
Plural of nucleus.



nuclei

plural of nucleus.
 ([10.sup.-11]-[10.sup.-10] meters)

* Atomic structure; e.g., organization of atoms relative to one another ([10.sup.-10]-[10.sup.-9] meters)

* Molecular structure of ingredients polymer, pigments, solvents, and additives ([10.sup.-9]-[10.sup.-7] meters)

* Larger scale polymer morphology morphology

In biology, the study of the size, shape, and structure of organisms in relation to some principle or generalization. Whereas anatomy describes the structure of organisms, morphology explains the shapes and arrangement of parts of organisms in terms of such
 ([10.sup.-7]-[10.sup.-4] meters)

* Pigment pigment, substance that imparts color to other materials. In paint, the pigment is a powdered substance which, when mixed in the liquid vehicle, imparts color to a painted surface.  particle size Particle size, also called grain size, refers to the diameter of individual grains of sediment, or the lithified particles in clastic rocks. The term may also be applied to other granular materials. , distribution, and packing ([10.sup.-8]-[10.sup.-4] meters)

* Latex particles and resulting cell structure from film formation ([10.sup.-8]-[10.sup.-6] meters)

* Macroscopic macroscopic /mac·ro·scop·ic/ (mak?ro-skop´ik) gross (2).

mac·ro·scop·ic or mac·ro·scop·i·cal
adj.
1. Large enough to be perceived or examined by the unaided eye.

2.
 structure of coating thickness and form, defects, etc. ([10.sup.-6]-[10.sup.-4] meters)

These structural aspects are interesting in that some levels of structure create composition (i.e., sub-atomic, atomic, molecular) and some levels of structure are created by composition (i.e., polymer morphology, pigment packing, latex cell structure, macroscopic structure). Nonetheless, all of these "structural" components affect coating properties, but it is not clear that practical commercial formulations have benefited to the fullest extent from an understanding of these effects. To illustrate the magnitude and importance these ingredients and interactions can have, pigment-polymer interactions and the resulting effects will be discussed in greater detail below.

Processing (Paint Manufacture and Application)

Processing a material usually refers to making the material. In the case of coatings, two types of processes must be considered: paint manufacturing and application. In the former, the wet coating is being produced, while the latter is the first step in producing the applied, dry coating. In essence, application is a step in producing or refurbishing the final product (e.g., car, appliance, etc.). Most concerns with paint manufacturing deal with obtaining the proper dispersion dispersion, in chemistry
dispersion, in chemistry, mixture in which fine particles of one substance are scattered throughout another substance. A dispersion is classed as a suspension, colloid, or solution.
 (pigment size and stability), combining ingredients to get thorough and stable mixing, and completing this in an energy-and time-efficient manner. Of course improper processing certainly can produce bad paint. Some potential problems include instability, incompatibility The inability of a Husband and Wife to cohabit in a marital relationship.


incompatibility n. the state of a marriage in which the spouses no longer have the mutual desire to live together and/or stay married, and is thus a ground for divorce
, pigment settling and compaction, and short shelf life. Subsequently, these problems can then lead to another broad set of unattractive symptoms that can cause premature failure of an applied coating.

Application procedures certainly can have major effects on coating properties. Most savvy people in the industry know and have experienced that the applicator ap·pli·ca·tor
n.
An instrument for applying something, such as a medication.


applicator,
n a device for applying medication; usually a slender rod of glass or wood, used with a pledget of cotton on the end.
 can "make or break" the coating. Experienced applicators have the knowledge and ability to do what needs to be done to make a coating work in an application. Some key factors are: surface preparation and paint preparation prior to application, application method and associated parameters, coating thickness, and environmental factors (e.g., temperature, humidity, air flow, sunlight). Fundamental research in this area is relatively thin. Most advances are made empirically at the manufacturing or application site. It is important to note that many application processes have been automated, for example OEM (Original Equipment Manufacturer) The rebranding of equipment and selling it. The term initially referred to the company that made the products (the "original" manufacturer), but eventually became widely used to refer to the organization that buys the products and  automotive, appliance, and can coating applications. These processes have improved efficiency, uniformity, and reliability--in general, overall performance. A broader knowledge of this area would assist in understanding paint properties and performance.

Properties and Performance

"Property" is a trait describing the kind and magnitude of response a material has to a specific imposed stimulus (e.g., the mechanical response a material has to a tensile tensile,
adj having a degree of elasticity; having the ability to be extended or stretched.
 force; chemical response to UV exposure; physical and thermal response to temperature changes). Typically, properties are defined solely by the composition, structure, and processing of a material, independent of the material's size and shape. However, with some types of materials, especially coatings, properties are affected dramatically by other imposed parameters. Coatings are specifically designed to be applied and dried under certain conditions (application method, substrate type, film thickness, temperature, humidity, etc.). It would be inappropriate and misleading to measure properties of coatings prepared outside the boundaries of these parameters; for example, measuring properties of a coating that is 10 mils thick while the coating was designed to be applied at 2 mils. Therefore, with coatings, it is important to understand all of the parameters associated with the intended application and service life to obtain an accurate assessment of properties and performance as measured within these parameters. It also is important to relate these properties to fundamental characteristics associated with composition, structure, and processing.

The "performance" of a material is its ability to provide its intended in-service function. For example, how long will the coating last; will it maintain appearance; will it prevent corrosion; will it perform the function(s) it was intended to provide? The relationship between properties and performance is interesting. Properties are normally evaluated in a laboratory or other controlled or documented environment and condition. Performance occurs in the "real world." While we can try to reproduce or simulate what happens in the real world over a coating's lifetime, it is extremely difficult to be exact or to provide a response that is always indicative. Nonetheless, extensive efforts to accomplish this are necessary and are being pursued. An excellent example is coating durability and weathering, which have been the focus of much intensive and fruitful research over recent years (for example, see references 5-8). Tremendous strides have been made at understanding natural weathering, mimicking and accelerating these conditions in a laboratory environment, and assessing their effects on coatings. Although advances have been made in this area, even leading experts profess pro·fess  
v. pro·fessed, pro·fess·ing, pro·fess·es

v.tr.
1. To affirm openly; declare or claim: "a physics major
 that further improvements are necessary. This body of work is an excellent example of the importance and value of a holistic perspective of coatings technology, including fundamental understandings of composition and structure, coating system interaction and properties, real-world performance, and analytical methods to assess these effects. Considering the work that has been reported in this area, it becomes even more evident that a holistic perspective of coatings technology is essential to understand factors that contribute to a coating's level of success.

[FIGURE 3 OMITTED]

To conclude these thoughts on properties and performance, it is important to recognize that properties suggest how a material will perform in service; they are not a guarantee of in-service performance. It also must be recognized that during a coating's service life, it will be subjected to multiple stimuli and stresses, often at the same time. In many cases, failure is not due to one specific stress or weak property; it is due to the cumulative effects of multiple stresses over a period of time. This often is not observable ob·serv·a·ble  
adj.
1. Possible to observe: observable phenomena; an observable change in demeanor. See Synonyms at noticeable.

2.
 or considered in the laboratory environment, sometimes this is not even considered when doing failure analysis.

Interactions Within Applied Coatings--An Example

As an applied solid film, coatings consist of dispersed dis·perse  
v. dis·persed, dis·pers·ing, dis·pers·es

v.tr.
1.
a. To drive off or scatter in different directions: The police dispersed the crowd.

b.
 pigment particles throughout a polymeric polymeric /poly·mer·ic/ (pol?i-mer´ik) exhibiting the characteristics of a polymer.

pol·y·mer·ic
adj.
1. Having the properties of a polymer.

2.
 matrix. In this regard, paints are a subset of a more general material type, namely polymeric composites and, more specifically, particulate-filled composites. There have been many studies on the variety of aspects related to the effects of pigments and fillers in paints. The geometry, size, and concentration of filler fill·er 1  
n.
One that fills, as:
a. Something added to augment weight or size or fill space.

b. A composition, especially a semisolid that hardens on drying, used to fill pores, cracks, or holes in wood, plaster,
 particles affect nearly all properties of a coating. One aspect that has been studied, but to a lesser extent, is that of pigment (filler)-polymer interactions, which result in polymer adsorbed onto pigment particle surface and the formation of an adsorbed polymer layer (adlayer) around the particle. This polymer adlayer has distinct features (conformational, morphological mor·phol·o·gy  
n. pl. mor·phol·o·gies
1.
a. The branch of biology that deals with the form and structure of organisms without consideration of function.

b.
, mechanical, etc.) that can be noticeably different from the bulk polymer. Although somewhat more obscure in their contributions than other factors, these interactions still play a major role in coating properties and performance. One vivid illustration of this is effects on mechanical properties. If there were no attractive interaction between a filler particle surface and the polymer matrix, the filler particle would be seen as a flaw within the polymer that would act as a stress concentrator and dramatically decrease mechanical properties of strength and modulus See modulo. . In contrast, strength and modulus can increase with addition of filler particles with favorable fa·vor·a·ble  
adj.
1. Advantageous; helpful: favorable winds.

2. Encouraging; propitious: a favorable diagnosis.

3.
 filler-polymer interactions. Particles can disperse disperse /dis·perse/ (dis-pers´) to scatter the component parts, as of a tumor or the fine particles in a colloid system; also, the particles so dispersed.

dis·perse
v.
1.
 an applied load; they also can stop crack propagation The transmission (spreading) of signals from one place to another. . They can help restrict plastic deformation plastic deformation,
n any irreversible deformation of tissues.
 thereby improving yield and tensile strength tensile strength

Ratio of the maximum load a material can support without fracture when being stretched to the original area of a cross section of the material. When stresses less than the tensile strength are removed, a material completely or partially returns to its
, as well as hardness. Figure 2 illustrates an example of this effect. Other observable and important effects from pigment-polymer interactions include: rheology modification, prohibited pigment settling, (9,10) increased [T.sub.g] (11-16) decreased permeability permeability /per·me·a·bil·i·ty/ (per?me-ah-bil´i-te) the property or state of being permeable.

per·me·a·bil·i·ty
n.
1. The property or condition of being permeable.

