History of Paint Science and TechnologyThis is a summarised history of the paint industry since 1920, approximately, andsometimes before. It includes some of the important dates for the development of crucialscientific understanding as well for more general elements of polymer science. It hasbeen arbitrarily assembled through the limited reading and incomplete understanding ofthe author, who triess to improve and extend this as more time and information becomesavailable. There are dates earlier than 1930; these have been inserted due to theirsignificance in establishing either the science or technology for what came later. Theamount of information is less for dates after 1980 since it seems to me that this is the“modern era” of paint technology that is still reasonably current and I have yet to decideabout what has been really significant – suggestions are welcome.The sources for the entries are in the bibliography if they are general in nature.Sometimes more than one source was used for an entry and sometimes there was somedisagreement in fact or timing that I have attempted to rationalise.This history is in three sections at present. The first deals with polymers, polymerscience and their impact on coatings technology, since that is where most of the focusresides. The current emphasis here is on water-borne latex paint systems. There is a verylimited section on the development of analytical characterization techniques, followed bya section that gives a timeline for the development of pigments.Three graphs here track the rise of paint technology overall according to my impressions.I have used a basically sigmoidal shape, in common with other presentations oftechnology maturation [P. A. Roussel, Research Management, 27(1), 29 (1984)]. Therise of paint technology is the same in each graph, but in one I have entered some of themajor, external, historical factors, and in the other I have included some of the majortechnology developments for acrylic latex paint and alkyd paint (although the curve is myvisualization of the whole of paint technology).In simple commercial context, the first graph below shows how, in the US at least (fromCensus Bureau data), the paint industry continues to be important and grows with theeconomy and suffers with the economy. In fact, as long as one needs to control theappearance of useful or amusing things, or they need protection, we will always needpaint. Even modern nano- or bio-materials are more often employed as coatings than anything else, so I cannot see the market for paints or other coatings diminishing.Stuart Croll20091NDSU

U S Annual Shipments of Paints, Varnishes and Lacquers, MillionsUpdated July 2009.Annual Shipments, Million250005.5 % compound growth2000015000100005% compound growth50000192019401960198020002020YearIn contrast with the sales figures before, the above graph places the rise of painttechnology in the context of some of the external influences.Stuart Croll20092NDSU

This graph above traces the rise of latex (emulsion) paint technology in terms of what Ibelieve are some of the principal technical, scientific events. Only the colour of the curvechanged from the previous graph.The last graph labels the rise in paint technology with events that were important fromthe point of view of alkyd paint. I chose green for the curve because oil and alkyd paintsuse some renewable resources as feedstock.Stuart Croll20093NDSU

In the US, the existence over the years of many hundreds (actually 1000) smallcompanies that made paint was the costs and difficulties of shipping the finished paint farafield so companies tended to be very regional in outlook. This has changed in themodern era now that suppliers‟ and manufacturers‟ distribution infrastructure hasimproved.The author apologises for the inconsistent style, but hopes that it will improve asadditional data arrives that forces him to rewrite the content.Stuart Croll, December, 2009.Stuart Croll20094NDSU

Historical Dates1844Charles Goodyear discovers that heating sulphur containing natural rubber produces avery elastic solid. This is “vulcanization” and the first crosslinked polymer.1846„Gun cotton‟ (cellulose trinitrate) was patented by Schönbein, although one can probablytrace nitrated cellulose back to Henri Braconnot (France) in 1832.1865Alexander Parks (England) treats cellulose nitrate with other materials (that we nowknow were plasticizers) to make (and patent) „Parkesine‟, with which he could makesome simple articles for display for the Royal Society of Arts. Later (1869) patented by J.W. and H. Hyatt in USA (the bounders!) when they improved Parkesine as Celluloid,being the first commercial plastic that modern users would recognize.1905Paint and coatings research starts at North Dakota Agricultural College, now NorthDakota State University.Phenol-formaldehyde resins („Novolac‟ resin) made by Leo Hendrik Baekeland, patentedin 1907: “Method of Making Insoluble Products of Phenol and Formaldehyde”. Theseare better known as Bakelite.A. H. Munsell, a painter and art teacher, publishes his color notation system; the firstuseful description of a colour space.1912Dispersion polymerization of isoprene patented in Germany by Kurt Gottlob (Germanpatents 254 & 255). Used egg albumin or starch as emulsifier.Acrylic resins patented.1913Rosin-modified phenolic resins1914Polyvinyl acetate patented by Klatte and Rollet.1914-18First synthetic detergents developed in Germany during World War I. They were shortchain alkyl naphthalene sulphonates. Similar materials are still used.1916Joel H. Hildebrand makes strides in solubility theory for non-electrolytes.1917Staudinger presents the macromolecular concept at a meeting of the Swiss ChemicalSociety. He received the Nobel prize for this discovery in 1953.Stuart Croll20095NDSU

1920Staudinger publishes macromolecular concept: Staudinger, H. Ber. Deut. Chem. Ges.1920, 53, 1073DuPont scientists make a fast-drying lacquer from nitrocellulose. Dupont had abackground with nitrocellulose since it had been making it for explosives since the 1890s.Patent applied for use of Aluminium and Zinc Stearates as pigment stabilizers in oilpaints (US 1,421,625 in 1922). Metal soaps had been known to help stabilize pigmentsfor some time before this.1922DuPont patents nitrocellulose lacquers.1923Cellulose nitrate lacquers first used on cars (“Duco” from DuPont). The use camebecause a low viscosity resin (sprayable at useful solids) was discovered by DuPont in1920 (see above), as opposed to the very high molecular weight resins that beeninvestigated prior to that. This was taken up by many of the companies that later becameGeneral Motors, Chrysler and Ford. Ford most famously used it as one of the enablersfor assembly line production. Previously, the oil paints had needed 3 – 6- weeks to cureand be dry to the touch on the vehicle.1925BASF (Glasurit-Werke) introduce nitrocellulose car paints in Europe.“Tamol” name first used for compounds in dying, tanning and textile industries (see1968).1921 – 1925Alkyd resins introduced but they were slow drying, even when baked. Note: one cantrace polyesters back to Berzelius who condensed glycerol tartrate in 1847.Maleated rosin varnish gums introduced.1920sSpray guns developed.R. H. Kienle of GE develops unsaturated alkyds.1926Paint Research Station founded in UK.GE introduce Glyptal resins (glycerol phthalate)DuPont introduce alkyd resin (glycerol/phthalic anhydride/linseed oil). Alkyd modifiedoil paints and then alkyd paints were eventually used on cars and household appliances.1927R. Kienle et al. of G.E. patents alkyds, but the patent is ruled invalid in 1935 due to priorart, which enables other companies to make and sell alkyds (after 1935). Kienle wasStuart Croll20096NDSU

probably responsible for the combination of the word alkyd – from the condensation ofalcohols and acids.1928R. H. Kienle and C. S. Ferguson present a paper at an ACS meeting in September,entitled “Alkyd Resins as Film-Forming Materials. This was published in 1929 in Ind.Eng. Chem.1929W. H. Carothers (DuPont) publishes on linear polyesters, J. Am Chem Soc, 51, 2560(1929). He is generally credited with formalizing the concept of functionality, althoughKienle had almost certainly been thinking along the same lines.1930Paul Flory starts work on molecular weight distributions (experimentally andtheoretically) and shows that step-growth polymerizations follow the Gaussiandistribution for molecular weight.Rehbinder, Lagutkina, Wenstrom, gain first insights into steric stabilization of colloidalparticles, Z. Physik. Chem. (1930).1931Commission Internationale de l‟ Éclairage, CIE, meets in Cambridge and defines theprimary stimuli for colour vision to be red (700 nm), green (546.1 nm) and blue (435.8nm). The meeting also defines several illumination standard spectra and the first standardobserver.DuPont makes TiO2 pigment by sulphate process, having purchased the CommercialPigments Corporation that held the patents. These pigments were sold by the KrebsPigment and Color Corporation (a DuPont subsidiary) as TiPure but it continued tomake a TiO2 enhanced lithopone as Duolith .1931-32DuPont introduce “Dulux” as a brand name for alkyd paint. However, DuPont and Nobelcollaborated in the early 1920s on explosives, as much as anything else, and Nobel usedthe name in Europe. DuPont and ICI (UK) started a technical collaboration in October1929 but dissolved the association in 1952. Clearly, the name “Dulux” stayed with ICIthereafter.Luther and Hück patent a method for making a SBR latex material (working for I. G.Farbenindustrie in Germany), US patent 1,864,078 (June 21, 1932)1930sStuart Croll20097NDSU