2.
, (17,18) and viscoelastic Adj. 1. viscoelastic - having viscous as well as elastic properties
natural philosophy, physics - the science of matter and energy and their interactions; "his favorite subject was physics"
 behavior. (19)

How and why do these effects occur? This question can be answered with an explanation of the thermodynamic and physical aspects of polymer adsorption adsorption, adhesion of the molecules of liquids, gases, and dissolved substances to the surfaces of solids, as opposed to absorption, in which the molecules actually enter the absorbing medium (see adhesion and cohesion).  onto filler particles and the subsequent effects on the properties of the composite. Before providing this explanation, or at least a summary of some salient issues, it should be noted that much of the research on this subject has been done for particulate-filled systems, but not necessarily coatings. Nonetheless, similar fillers and polymers have been used in these studies and the findings certainly can be and should be applied to coatings technology.

The interaction between filler particle surface and an adsorbing polymer species is caused most commonly by Van der Waal forces, the most notable of these being London (dispersion) and Keesom (polar) forces. It is informative to compare the potential energy-distance relationships for various types of bonds (Figure 3). At relatively close distances (1-3 [Angstrom angstrom (ăng`strəm), abbr. Å, unit of length equal to 10−10 meter (0.0000000001 meter); it is used to measure the wavelengths of visible light and of other forms of electromagnetic radiation, such as ultraviolet ]), primary bonds have a deep energy well, indicating strong but highly localized forces. In contrast, dispersion forces have lower potential energy but they are more significant at longer distances. The implications are that intermolecular forces intermolecular forces, forces that are exerted by molecules on each other and that, in general, affect the macroscopic properties of the material of which the molecules are a part. Such forces may be either attractive or repulsive in nature. , especially dispersion forces, not only cause polymer adsorption onto pigment, but they have effects well past the immediate adsorbed surface. In fact, Fowkes suggested that only dispersive dispersive /dis·per·sive/ (-per´siv)
1. tending to become dispersed.

2. promoting dispersion.
 forces transcend phase boundaries. (20) Both theory and empirical results indicate that polymers adsorbed onto filler particles can have noticeable effects tens, possibly hundreds, of nanometers into the polymer matrix of the material. The strength of these interactions can range up to 80 kJ/mole. Some evidence strongly suggests that an increased attraction (strength of interaction) between adsorbent adsorbent /ad·sor·bent/ (ad-sor´bent)
1. pertaining to or characterized by adsorption.

2. a substance that attracts other materials or particles to its surface by adsorption.
 and adsorbate ad·sor·bate  
n.
An adsorbed substance.

Noun 1. adsorbate - a material that has been or is capable of being adsorbed
 produces a tighter and denser layer of polymer, with decreased overall mobility, and morphological and physical properties distinct from that of the bulk matrix polymer phase. (21,22)

One method of characterizing pigment surfaces and potential interactions with polymers is inverse gas chromatography (IGC (Integrated Graphics Controller) The inclusion of the video display circuitry on the motherboard. An IGC is typically contained in the chipset, such as the Northbridge. See integrated graphics and IGP.

IGC - Institute for Global Communications
). In this technique, a column is packed with solid particles of interest (e.g., pigment, polymer particles). Specific probes are introduced into the column to measure their distinct retention times through the packed column, which is affected by a number of factors including secondary bonding forces between the probe and particles. Retention times can then be used to calculate thermodynamic parameters of the system, such as surface tension of the particles, as well as the free energy, enthalpy enthalpy (ĕn`thălpē), measure of the heat content of a chemical or physical system; it is a quantity derived from the heat and work relations studied in thermodynamics. , entropy entropy (ĕn`trəpē), quantity specifying the amount of disorder or randomness in a system bearing energy or information. Originally defined in thermodynamics in terms of heat and temperature, entropy indicates the degree to which a given , and work of adhesion. Although polymers and pigments must be analyzed separately, they are done so with common probes so that both qualitative and quantitative associations between pigments and polymers can be concluded from the analysis. Reference 23 provides a review of IGC technique and analysis.

IGC studies have illustrated the potential magnitude of these thermodynamic parameters of pigment surfaces and polymer-filler interactions. (24-26) For several grades of titanium titanium (tītā`nēəm, tĭ–) [from Titan], metallic chemical element; symbol Ti; at. no. 22; at. wt. 47.88; m.p. 1,675°C;; b.p. 3,260°C;; sp. gr. 4.54 at 20°C;; valence +2, +3, or +4.  dioxide with various surface treatments, the dispersive component of the solid surface tension, [[gamma].sup.D], ranged from 50 to 125 mJ/[m.sup.2], with higher surface tension for grades with greater surface treatments of alumina alumina (əl`mĭnə) or aluminum oxide, Al2O3, chemical compound with m.p. about 2,000°C; and sp. gr. about 4.0.  and silica--also commercially promoted as "high quality" grades. [[gamma].sup.D] for poly(methyl methacrylate methyl methacrylate
(meth´il methak´rilāt),
n an acrylic resin, CH2 = C(CH3)COOCH3, derived from methyl acrylic acid. Monomer is the single molecule and polymer is the polymerization product.
) and poly(acrylic acid acrylic acid /acryl·ic ac·id/ a readily polymerizing liquid used as a monomer for acrylic polymers. ) was around 41 mJ/[m.sup.2], indicating that these polymers fulfill the thermodynamic requirement to wet all of the pigments evaluated. (27) This result would hold for most common pigment-polymer combinations but the specific magnitude of the interactions can vary dramatically. This is illustrated by comparing the dispersive work of adhesion, which ranged from 91 to 145 mJ/[m.sup.2] for the particular pigment-polymers assessed. The free energy, enthalpy, and entropy of adsorption also provide a quantitative means for assessing interactions. Free energy of adsorption ranged from -15 to -30 kJ/mole, indicating spontaneous and stable interactions. Enthalpies of adsorption up to -80 kJ/mole were measured, which is quite impressive. In comparison, the strength of hydrogen bonding hydrogen bonding

Interaction involving a hydrogen atom located between a pair of other atoms having a high affinity for electrons; such a bond is weaker than an ionic bond or covalent bond but stronger than van der Waals forces.
 can be up to 30 kJ/mole. Free energy and enthalpy of adsorption were more negative (indicating more favorable and stronger interactions) with probes that had greater polarity (1) The direction of charged particles, which may determine the binary status of a bit.

(2) In micrographics, the change in the light to dark relationship of an image when copies are made.
. However, in comparing the dispersive versus polar contributions, it is interesting that the dispersive component can contribute up to 90% of the adsorption enthalpy, even for highly polar probes. These parameters certainly help provide a quantitative understanding of the likelihood, strength, and stability of interactions that can occur between polymers and pigments in paints.

Another technique that has been used to study polymer adsorption onto filler particles is flow calorimetry calorimetry (kăl'ərĭm`ətrē), measurement of heat and the determination of heat capacity , which entails percolating a polymer solution through a bed of pigment particles and measuring the heat produced. (28-30) By subsequently flowing just the solvent through the column and "rinsing" the pigment bed, a measure of reversibility re·vers·i·ble  
adj.
1. That can be reversed, as:
a. Finished so that either side can be used: a reversible fabric.

b.
 of the polymer adsorption can be obtained. Several benefits of this technique are: (1) solutions of monomers and polymers can be used as opposed to model or probe compounds; (2) the measurement is a direct enthalpy of adsorption as opposed to a calculated value; (3) irreversible irreversible (ir´ēvur´sebl),
adj incapable of being reversed or returned to the original state.
 adsorptions can be studied and a measure of reversibility can be obtained; and (4) the amount of polymer adsorbed can be determined by using a detector (refractometer refractometer /re·frac·tom·e·ter/ (re?frak-tom´e-ter)
1. an instrument for measuring the refractive power of the eye.

2.
 or UV spectrophotometer spectrophotometer, instrument for measuring and comparing the intensities of common spectral lines in the spectra of two different sources of light. See photometry; spectroscope; spectrum. ) on the effluent effluent

waste from an abattoir carried away in liquid form. Disposal is a major problem because of the need to avoid pollution of waterways. See aerobic effluent treatment, anaerobic effluent treatment.
 stream of the calorimetry column.

Using flow calorimetry, the same pigment-polymer interactions were studied as those discussed above with IGC. (31) Enthalpies of adsorption of methyl methacrylate onto various grades of Ti[O.sub.2] ranged from 0.04 to 0.99 J/gr of adsorbent and, normalizing per pigment surface area, 5 to 28 mJ/[m.sup.2]. As with the IGC analysis, pigments with greater surface treatments had higher adsorption enthalpy. Desorption Desorption

A process in which atomic and molecular species residing on the surface of a solid leave the surface and enter the surrounding gas or vacuum.
 endotherms, measured by "rinsing" with the carrier solvent, indicated most of these adsorptions were nearly 95% irreversible. In addition to the strength of the interaction, another contributing factor is the concentration of potential interaction sites on a filler. For example, some silica silica or silicon dioxide, chemical compound, SiO2. It is insoluble in water, slightly soluble in alkalies, and soluble in dilute hydrofluoric acid. Pure silica is colorless to white.  treatments can have about 2 SiOH sites/n[m.sup.2]. Consider a Ti[O.sub.2] grade that has a silica surface treatment, an average particle size of 0.3 nm, and a specific surface area of 15 [m.sup.2]/gr. This pigment can have up to [10.sup.7] SiOH groups/particle, resulting in about 3 X [10.sup.19] SiOH groups/gr pigment. A paint formulated at 20% pigment volume concentration with this Ti[O.sub.2] would contain about 2.5 X [10.sup.19] SiOH sites per milliliter milliliter /mil·li·li·ter/ (mL) (-le?ter) one thousandth (10-3) of a liter.

mil·li·li·ter
n. Abbr.
 of applied dry paint. Considering both the strength of adsorption and the number of available sites, this certainly allows for ample opportunity for extensive pigment-polymer interaction throughout the applied film.

What are the physical consequences of these interactions from an adsorbed layer perspective? As mentioned above, a number of researchers have proposed that stronger interactions result in thicker and more influential polymer adlayers on filler particle surface. There are a number of experimental approaches to measuring this adsorbed layer thickness. Table 2 summarizes various techniques and previous findings with various filler-polymer systems. One observation from these results is the wide range in the magnitude of the adlayer thickness, from several nanometers up to microns. This apparent discrepancy may be due to differences in size and concentration of filler particles, the chemical differences in the systems studies, the technique used to measure this thickness, and/or to the variation in interpretation of the adlayer (i.e., where it ends in relation to the bulk polymer phase). For the Ti[O.sub.2] systems discussed above, the adlayer of PMMA PMMA polymethyl methacrylate.  was measured using both centrifugation Centrifugation

A mechanical method of separating immiscible liquids or solids from liquids by the application of centrifugal force. This force can be very great, and separations which proceed slowly by gravity can be speeded up enormously in centrifugal
 and rheological rhe·ol·o·gy  
n.
The study of the deformation and flow of matter.



rheo·log
 energy dissipation Dissipation
See also Debauchery.

Breitmann, Hans

lax indulger. [Am. Lit.: Hans Breitmann’s Ballads]

Burley, John

wasteful ne’er-do-well. [Br. Lit.
. (32) PMMA adlayers ranged from 10 to 100 nm depending upon the measurement technique, Ti[O.sub.2] grade, and PMMA molecular weight. Using these measurements, the effective filler volume concentration in an applied film (i.e., volume of pigment and adsorbed polymer) was calculated to be nearly double that of the pigment volume concentration alone. In addition, there was a definite trend that pigment-polymer systems having stronger adsorption had thicker adsorbed layer. This work led to a proposed scheme for the adlayer being tightly bound and very immobile im·mo·bile
adj.
1. Immovable; fixed.

2. Not moving; motionless.



immo·bil
 near the pigment surface but farther from the surface polymer chains that are not directly anchored to the surface are more mobile than the tight adlayer but not as mobile as the bulk polymer. Figure 4 illustrates the concept in terms of rigidity rigidity /ri·gid·i·ty/ (ri-jid´i-te) inflexibility or stiffness.

clasp-knife rigidity
 of the adlayer as a function of distance from the filler particle surface.

With some understanding of the thermodynamic and physical extent of filler-polymer interactions, what practical implications do they have and how can we take advantage of these interactions in real world formulations? To answer this we can look at effects on coating properties. To extend the study of the above systems, a number of coatings were formulated and evaluated. (33) Some definitive trends in properties were observed. As filler-polymer interactions increased, pigment particles were less likely to settle. This is caused by the bonding between polymer and particles, which minimizes the potential for particle-particle interaction by providing steric steric /ste·ric/ (ster´ik) pertaining to the arrangement of atoms in space; pertaining to stereochemistry.

ster·ic or ster·i·cal
n.
 stabilization. This allows the particles to remain suspended throughout both the wet and applied coating. As a result of this effect, contrast ratio also is improved. Improved pigment dispersion generally enhances coating opacity Refers to being "opaque," which means to prevent light from shining through. For example, in an image editing program, the opacity level for some function might range from completely transparent (0) to completely opaque (100).  due to more efficient light scattering.

Flexibility tests indicated that coatings with stronger pigment-polymer interactions were less flexible. Scrape See scraping.  adhesion evaluations indicated the same trend because of brittle (jargon) brittle - Said of software that is functional but easily broken by changes in operating environment or configuration, or by any minor tweak to the software itself. Also, any system that responds inappropriately and disastrously to abnormal but expected external stimuli; e.  failure of the film. It has been reported that glassy type polymer coatings follow a general trend of poorer adhesion with decreasing flexibility. (34) In addition, other reports have indicated that coatings with higher internal stresses exhibit lower adhesion to their substrate. (35,36) These internal stresses cause the coating to be less flexible and to fail (adhesively and/or cohesively) when external forces are applied. For the systems evaluated, filler-polymer interactions may decrease adhesion because polymer chains that firmly attach to the filler surface decrease mobility and may increase the internal stress within the polymer matrix, resulting in reduced adhesion to the substrate.

Finally with regards to coating performance, there was a definite trend of improved coating performance during salt spray exposure (i.e., less blistering blis·ter·ing
n.
See vesiculation.
 and uplifting) with improved pigment-polymer interactions. This is probably caused by decreased permeability due to increased immobilization Immobilization Definition

Immobilization refers to the process of holding a joint or bone in place with a splint, cast, or brace. This is done to prevent an injured area from moving while it heals.
 of the polymer adlayer or, stated another way, increased effective filler volume concentration. These coating performance test results, when studied in light of the thermodynamic and adlayer thickness results, clearly indicate the potential effects of these interactions and the role they can play on properties and in-service performance.

The message of this section is that ultimately, the function of the "coatings technologist," whatever specific role they may play, is to provide coatings that perform as intended when applied to the real-world end product. One contributing factor to succeeding at this goal is to understand how coatings behave as materials, and to use that knowledge to develop better raw materials, to formulate better coatings, to manufacture and apply better coatings, to specify better coatings, and to understand how coatings perform when applied to their end product. We must create the composition and structure, and use processing techniques that will give coatings desirable properties to perform as desired--in paint systems and on final end products.

COATINGS AS PART OF A PAINT SYSTEM

Paints are almost always applied as a system of layered coatings. In some cases, these systems are comprised of three to four coatings plus a substrate and usually some form of substrate pretreatment pretreatment,
n the protocols required before beginning therapy, usually of a diagnostic nature; before treatment.

pretreatment estimate,
n See predetermination.
(s). More demanding applications typically require multiple coatings to meet a multitude of stringent requirements. Vivid examples of demanding applications are automotive, aircraft, and structural steel, all of which have different requirements but typically contain multiple coatings in their finishing systems. To further illustrate, Figure 5 shows sample coating systems for metal and plastic automotive exterior substrates.

As exemplified by automotive paint systems, all of the individual coatings in multi-coat systems provide critical functions for the entire system to succeed. Each of the individual coatings has its own set of attributes, and they also have interfaces between them, at the substrate, and at the surface. Aside from properties of the individual coatings, the layers of coatings and their respective interfaces (including the top surface) have chemical and mechanical interactive effects, some of which may be quite substantial and possibly unexpected. These effects can be synergistic synergistic /syn·er·gis·tic/ (sin?er-jis´tik)
1. acting together.

2. enhancing the effect of another force or agent.


syn·er·gis·tic
adj.
1.
, and they can be beneficial or detrimental. It is essential to consider not only individual coatings, but also their interactions and performance in the coating system design and assessment. The following examples of substrate and coating layer interactions illustrate the potential magnitude of these effects and the importance of such a perspective--to view not only individual coatings, but also their properties, as a system of layered materials, from substrate to surface.

Chemical Interactions between Coatings and Metal Substrates

Along with a myriad of other functions, corrosion prevention is one of the main responsibilities of coating systems in high performance applications, such as automotive, aerospace, and structural steel. By definition, coatings are applied to a substrate. The origin of interactions between the layers within a coating system begins at the substrate-coating interface. The most obvious property affected is adhesion, but there are many others. One illustration of this is the work presented by Kumins. (37) From the previous discussion concerning polymer adsorption onto filler particles, one can deduce de·duce  
tr.v. de·duced, de·duc·ing, de·duc·es
1. To reach (a conclusion) by reasoning.

2. To infer from a general principle; reason deductively:
 that similar adsorption processes can occur when a coating is applied to a substrate, especially a metal substrate; that is, the polymeric binder binder: see combine.


An earlier Microsoft Office workbook file that let users combine related documents from different Office applications. The documents could be viewed, saved, opened, e-mailed and printed as a group.
 can adsorb adsorb /ad·sorb/ (ad-sorb´) to attract and retain other material on the surface; to conduct the process of adsorption.

ad·sorb
v.
To take up by adsorption.
 onto the substrate in a similar fashion as adsorption onto pigment particles. This adsorption anchors polymer chains onto the substrate, thereby restricting segment mobility. Although there is an immediate and distinct adsorbed polymer layer, other polymer chains further from the substrate also are affected and this may extend well into the coating, up to 500 nm (yet another structural feature within the coating). This is consistent with the model proposed and described previously for adsorption of polymer onto pigment particles (Figure 4). This adsorption can cause properties of the polymer to be striated striated /stri·at·ed/ (stri´at-ed) having stripes or striae.

striate, striated

having streaks or striae, e.g. striate retinopathy.


striate border
see brush border.
 throughout the film. Restriction of the adsorbed polymer increases [T.sub.g], decreases diffusion of foreign species, decreases solvent solubility solubility

Degree to which a substance dissolves in a solvent to make a solution (usually expressed as grams of solute per litre of solvent). Solubility of one fluid (liquid or gas) in another may be complete (totally miscible; e.g.
, and increases strength and stiffness. Kumins focused on adhesion and corrosion protection. Stronger adsorbed polymer yields stronger adhesion along with less diffusion of corrosive corrosive /cor·ro·sive/ (kor-o´siv) producing gradual destruction, as of a metal by electrochemical reaction or of the tissues by the action of a strong acid or alkali; an agent that so acts.  contaminants, and therefore, noticeable improvements in corrosion protection can be realized. However, in more general terms, Kumins' work illustrates that chemical interactions at interfaces can change a number of physical and mechanical properties of coatings and these changes can be observed throughout the coating system.

Interactions at coating-metal interfaces are complicated even further when contaminants (e.g., water, oxygen, ions) reach this interface with subsequent effects on adhesion and corrosion processes. Of these contaminants, water is generally the most insidious insidious /in·sid·i·ous/ (-sid´e-us) coming on stealthily; of gradual and subtle development.

in·sid·i·ous
adj.
Being a disease that progresses with few or no symptoms to indicate its gravity.
. The majority of coatings allow enough water diffusion to the coating-metal interface to allow corrosion. (38) However, it is generally considered that a prerequisite for corrosion processes to occur under paint films is the loss of adhesion or disbondment of the coating from the surface. A large body of research has illustrated the myriad of potential mechanisms for corrosion processes and coating failure in the presence of water, as well as corrosion inhibition mechanisms (see, for example, references 39-41). One common feature through this work is that good adhesion of coatings to metal substrates, especially with the presence of water, is a great contributing factor to corrosion prevention. Furthermore, yet another contributing factor is the resistance of the interface to attack. Both coating and metal substrate can be prone to chemical attack via a number of mechanisms during corrosion. (42) Degradation of either can lead to additional corrosion. But stability of the coating and the metal surface (including pretreatments) improves chances of preventing corrosion. Our understanding of how various adhesion phenomena and adhesion loss processes affect corrosion performance is a focused example of the need and benefits to take a broader view of coating performance-substrate material and preparation, pretreatment, coating types and systems, application processes, product design, test details, real world environment, and so on.

[FIGURE 4 OMITTED]

Interactions within Coating Systems on Plastic Substrates

Plastic materials provide numerous benefits, including cheaper and easier processing, lower weight, and inherent corrosion resistance. This is especially true in automotive applications. However, as with all materials, plastics have their own set of drawbacks and one drawback DRAWBACK, com. law. An allowance made by the government to merchants on the reexportation of certain imported goods liable to duties, which, in some cases, consists of the whole; in others, of a part of the duties which had been paid upon the importation.  is generally poor adhesion of applied coatings. Thermoplastic A polymer material that turns to liquid when heated and becomes solid when cooled. There are more than 40 types of thermoplastics, including acrylic, polypropylene, polycarbonate and polyethylene.  polyolefin (TPO (Twisted Pair Only) Refers to the use of twisted pair wire when other options are available. For example, a TPO suffix at the end of 3com Ethernet adapter model numbers indicates the card has only an RJ45 connector. ) is a particularly problematic substrate. Ryntz and co-workers have led the research of paint adhesion to and mechanical effects on plastic. (43-46)

Traditional explanations for the lack of coating adhesion to TPO are its low surface energy and "inertness in·ert  
adj.
1. Unable to move or act.

2. Sluggish in action or motion; lethargic. See Synonyms at inactive.

3. Chemistry Not readily reactive with other elements; forming few or no chemical compounds.
," which prohibit favorable coating-substrate interactions. A number of pretreatments are used to promote adhesion to plastics, including flame and plasma treatments, as well as chlorinated chlorinated /chlo·ri·nat·ed/ (klor´i-nat?ed) treated or charged with chlorine.

chlorinated

charged with chlorine.


chlorinated acids
some, e.g.
 polyolefin (CPO (Chief Privacy Officer) An individual who manages the privacy issues within an organization. Arising out of the privacy regulations in finance and health care in the late 1990s, the CPO position eventually crossed over to all industries. ) primers. Focusing on CPO treatments, Ryntz, et al. have presented a mechanism for paint system adhesion and causes for failure. Upon application of the CPO coating, solvent and CPO polymer chains diffuse through the crystalline Like a crystal. It implies a uniform structure of molecules in all dimensions. For example, phase change technology, widely used for rewritable optical discs, uses crystalline spots (bits) to reflect the laser beam. Amorphous, non-crystalline bits do not reflect light.  polypropylene polypropylene (pŏl'ēprō`pəlēn), plastic noted for its light weight, being less dense than water; it is a polymer of propylene. It resists moisture, oils, and solvents.  at the TPO surface and into the underlying region containing rubber domains. Although the CPO primer thickness is only 10-15 microns, solvent may penetrate hundreds of microns into the TPO, and CPO chains may penetrate up to 14 microns. This diffusion causes solvent to swell rubbery domains within the TPO while CPO chains interact with the TPO by dispersion forces and molecular entanglements. This CPO-TPO interaction is responsible for increasing adhesion of the primer and subsequent coating system. An interesting anecdote anecdote (ăn`ĭkdōt'), brief narrative of a particular incident. An anecdote differs from a short story in that it is unified in time and space, is uncomplicated, and deals with a single episode.  is that often times apparent paint system damage is actually cohesive failure within the TPO. The cause for this can be solvent retention within the TPO, causing rubbery domains to remain swollen, thereby decreasing the mechanical integrity of the TPO. To maximize adhesion of the coating system, the CPO formulation requires a solvent system that will diffuse into the TPO; however, to minimize extended weakening of the TPO, the solvent system must diffuse out of the substrate and coating system during the coating cure (bake) process.

The contribution of the coating system on automotive plastics does not end there. These researchers also have shown that surface and mechanical properties of the topcoat (topcoat/clearcoat) assist the mechanical integrity of coated plastic components. Decreasing the topcoat's coefficient of friction improves the damage resistance of freshly painted plastic parts by causing the impacting object to be more prone to slide across the surface as opposed to gouging Gouging can be:
  • The action of cutting or scooping with a gouge
  • Price gouging
  • Eye gouging or Fish-hooking in violent altercations or combat sports.
 into it. However, this effect usually is temporary since coefficient of friction frequently increases through a coating's lifetime due to surface chemistry and topography topography (təpŏg`rəfē), description or representation of the features and configuration of land surfaces. Topographic maps use symbols and coloring, with particular attention given to the shape and elevations of terrain.  changes from weathering and other exposures. Increasing topcoat toughness, hardness, and tensile strength improves performance of the painted plastic by absorbing and dissipating potentially damaging energy during impact events and this effect is more permanent throughout the coating system's lifetime if it can maintain mechanical properties. In addressing these performance issues, these researchers have noted: "It is not the CPO alone, the solvent blend alone, the substrate alone, or the topcoat alone that affects the adhesion/cohesion level in the painted plastic, but rather the system attributes that do."

Mechanical Interactions within Coating Systems

Stresses can form within applied coatings from a number of sources. One source is their application to and drying on a substrate. As they dry, coatings adhere to adhere to
verb 1. follow, keep, maintain, respect, observe, be true, fulfil, obey, heed, keep to, abide by, be loyal, mind, be constant, be faithful

2.
 the surface but they typically also shrink because of solvent evaporation evaporation, change of a liquid into vapor at any temperature below its boiling point. For example, water, when placed in a shallow open container exposed to air, gradually disappears, evaporating at a rate that depends on the amount of surface exposed, the humidity  and/or polymer cure. These conflicting forces give rise to tensile stress tensile stress

See under axial stress.
 within the coating. Another source of stress is that multi-coat systems are layers of different materials, each going through the phenomena of adhesion versus shrinkage Shrinkage

The amount by which inventory on hand is shorter than the amount of inventory recorded.

Notes:
The missing inventory could be due to theft, damage, or book keeping errors.
 during drying. In addition, there are differences in how these materials react to imposed stresses such as changes in temperature, humidity, and other environmental factors, as well as mechanical stresses such as flexing. A third source of stress may be chemical changes in the various coatings caused by aging and environmental exposure (e.g., chemical reactions This is the 18th episode of television drama Men in Trees. It originally aired on June 25, 2007 on the TV2 network in New Zealand as a continuation of season 1. Recap
Marin and Cash have a stew cook off, she admits his is better than hers.
 causing increased crosslinking and/or chain scission scis·sion
n.
1. A separation, division, or splitting, as in fission.

2. See cleavage.
, loss of plasticizer plas·ti·ciz·er  
n.
Any of various substances added to plastics or other materials to make or keep them soft or pliable.


plasticizer or -ciser
Noun
). A fourth source of internal stress may be irregularities of the substrate (e.g., porosity porosity /po·ros·i·ty/ (por-os´it-e) the condition of being porous; a pore.

po·ros·i·ty
n.
1. The state or property of being porous.

2.
, corners, edges, or screws and fasteners fasteners

In construction, connectors between structural members. Bolted connections are used when it is necessary to fasten two elements tightly together, especially to resist shear and bending, as in column and beam connections.
) that demand conformation con·for·ma·tion
n.
One of the spatial arrangements of atoms in a molecule that can come about through free rotation of the atoms about a single chemical bond.
 of the applied coating system.

Internal stress may lead to immediate failure, such as delamination delamination /de·lam·i·na·tion/ (de-lam?i-na´shun) separation into layers, as of the blastoderm.

de·lam·i·na·tion
n.
1. A splitting or separation into layers.

2.
 or cracking, or it may lend a contributing factor when other stresses are applied. As stated previously in the discussion on properties and performance, coatings frequently fail from the cumulative effects of multiple stresses. For example, a coating may have adequate adhesive and cohesive strength to withstand an internal stress, but if the coating system experiences some other stress such as thermal shock Thermal shock in mechanical models

Thermal shock is the name given to cracking as a result of rapid temperature change. Glass and ceramic objects are particularly vulnerable to this form of failure, due to their low toughness, low thermal conductivity, and high
 or mechanical flexing, the infliction in·flic·tion  
n.
1. The act or process of imposing or meting out something unpleasant.

2. Something, such as punishment, that is inflicted.

Noun 1.
 of multiple stresses along with the existing internal stress may lead to failure. On the other hand, development of internal stress can be used for benefit. For example, aircraft coating systems traditionally consist of epoxy epoxy

Any of a class of thermosetting polymers, polyethers built up from monomers with an ether group that takes the form of a three-membered epoxide ring. The familiar two-part epoxy adhesives consist of a resin with epoxide rings at the ends of its molecules and a curing
 primer and polyurethane polyurethane

Any of a class of very versatile polymers that are made into flexible and rigid foams, fibres, elastomers (elastic polymers), surface coatings, and adhesives.
 topcoat. Periodically, usually every four to six years, aircraft are refurbished, which includes re-painting. The old paint must be removed and this was done almost exclusively with chemical paint strippers paint stripper paint nAbbeizmittel nt . The paint strippers contained methylene chloride Noun 1. methylene chloride - a nonflammable liquid used as a solvent and paint remover and refrigerant
dichloromethane

chloride - any compound containing a chlorine atom
, which diffuses through the polyurethane topcoat and dramatically swells the epoxy primer. The forces caused by swelling of the primer overcome the adhesive strength of the system, causing it to delaminate de·lam·i·nate  
intr.v. de·lam·i·nat·ed, de·lam·i·nat·ing, de·lam·i·nates
To split into thin layers.
 from the substrate, thereby stripping the paint. In short, the internal stress from the swelling of the paint would cause it to "pop off" the substrate.

Perera and co-workers have led the research in the area of internal stress of coatings. They have looked at crack formation and stress development, (47) environmental contributions, (48) coating compositional effects, and measurement in multi-coat systems. (49,50) When investigating a multi-coat system containing a primer, basecoat, and polyurethane clearcoat, these researchers found noticeable changes in coatings and the coating system during QUV QUV Relative Magnetic Bearing (radiotelegraphy)  accelerated weathering exposure (1000 hr), which led to paint system failure. Exposure to UV, water, and oxygen caused breaking of bonds in the polyurethane clearcoat and formation of new crosslinks and groups, including hydroxyls, hydroperoxides, and carbonyls. These new groups are more hydrophilic hydrophilic /hy·dro·phil·ic/ (-fil´ik) readily absorbing moisture; hygroscopic; having strongly polar groups that readily interact with water.

hy·dro·phil·ic
adj.
, causing the clearcoat to be more susceptible to water uptake as evidenced by water absorption of an unexposed coating versus one exposed for 725 hr being 2.2% vs 10.3%, respectively. This extent of water uptake leads to swelling, which causes compressive com·pres·sive  
adj.
Serving to or able to compress.



com·pressive·ly adv.
 internal stresses. Chemical changes also caused an increase in the clearcoat [T.sub.g] from 70 to 106[degrees]C (over 30[degrees]C increase as measured by dynamic mechanical analysis) during the first 336 hr of exposure. This increasing [T.sub.g] suggests embrittlement Embrittlement

A general set of phenomena whereby materials suffer a marked decrease in their ability to deform (loss of ductility) or in their ability to absorb energy during fracture (loss of toughness), with little change in other mechanical properties, such
 of the coating and formation of internal tensile stresses. Stress development over the entire exposure period of 1000 hr can nearly double or triple. The QUV exposure was a repetitive eight-hour cycle composed of four hours UV exposure followed by four hours of condensation. In addition to the ongoing chemical changes, this cyclic cyclic /cyc·lic/ (sik´lik) pertaining to or occurring in a cycle or cycles; applied to chemical compounds containing a ring of atoms in the nucleus.

cy·clic or cy·cli·cal
adj.
1.
 exposure introduced repetitive physical changes (e.g., swelling and shrinkage) and the resulting mechanical stresses, which is a fatigue cycle. Materials generally will fail under fatigue at lower stress levels than a single stress event. The exposure causes chemical and mechanical property changes, as well as fatigue stresses, which cause the coating system to crack.

In a subsequent study, these researchers noted that most multi-coat systems have coatings with noticeably different chemistries, mechanical and physical properties. Each of these layers reacts differently to applied stresses. This difference is due in part to interlayer Noun 1. interlayer - a layer placed between other layers
layer, bed - single thickness of usually some homogeneous substance; "slices of hard-boiled egg on a bed of spinach"
 interactions which include adhesion, diffusion of species across interface boundaries, etc. The greater the difference in mechanical properties of the various coatings, the more susceptible the system is to development of more substantial internal stress. Of course, it is common in materials for stresses to be transmitted throughout the material and ultimately concentrate at the weakest areas such as flaws and defects. In the case of coatings, this can be an interface at the substrate or between coatings. When the adhesion between two films is less than cohesion of the coatings, adhesive failure (delamination) of coatings within the coating system can readily occur. Stress also will concentrate at surface defects and irregularities such as pinholes and irregular geometries, which can cause cracking and delamination failures.

The above discussions illustrate that coatings are not stand-alone entities when they are applied in a coating system. They chemically and mechanically interact with each other and their substrate; and they interact with their environment. These interactions can vary dramatically throughout the lifetime of the coating system, rendering substantial contributions to the coating system's success or failure. It is incumbent to understand not only the basic material aspects of coatings, but also their function and performance within the intended coating system.

COATINGS AS PART OF AN END PRODUCT

An important yet often unappreciated concept related to coatings is their value-to-performance ratio. This concept was emphasized by Wismer in his 1989 Mattiello Lecture. (51) This ratio is the cost of a coating system (and its application) relative to the cost of the end product on which it is applied. Table 3 lists Wismer's estimates for various applications, which generally hold true today. The cost of a coating is just a small fraction of the end product, often less than 1%, yet it provides a disproportionately high value to that product. For example, consider the appearance, corrosion prevention, chip resistance, etc. that a coating system provides to an automobile during the course of its lifetime. Picture what that automobile would look like without a coating, and what it would look like after several years of service. Relating this value-to-performance concept to earlier examples: What is the cost of an intumescent coating versus the loss of life and property experienced on the USS Forrestal? What is the cost of a thermal insulating coating versus the loss experienced from the 9/11 tragedy?

The initial and premier thought of all those working in the coatings industry, and especially coatings technologists (e.g., polymer chemist, applications chemist, formulator, applicator, design engineer, etc.) should be: The ultimate value of a coating is the value it provides during the application to and performance on the end product through its desired lifetime. Without an understanding and consideration of a coating's requirements and value, the success of that coating, or any technology associated with it (e.g., raw materials, equipment), is highly unlikely. Yet another example will illustrate the point further.

The U.S. Navy operates in a highly corrosive environment. These operations often involve the use of expensive and critical equipment, such as high performance aircraft. A constant, diligent dil·i·gent  
adj.
Marked by persevering, painstaking effort. See Synonyms at busy.



[Middle English, from Old French, from Latin d
 effort is required to maintain this equipment for operational readiness The capability of a unit/formation, ship, weapon system, or equipment to perform the missions or functions for which it is organized or designed. May be used in a general sense or to express a level or degree of readiness. Also called OR. See also combat readiness.  and mission success and this includes corrosion prevention procedures. Because of these issues, the Navy and related organizations have performed much research and development related to corrosion prevention, including structural material development, coating pretreatments, organic coatings, cleaners, and corrosion preventive compounds. The constant close proximity to water, especially seawater seawater

Water that makes up the oceans and seas. Seawater is a complex mixture of 96.5% water, 2.5% salts, and small amounts of other substances. Much of the world's magnesium is recovered from seawater, as are large quantities of bromine.
, causes surfaces to be susceptible to water condensates and spray, which cause a corrosion problem. To address this problem, a type of corrosion preventive commonly used is water-displacing compound. These materials are designed to be applied to corrosion prone areas, displace dis·place  
tr.v. dis·placed, dis·plac·ing, dis·plac·es
1. To move or shift from the usual place or position, especially to force to leave a homeland:
 water from the substrate upon application, and subsequently prevent corrosion of the underlying metal. A wide variety of corrosion preventive compounds exists for a number of end uses.

About 22 years ago, an effort was started to extend the menu of corrosion preventive compounds to include water-displacing paint. This paint was designed to be applied in the field for touch-up repair of damaged original paint. The principle investigator for the effort reviewed the considerable body of scientific literature on the subject and proceeded to develop the product. References 52-55 describe some of the associated technical findings, including the development of the coating. To summarize, the displacement of water from a metal surface by an applied coating is a complicated event that is dependent upon a number of contributing factors, most critically:

(1) Even and efficient flow and wetting of the coating when applied to the substrate. As with all coatings, this is necessary for thorough coverage. It is even more critical in this application since the coating must remove and isolate water away from the substrate. Typically, lower viscosity, better wetting coatings are more favorable.

(2) Preferential adsorption of the coating onto the substrate versus water. When the coating contacts the surface, at some point it will come into contact with water and the substrate. Water generally has a high affinity for metal substrates; however, the coating (actually components within the coating) can preferentially adsorb onto the metal substrate, diffuse under the water, and cause the water to flow or rise from the surface over top of the applied coating. This can be facilitated by additives that have a high affinity for metal such as petroleum sulfonate sul·fo·nate
n.
A salt or ester of sulfonic acid.

v.
1. To introduce one or more sulfonic acid groups into an organic compound.

2. To treat with sulfonic acid.
 salts similar to those used in penetrating oils Penetrating oil or penetrating fluid is very low viscosity oil. It can be used to free rusted mechanical parts (such as nuts and bolts) so that they can be removed, because it can penetrate into the narrow space between the threads of two parts.  and lubricating fluids.

(3) A designed limit of water solubility Water is a bent, polar compound and possesses the ability to Hydrogen bond. As a result, it has unique solubility characteristics as a solvent and functions differently at different temperatures. Polarity
Bonding
Sources
Water Solubility, US Geological Survey
. Limited solubility of water in the coating is required to ensure that no substantial amounts of water remain near the metal surface or within the coating. Again, this can be designed into the coating by selecting ingredients, especially solvents, that have low water solubility.

The performance of the coating is further complicated with the requirement of corrosion inhibition after application and cure. This is accomplished with the use of corrosion inhibiting pigments such as molybdates and phosphates. Of course, the ingredients within the coating formulation determine its performance and they were selected and formulated based on scientific principles and empirical results to yield the desired properties. Certainly, many of the concepts previously discussed in this paper were considered and utilized to develop a coating that would successfully fulfill its desired function.

The R & D efforts leading to this coating were followed by development of a product specification and introduction to the fleet. Several months later, a conference of Navy corrosion field engineers, who experience the day-to-day problems, was held. One of the topics discussed was the water displacing paint that was recently introduced. Following a presentation by the inventor, one of the engineers vehemently commented that his maintenance crews could not use this product because it would not dry on their equipment. In fact, there were times when the coating would not spray from its aerosol aerosol (âr`əsōl,–sŏl): see colloid.
aerosol

System of tiny liquid or solid particles evenly distributed in a finely divided state through a gas, usually air.
 container. The scientist questioned how that could be possible when the coating clearly was applicable and dried in the laboratory and during other real-world scenarios. The field engineer sharply replied, "We are stationed in Alaska!" Upon hearing this, it struck me that in all of my research on the subject, I never talked with anyone in the field about their needs and perspectives of this application. I had formulated a coating that could be applied and cured in a laboratory setting, but not in a number of areas where the Navy is stationed, in this case at temperatures at or below 40[degrees]F. This coating did not add value to a notable number of end users because it could not be adequately applied and cured.

This example illustrates that, although successful application of scientific principles may be a requirement for a successful technological development, it is not the sole requirement. As stated above, without an understanding and consideration of a coating's requirements and value, the success of that coating is highly unlikely. In a broader sense, a fuller holistic approach holistic approach A term used in alternative health for a philosophical approach to health care, in which the entire Pt is evaluated and treated. See Alternative medicine, Holistic medicine.  to and understanding of the coating and its application requirements would have provided better chances for success.

FINAL THOUGHTS

The discussion throughout this paper, including the examples, was presented to illustrate a myriad of concepts from R & D through commercial use that are responsible for the success of a coating. It is not always important to understand the detailed chemistry of every ingredient within a formulation, or the fundamental materials science of ingredients and coatings, or the thermodynamics thermodynamics, branch of science concerned with the nature of heat and its conversion to mechanical, electric, and chemical energy. Historically, it grew out of efforts to construct more efficient heat engines—devices for extracting useful work from expanding  of all the interactions that may occur within a coating, or all of the chemical and mechanical effects within a coating system. However, it is important to understand that these effects exist and they in turn determine a coating's performance. The broader and deeper the understanding, the more potential for success.

The theme of this paper is to suggest a holistic perspective of coatings technology, to illustrate that diversity of knowledge, thought, and approach in designing raw materials, coatings, coating systems, and final products will yield better science, better coatings, and better final products. A holistic view of the various aspects of coatings technology can provide tangible benefits in R & D, application, and performance of coatings. Of course, it would be beneficial if we all expanded our horizons to have a broader knowledge and perspective of these issues. Many of the previous Mattiello Lecturers display(ed) great insight in a broad spectrum of coatings technology. This diversity can be obtained by individuals who have the ability, desire, and fortitude to learn and practice multiple disciplines. However, this holistic perspective does not have to be displayed or employed by individuals, it also can be displayed by teams of people with diverse abilities and disciplines, each providing their own knowledge, experience, and perspective.

In reading previous Mattiello Lectures, it is interesting and informative to note numerous discussions of "coatings engineer," "paint engineer," and "paint as an engineering material." (56-58) In fact, Joe Mattiello's Edgar Marburg Lecture at a national ASTM ASTM
abbr.
American Society for Testing and Materials
 meeting in 1946 was entitled en·ti·tle  
tr.v. en·ti·tled, en·ti·tling, en·ti·tles
1. To give a name or title to.

2. To furnish with a right or claim to something:
 "Protective Organic Coatings as Engineering Materials." (59) This is interesting since for many years the coatings industry strived to transition from an "art" to a "science," and it has done so as exemplified by great scientific and performance advancements which extend far beyond the coatings industry. However, these authors were not debating coatings as a science versus an engineering discipline, nor were they commenting on the art form associated with coatings formulation and performance. They were discussing how coatings technologists were well rounded in knowledge and ability, and that coating materials function in the real world as engineering materials. There are those in the industry that display this quality, and there are groups that display this quality; however, the terms "coatings engineer" and "paint engineer" are rarely used these days, literally or figuratively fig·u·ra·tive  
adj.
1.
a. Based on or making use of figures of speech; metaphorical: figurative language.

b. Containing many figures of speech; ornate.

2.
. In some respects it appears that many working in the area of coatings technology have become extremely specialized, and knowledge within the industry has become overly focused and somewhat fragmented. Specialized knowledge in many cases is necessary for technological advancement; however, a broader knowledge of the entire coatings technology pipeline and industry also would greatly increase probability of successful development, application, and service life of coatings. These thoughts lead to a principle: The more you learn, the more you can do; the more you do, the more you learn. This applies to nearly every facet of life, but it certainly would be a benefit if applied within the coatings industry.

And now I thank those that have helped and continue to help me form my perspective and understanding of coatings technology ...
Table 1 -- A Sample Coating Formulation, Chemistry of Ingredients, and
Properties Affected. Low Gloss Interior Wall Paint, Low VOC

Material                            Chemistry          Function

GRIND
Water                               Water              Solids, viscosity
Tamol 850 (Rohm & Haas)             Polymethacrylic    Dispersion
                                    acid               stability
KTPP (FMC)                          Potassium          Dispersion
                                    tripolyphosphate   stability
AMP-95 (ANGUS)                                         pH
                                    Amine              neutralization
Igepal CO-630 (Rhodia)              Ethoxylated nonyl
                                    phenol             Surfactant
Drewplus L-475 (Ashland)            Silica             Foam control
Nuosept 95                          Hydroxymethyl      Formaldehyde-
                                    dioxabicyclo       releasing
                                    octane             preservative
Add the following under agitation:
TiONA RCL-3 (Millennium)            Titanium dioxide   Color, hiding
Mattex (Engelhard)                  Clay               Extender filler
No. 10 White (Imerys)               Calcium carbonate  Extender filler
Celatom MW-27 (Eagle Picher)        Diamatomaceous     Extender filler
Attagel 40 (Engelhard)              Attapulgite clay   Rheology modifier
Sub-Total:
Grind to 4+ H.S.

LET-DOWN
Airflex EF811 (Air Products)        VAE emulsion       Resin binder
Drewplus L-475                      Silica             Foam control
Bermocol CST-347, 2.5%
 Solon (Akzo)                       Cellulose          Rheology modifier
Water                               Water              Solids, viscosity
Add the following under agitation:
Texanol (Eastman)                   Ester alcohol      Coalescing
                                                       solvent
Yellow iron oxide "C" colorant      Iron oxide         Colorant
Red iron oxide "F" colorant         Iron oxide         Colorant
Lampblack "B" colorant              Iron oxide         Colorant
Total

PHYSICAL PROPERTIES
Density (lb/gal)                     11.4
% Solids, by weight                  46.3
% Solids, by volume                  27.2
% PVC                                65.9
% C.S. on latex NVM                   5.0
% Disp. solids on pigment             0.6
Lb/gal of water                     582.2/69.9
VOC (g/L)                            25.2

Material                             Pounds  Gallons  NVM-Lb  NMVM-Gal

GRIND
Water                                170.0    20.41
Tamol 850 (Rohm & Haas)                9.0     0.91     2.7
KTPP (FMC)                             1.5     0.08
AMP-95 (ANGUS)                         2.0     0.25
Igepal CO-630 (Rhodia)                 3.5     0.45
Drewplus L-475 (Ashland)               2.0     0.27
Nuosept 95                             1.5     0.18
Add the following under agitation:
TiONA RCL-3 (Millennium)             140.0     4.46   140.0    4.46
Mattex (Engelhard)                   100.0     4.57   100.0    4.57
No. 10 White (Imerys)                150.0     6.64   150.0    6.64
Celatom MW-27 (Eagle Picher)          45.0     2.34    45.0    2.34
Attagel 40 (Engelhard)                 5.0     0.25     5.0
Sub-Total:                           629.5    40.55   440.0   18.01
Grind to 4+ H.S.

LET-DOWN
Airflex EF811 (Air Products)         159.0    17.87    87.5    9.30
Drewplus L-475                         1.0     0.14
Bermocol CST-347, 2.5%
 Solon (Akzo)                        267.0    32.05     6.7
Water                                 74.0     8.88
Add the following under agitation:
Texanol (Eastman)                      4.4     0.56
Yellow iron oxide "C" colorant         2.2     0.12
Red iron oxide "F" colorant            0.2     0.01
Lampblack "B" colorant                 0.7     0.06
Total                               1138.0   100.24   527.5   27.31

PHYSICAL PROPERTIES
Density (lb/gal)
% Solids, by weight
% Solids, by volume
% PVC
% C.S. on latex NVM
% Disp. solids on pigment
Lb/gal of water
VOC (g/L)

Table 2 -- Polymer Absorbed Layer Thickness on Filler Particles for
Various Polymer-Filler Systems

                                   Measurement           Thickness
System                             Method                (nanometers)

Polyurethane/glass                 Energy dissipation--
                                   viscosity             2500
PS & PMMA/glass & mica             Energy dissipation--
                                   dynamic mechanical
                                   analysis (DMA)          60-1400
CPE/Ti[O.sub.2]                    Energy dissipation--
                                   DMA                      1-20
PVC & PVAc/Fe203 & Ti[O.sub.2]     Energy dissipation--
                                   DMA                     30-110
PVAc/PS particles                  Ultracentrifuge          3-25
PVAc/PS particles                  Ultracentrifuge
                                   Slow-speed centrifuge
                                   Intensity fluctuation
                                   Electrophoreses          3-40
SBR/carbon black                   Dilatometry
                                   Thermal expansion        3
Alkyd/Ti[O.sub.2]                  Viscosity                2-40
Linseed oil/carbon black           Oil absorption           2.5
SBR/carbon black                   DMA                      2
Sulphonic acid/calcium carbonate   Neutron scattering       2
Elastomer/carbon black             Bound (unextractable)
                                   rubber                   2.2-5.5
Linoleic triglyceride/Ti[O.sub.2]  Oil absorption/
                                   theoretical model       12
Polymethacrylate/Ti[O.sub.2]       Adsorption isotherm      1.8-9.6

                                   Adlayer Thickness/
System                             Filler Radius       References

Polyurethane/glass                   0.14                 19
PS & PMMA/glass & mica               0.04                 63
CPE/Ti[O.sub.2]                      0.01-0.20            22
PVC & PVAc/Fe203 & Ti[O.sub.2]       0.20-0.35            64
PVAc/PS particles                    0.08-0.70            65
PVAc/PS particles                    0.08-1.1             66
SBR/carbon black                     Not reported         12
Alkyd/Ti[O.sub.2]                    0.02-0.40             9
Linseed oil/carbon black             1.0                  57
SBR/carbon black                     Not reported         67
Sulphonic acid/calcium carbonate     0.3-1.0              68
Elastomer/carbon black               0.06-1.14            69
Linoleic triglyceride/Ti[O.sub.2]    0.06                 70
Polymethacrylate/Ti[O.sub.2]         0.01-0.05            71

Clearcoat 40-50 microns
Basecoat ~20 microns
Primer (~30 microns)
Electrocoat (~0.25 microns)
Zinc phosphate treatment
Metal substrate
Clearcoat 40-50 microns
Basecoat ~20 microns
Primer (~30 microns)
Plastic substrate

Figure 5 -- Schematic representation of automotive exterior coating
systems for metal and plastic. (73)

Table 3 -- Wismer's Estimates of the Percentage of the Cost of Coatings
to the Total Cost of Various End Products (51)

Automotive paint                         0.9%
Fire protective mastic on oil platform   1.0%
Cable coating on ship                    0.2%
Ink on paper                            <6.0%
Ink on packaging                        <0.5%
Paint on whole house                     0.5%


ACKNOWLEDGMENTS, THANKS, AND DEDICATION

I did not know Joseph Mattiello but I have read about him, mainly in previous Mattiello Lectures and especially from the brief biography written by Bob Brady
For the economist see Robert A. Brady (economist), and for the sculptor see Robert David Brady


Robert A. "Bob" Brady (born April 7 1945) is a politician from the U.S. state of Pennsylvania.
. (60) Without exception, the words used to describe him are: creative, visionary, dedicated, inspirational, leader, and friend. One of the most touching testimonials was stated by Bill Greco: "Joe Mattiello, the charismatic individual, the man of human and humane qualities, the warm-hearted devoted human being, devoted to his family, his profession, his country, and to the coatings industry--he gave so much of his time and energy to transform the industry from an art to a science and to take its rightful place in the science of chemistry. If there is one outstanding quality of Joe Mattiello that should be stressed, it was the friendship he offered, sincere and heartfelt heart·felt  
adj.
Deeply or sincerely felt; earnest.


heartfelt
Adjective

sincerely and strongly felt: heartfelt thanks

Adj. 1.
, which brought its just reward with the legion of friends he made not only in the U.S., but all over the world." (61) In short, Joseph Mattiello was a great scientist and a fabulous person. I urge all of you to read about this great man to appreciate his character and achievements and to be inspired by them.

I do know a number of recent Mattiello Lecturers. They are reflections of Joe Mattiello, providing great contributions to this industry and society. Many of their contributions have been captured within the JOURNAL OF COATINGS TECHNOLOGY, both in their Lectures and other published works. I urge you to read their writings to learn, to explore, and to help create your own holistic view of and approach to coatings technology. It is an overwhelming honor to be considered among these previous Lecturers and I thank the Mattiello Lecture Committee for this tribute. I would also like to extend my sincere and deep appreciation to all of the FSCT FSCT Federation of Societies for Coating Technology
FSCT Fire Support Control Terminal
 Staff, especially Pat Ziegler, Bob Ziegler, Rod Moon, Alicia Hoffmayer, and the always pleasant Dottie Kwiatkowski, for their support throughout my career.

Success can be defined and perceived in many ways, but regardless of the definition or perception, teamwork is an absolute requirement for successful achievements and a successful career. I have had the fantastic fortune of working with talented, dedicated, and selfless self·less  
adj.
Having, exhibiting, or motivated by no concern for oneself; unselfish: "Volunteers need both selfish and selfless motives to sustain their interest" Natalie de Combray.
 people throughout my entire professional life, and an even greater fortune to call these people friends--many of them "Best Friends." They have taught me things that could not be learned from books, provided creative and challenging ideas, performed meticulous lab work, kept me motivated, and most importantly Adv. 1. most importantly - above and beyond all other consideration; "above all, you must be independent"
above all, most especially
 increased the joy in my life. All of my professional successes are a direct result of and credited to these friends. Therefore, I thank them and accept this honor on behalf of all my former, current, and future teammates and colleagues, and most notably those listed below who have had an amazingly positive impact on my life.

From the Naval Air Development Center: Don Hirst, Gabe Pilla, Steve Spadafora, Tony Eng, John De Luccia, Irv Shaffer, Ken Clark, Paul G. Prale.

From Air Products and Chemicals: Frank Pepe, Jeanine Snyder, Denise Lindenmuth, Sherri Bassner, Fritz Walker, John Dickenson, Renee Keller, Tom Panunto.

From industry and academia: Bob Brady, Ray Dickie, Clive Hare hare, name for certain herbivorous mammals of the family Leporidae, which also includes the rabbit and pika. The name is applied especially to species of the genus Lepus, sometimes called the true hares. , Cliff Schoff, Darlene Brezinski, Loren Hill, Kurt Best, Dave McClurg, Leon Boretsky, Ihab Kamel, Roger Corneliussen.

On a final, but most important note, my father worked hard his entire life to make my life better. I have tried to do the same for my son, Tony. I dedicate ded·i·cate  
tr.v. ded·i·cat·ed, ded·i·cat·ing, ded·i·cates
1. To set apart for a deity or for religious purposes; consecrate.

2.
 all that this award represents to him, the proudest part of my life.

References

(1) Situation Critical: USS Forestal (video), Henninger Media Development Publication, New York New York, state, United States
New York, Middle Atlantic state of the United States. It is bordered by Vermont, Massachusetts, Connecticut, and the Atlantic Ocean (E), New Jersey and Pennsylvania (S), Lakes Erie and Ontario and the Canadian province of
, 1997.

(2) Why the Towers Fell (video), BBC BBC
 in full British Broadcasting Corp.

Publicly financed broadcasting system in Britain. A private company at its founding in 1922, it was replaced by a public corporation under royal charter in 1927.
 (New York)/WGBH (Boston) co-production, 2002.

(3) Coatings Encyclopedic Dictionary An encyclopedic dictionary typically includes a large number of short listings, arranged alphabetically, and discussing a wide range of topics. Encyclopedic dictionaries can be general, containing articles on topics in many different fields; or they can specialize in a particular , LeSota, S. (Ed.), Federation of Societies for Coatings Technology, Blue Bell, PA, 1995.

(4) Callister, W.D., Jr., Materials Science and Engineering, J. Wiley and Sons, Inc., New York, p. 2-3, 2003.

(5) Service Life Prediction of Organic Coatings: A Systems Approach, Bauer, D.R. and Martin, J.W. (Ed.), ACS (Asynchronous Communications Server) See network access server.  Symposium Series 722, Oxford University Press, 1999.

(6) Service Life Predictions: Methodology and Metrologies, Martin, J.W., and Bauer, D.R. (Ed.), ACS Symposium Series 805, Oxford University Press, 2001.

(7) Papers in JOURNAL OF COATINGS TECHNOLOGY, 74, No. 924 (2002).

(8) Gerlock, J.L, Peters, C.A., Kucherov, A.V., Misovski, T., Seubert, C.M., Carter, R.O. III, and Nichols, M.E., "Test Accelerated Weathering Tests for Appropriate Weathering Chemistry: Ozone Filtered Xenon xenon (zē`nŏn) [Gr.,=strange], gaseous chemical element; symbol Xe; at. no. 54; at. wt. 131.29; m.p. −111.9°C;; b.p. −107.1°C;; density 5.86 grams per liter at STP; valence usually 0. ," JOURNAL OF COATINGS TECHNOLOGY, 75, No. 963, 34 (2003).

(9) Rothstein, E.C., "Role of the Adsorbed Resin Layer in the Dispersion of Pigmented Alkyd al·kyd  
n.
A widely used durable synthetic resin derived from glycerol and phthalic anhydride. Also called alkyd resin.



[alky(l) + (aci)d.]

Noun 1.
 Systems," Official DIGEST, 36, 1448 (1964).

(10) Buttignol, V. and Gerhart, H.L., Ind. Eng. Chem., 60, 8, 69 (1968).

(11) Kamel, I., "Thermal and Mechanical Stability of Submicron Fillers Reinforced Composites," North American North American

named after North America.


North American blastomycosis
see North American blastomycosis.

North American cattle tick
see boophilusannulatus.
 Thermal Analysis Thermal analysis is a branch of materials science where the properties of materials are studied as they change with temperature. Techniques include:
  • Differential scanning calorimetry
  • Dynamic mechanical analysis
  • Thermomechanical analysis
 Society Conference, Cincinnati, OH, Sept. 1986.

(12) Kraus, G. and Gruver, J.T., J. Poly. Sci, Polymer Physics Polymer physics is the field of physics associated to the study of polymers, their fluctuations, mechanical properties, as well as the kinetics of reactions involving degradation and polymerisation of polymers and monomers respectively.  Ed., 8, 571 (1970).

(13) Howard. G.J. and Shanks
For other meanings, see Shanks (disambiguation)


The shanks and tattlers are wading bird species in a number of genera characterised by a medium length bill and long, often brightly coloured legs.
, R.A., J. Macromol. Sci.-Chem, A17, 2, 287 (1982).

(14) Greenberg, A. R., Messaros, M., and Kamel, I., Poly. Preprints, 6, 28 (1985).

(15) Greenburg, A.R., J. Mat. Sci. Let., 6, 78 (1987).

(16) Reid, C.G. and Greenbergy, A.R., J. Appl. Poly. Sci., 39, 995 (1990).

(17) Manson, J.A. and Sperling, L.H., Polymer Blends A polymer blend, polymer alloy, or polymer mixture is a member of a class of materials analogous to metal alloys, in which two or more polymers are blended together to create a new material with different physical properties.  and Composites, Plenum In a building, the space between the real ceiling and the dropped ceiling, which is often used as an air duct for heating and air conditioning. It is also filled with electrical, telephone and network wires. See plenum cable.  Press, New York, 1976, p. 411.

(18) Kwei, T.K., J. Poly. Sci., A3, 3229 (1970).

(19) Ziegel, K.D., J. Coll. Inter. Sci., 29, 72 (1969).

(20) Fowkes, F.M., Ind. Eng. Chem., 56, 40 (1964).

(21) Schrieber, H.P., Org. Coat. App. Poly. Sci., 45, 22 (1982).

(22) Boluk, M.Y. and Schreiber, H.P., Poly. Comp., 7, 295 (1986).

(23) Hegedus, C.R. and Kamel, I.L., "A Review of Inverse Gas Chromatography Theory Used in the Thermodynamic Analysis of Pigment and Polymer Surfaces," JOURNAL OF COATINGS TECHNOLOGY, 65, No. 820, 23 (1993).

(24) Papirer, E., Vidal, A., and Balard, H., "Analysis of Solid Surface Modification," Inverse Gas Chromatography: Characterization of Polymers and Other Materials, Lloyd, D.E., Ward, T.C., and Schreiber, H.P. (Ed.), ACS Symposium Series 391, American Chemical Society The American Chemical Society (ACS) is a learned society (professional association) based in the United States that supports scientific inquiry in the field of chemistry. Founded in 1876 at New York University, the ACS currently has over 160,000 members at all degree-levels and in , Washington, D.C., 1989.

(25) Ziani, A., Xu, R., Schreiber, H.P., and Kobayashi, T., "Inverse Gas Chromatography, Surface Properties, and Interactions Among Components of Paint Formulations," JOURNAL OF COATINGS TECHNOLOGY, 71, No. 893, 53 (1999).

(26) Burness, J.H. and Dillard, J.G., Langmuir, 7, 1713 (1991).

(27) Hegedus, C.R. and Kamel, I.L., "Thermodyamic Analysis of Pigment and Polymer Surfaces Using Inverse Gas Chromatography," JOURNAL OF COATINGS TECHNOLOGY, 65, No.820, 31 (1993).

(28) Lloyd, T.B., Li, J., Fowkes, F.M., Brand, J.R., and Dizikes, L.J., "Surface Studies of Hydrous hydrous

containing water.
 Oxide Coated Rutile rutile, mineral, one of three forms of titanium dioxide (TiO2; see titanium). It occurs in crystals, often in twins or rosettes, and is typically brownish red, although there are black varieties.  in Non-Aqueous Media," Presented at the Federation of Societies for Coatings Technology Annual Meeting, Washington, D.C., 1990.

(29) Fowkes, F.M., Dwight, D.W., and Cole, D.A., J. Non-Crystalline Solids, 120, 47 (1990).

(30) Joslin, S.T. and Fowkes, F.M., Ind. Eng. Chem. Prod. Res. Dev., 24, 369 (1985).

(31) Hegedus, C.R., "Pigment-Resin Interactions in Coating Systems," Ph.D. Thesis, Drexel University Drexel University, at Philadelphia, Pa.; coeducational; founded 1891 by Anthony J. Drexel, opened 1892, chartered 1894 as Drexel Institute of Art, Science, and Industry. It was renamed Drexel Institute of Technology in 1936 and gained university status in 1970. , Philadelphia, June 1991.

(32) Hegedus, C.R. and Kamel, I.L., "Adsorption Layer Thickness of Poly(methyl methacrylate) on Titanium Dioxide and Silica," JOURNAL OF COATINGS TECHNOLOGY, 65, No. 821, 49 (1993).

(33) Hegedus, C.R. and Kamel, I.L., "Polymer-Filler Interaction Effects on Coating Properties," JOURNAL OF COATINGS TECHNOLOGY, 65, No. 822, 37, 1993.

(34) Payne, H.F., Organic Coating Technology: Volume I, John Wiley John Wiley may refer to:
  • John Wiley & Sons, publishing company
  • John C. Wiley, American ambassador
  • John D. Wiley, Chancellor of the University of Wisconsin-Madison
  • John M. Wiley (1846–1912), U.S.
 and Sons, 1954, p. 17.

(35) Croll, S.G., "Adhesion Loss Due to Internal Strain," JOURNAL OF COATINGS TECHNOLOGY, 52, No. 665, 35 (1980).

(36) Nate, K. and Kobayashi, T., "Adhesive Characteristics of Ultraviolet Curable cur·a·ble
adj.
Capable of being cured or healed.
 Resins," JOURNAL OF COATINGS TECHNOLOGY, 52, No 668, 57 (1980).

(37) Kumins, C.A., "Physical Models for Organic Protective Coatings," JOURNAL OF COATINGS TECHNOLOGY, 52, No. 664, 39 (1980).

(38) Haagen, H. and Funke, W., J. Oil & Color Chemists' Assoc., 58, 359 (1975).

(39) Funke, W., Ind. Eng. Chem. Prod. Res. Dev., 24, 343 (1985).

(40) Leidheiser, H., Wang, W., and Igetoft, C.L., Prog. Org. Coat., 11, 19 (1983).

(41) Nguyen, T., Bentz, D., and Byrd, E., "A Study of Water at the Organic Coating/Substrate Interface," JOURNAL OF COATINGS TECHNOLOGY, 66, No. 834, 39 (1994).

(42) Dickie, R.A., "Chemical Studies of the Organic Coating-Steel Interface After Exposure to Aggressive Environments," in Polymer Materials for Corrosion Control, Dickie, R.A. and Floyd, F.L. (Ed.) ACS Symposium Series 322, American Chemical Society, Washington, D.C., pp 136-154, 1986.

(43) Ryntz, R.A., Xie, Q., and Ramamurthy, A.C., "Effects of Coating Solvents on the Morphology of Thermoplastic Polyolefins (TPO)," JOURNAL OF COATINGS TECHNOLOGY, 67, No. 843, 45 (1995).

(44) Prater prate  
v. prat·ed, prat·ing, prates

v.intr.
To talk idly and at length; chatter.

v.tr.
To utter idly or to little purpose.

n.
, T.J., Kaberline, S.L., Holubka, J.W., and Ryntz, R.A., "Examination of the Distribution of TPO Adhesion Promoter Material in a Painted TPO System," JOURNAL OF COATINGS TECHNOLOGY, 68, No. 857, 83 (1996).

(45) Ryntz, R.A. and Mihora, D.M., "SAE sae abbr (BRIT) (= stamped addressed envelope) → sobre con las propias señas de uno y con sello  Technical Paper # 1999-01-1205," SAE International, Warrendale, PA, 1999.

(46) Ryntz, R.A., Britz, D., Mihora, D.M., and Pierce, R., "Measuring Adhesion of Poly(Olefins): The Role of Adhesion Promoter and Substrate," JOURNAL OF COATINGS TECHNOLOGY, 73, No. 921, 107 (2001).

(47) Oosterbroek, M., Lammers, R.J., Vander Ven, L.G.J., and Perera, D.Y., "Crack Formation and Stress Development in an Organic Coating," JOURNAL OF COATINGS TECHNOLOGY, 63, No. 797, 55 (1991).

(48) Perera, D.Y. and Oosterbroek, M., "Hygrothermal Stress Evolution During Weathering in Organic Coatings," JOURNAL OF COATINGS TECHNOLOGY, 66, No. 833, 83 (1994).

(49) Boerman, A.E. and Perera, D.Y., "Measurement of Stress in Multicoat Systems," JOURNAL OF COATINGS TECHNOLOGY, 70, No. 881, 69 (1998).

(50) Perera, D.Y., "Stress Phenomena in Organic Coatings," in Painting and Coatings Testing Manual, Koleske, J.V. (Ed.), 14th Edition of the Gardner-Sward Handbook (ASTM, MNI See Merom New Instructions.  17), 585 (1995).

(51) Wismer, M., "Learning to Leap: Rising to the Technical Challenge of Today's Coatings Industry," JOURNAL OF COATINGS TECHNOLOGY, 62, No. 780, 83 (1990).

(52) Hegedus, C.R., "Displacement of Water from a Steel Surface," JOURNAL OF COATINGS TECHNOLOGY, 56, No. 711, 51 (1984).

(53) Hegedus, C.R., Metal Finishing, 81, No. 6, 53 (1983).

(54) Hegedus, C.R., "Water Displacing Corrosion Preventive Compounds," in Corrosion Control by Coatings, Leidheiser, H. Jr. (Ed.), National Association of Corrosion Engineers, Houston, TX, 1981.

(55) Hegedus, C.R. and Clark, K.C., U.S. Patent 4,359,543, "Water Displacing Paint," Issued Nov. 16,1982.

(56) E.G. Bobalek, "Paint Among Engineering Materials," Official DIGEST, 34, No. 455, 1293 (1962).

(57) Patton, T.C., "Reflections of a Paint Engineer on Paint Flow, Interface Physics, and Pigment Dispersion," JOURNAL OF PAINT TECHNOLOGY, 42, No. 551, 665 (1970).

(58) Gerhart, H.L., "The Coatings Engineer, the Corporation and the University," JOURNAL OF COATINGS TECHNOLOGY, 49, No. 624, 37 (1977).

(59) Mattiello, J.J., Am. Soc. Testing Materials Proc., 46, 493 (1946).

(60) Brady Jr., R.F., "Clean Hulls Without Poisons: Devising and Testing Nontoxic Marine Coatings," JOURNAL OF COATINGS TECHNOLOGY, 72, No. 900, 44 (2000).

(61) Glaser, M.A., "Innovation in Organic Coatings," JOURNAL OF PAINT TECHNOLOGY, 46, No. 599, 39 (1974).

(62) Coating formulation supplied by Andy Defusco, Air Products and Chemicals, Inc., Allentown, PA.

(63) Iisaka, K. and Shibayama, K., J. Appl. Poly. Sci., 22, 3135 (1978).

(64) Isobe, Y., Okuyama, K., Hosaka, A., and Kubota, Y., "Effect of the Pigment Vehicle Interaction on the Properties of Magnetic Coatings," JOURNAL OF COATINGS TECHNOLOGY, 55, No. 698, 23 (1983).

(65) Garvey, M.J., Tadros, T.F., and Vincent, B., J. Coll. Inter. Sci., 49, 57 (1974).

(66) Garvey, M.J., Tadros, T.F., and Vincent, B., J. Coll. Inter. Sci., 55, 440 (1976).

(67) Smit, P.P.A., Rubber Chem. Tech., 41, 1194 (1968).

(68) Markovic, I., Ottewill, R.H., Cabula, D.J., Field, I., and Marsh, J.F., Coll. Poly. Sci., 262, 648 (1984).

(69) Pliskin, I., and Tokita, N., J. Appl. Poly. Sci., 16, 473 (1972).

(70) Long, J.S., "Creative Imagination as It Applies to the Decorative and Protective Coatings Industry," Official DIGEST, 26, No. 358, 989 (1954).

(71) Idogawa, H., Shimizu, O., and Esumi, K., "Adsorption Phenomena of Polymers Having Functional Groups on Ti[O.sub.2] Particles in Nonpolar nonpolar

not having poles; not exhibiting dipole characteristics.
 Solvent," JOURNAL OF COATINGS TECHNOLOGY, 65, No. 823, 67 (1993).

(72) Sumita, M., Shizuma, T., Miyasaka, K., and Ishikawa, K., J. Macromol. Sci.--Phy., B22 (4), 601 (1983).

(73) Adamsons, K., "Chemical Depth Profiling of Automotive Coating Systems Using Slab Microtome microtome /mi·cro·tome/ (mi´krah-tom) an instrument for cutting thin sections for microscopic study.

mi·cro·tome
n.
 Sectioning with IR/UV-VIS Spectroscopy spectroscopy

Branch of analysis devoted to identifying elements and compounds and elucidating atomic and molecular structure by measuring the radiant energy absorbed or emitted by a substance at characteristic wavelengths of the electromagnetic spectrum (including gamma ray,
 and Optical Microscopy microscopy /mi·cros·co·py/ (mi-kros´kah-pe) examination under or observation by means of the microscope.

mi·cros·co·py
n.
1. The study of microscopes.

2.
," JOURNAL OF COATINGS TECHNOLOGY, 74, No. 924, 47 (2002).

Charles R. Hegedus--Air Products and Chemicals, Inc.*

Presented at the 81 st Annual Meeting of the Federation of Societies for Coatings Technology, Philadelphia, PA, Nov. 12-14, 2003.

* 7201 Hamilton Blvd., Allentown, PA 18195-1501.
COPYRIGHT 2004 Federation of Societies for Coatings Technology
No portion of this article can be reproduced without the express written permission from the copyright holder.
Copyright 2004, Gale Group. All rights reserved. Gale Group is a Thomson Corporation Company.

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Title Annotation:2003 Mattiello Memorial Lecture
Author:Hegedus, Charles R.
Publication:JCT Research
Date:Jan 1, 2004
Words:12309
Previous Article:2003 Joseph J. Mattiello Memorial Lecture.
Next Article:2002 Roy W. Tess Award.



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