Wallace Carothers at DuPont synthesizes aliphatic polyesters, polychloroprene andpolyamide 6,6 (Nylon, patented 1937). Work supported the macromolecular concept andhis definition of a polymer is one that fits modern usage better than Staudinger‟s.Herman Mark, Werner Kuhn, Eugene Guth find that polymers in solution are flexible andthat viscosity is related to molecular weight of the polymer.P. Castan (Switzerland) and S. Greenlee (USA) patent epoxy resins.Triton surfactants invented by Herman Bruson (for Rohm and Haas?).1933National Grid for supplying electricity was established in the United Kingdom byinterconnecting regional grids and was more fully integrated in 1938. Electrical powerwas becoming much more available during the 30s‟. Plenty of coal was available in theUK and elsewhere for fuel.1934Mark, Kuhn and Guth generate first statistical mechanical theory for rubber elasticity.1930 – 1935Urea formaldehyde resins combined with alkyd resins; vinyl chloride was made usefulfor coatings (soluble) by copolymerizing with vinyl acetate.Ford and Chrysler use alkyd enamel topcoats.1933Schlak patents the first epoxy resins: diglycidyl ethers made from epichlorhydrin andbisphenol A: German Patent 676,117. Styrene-Butadiene rubber made in Germany1935Polyvinyl butyral made for use in wash primers.1936Joel H. Hildebrand identifies the square root of the cohesive energy density as aquantification of solvency.1937Urethane resins produced by Bayer for elastomers and foams (urea reaction producesCO2 naturally).First commercial production of pentaerythritol – important for alkyd chemistry.1937Patent 2,071,250 (filed in 1931) Linear Condensation Polymers granted for the work thatleads to Nylon W. H. Carothers (DuPont)1939Thermosetting acrylics developed by D. E. Strain (U.S. Patent 2173005 to DuPont,1939).1940Stuart Croll20098NDSU

Melamine formaldehyde resins.The paint roller was invented by Norman Breakey of Toronto.1940sStyrene-Butadiene synthetic rubber latex developed as the “Mutual Recipe” in the USA(75% butadiene, 25% styrene with a rosin soap and a little mercaptan) since isoprene didnot give a useful material. Production started in 1943. This project involved a number ofuniversities and large chemical companies in the US at the time and it is claimed that theproject rivaled the Manhattan Project in size and about2.html ).Flory develops his version of rubber elasticity theory to model the properties ofcrosslinked polymers (with Rehner for solvent swelling).For some historians the “2nd Chemical Revolution” starts in this period (1st chemicalrevolution took place with the work of Lavoisier and Berzelius, 1780 etc)1941 – 1945German warplanes use urethane paints (and baffle Allies initially).1941Derjaguin and L. Landau, publish their version of the DLVO theory [Acta Physicochim.(URSS) 14 (1941) 633–662.].First widely sold commercial water based paint: Sherwin-Williams sell „Kemtone .‟The binder used casein, corn protein, rosin and a small amount of linseed oil in anemulsion with TiO2, chalk, clay and mica.1942Flory and Huggins in 1942 independently [P. J. Flory, J. Chem. Phys., Vol. 10, 51(1942); M. L. Huggins, J. Am. Chem. Soc, 64, 1712 (1942)] developed a theory ofsolubility and interactions to improve regular solution theory to include better theconnected nature of polymer molecules. Originated “theta” solvent concept.1944Germans use waterborne paint similar to PVA, for Tiger tanks. Linseed oil was in veryshort supply in Germany and it was known their railway rolling-stock was also beingpainted with a waterborne finish. [Keith Hammond series in PPCJ, Polymers PaintColour Journal Feb-July 2003]1945GE and Dow Corning announce silicone rubbers for gaskets etc. Silicone polymers areused in high temperature and weather resistant applications since the silicon is fullyoxidized and cannot oxidize more. They have been used in a wide variety of chemicalresistant applications, coil coatings etc.UV curing patent to DuPont US patent 2367670, R. E. ChristPentarythritol used in alkyds instead of glycerol.Styrenated alkyds appear.Stuart Croll20099NDSU

1946Ciba commercialises an epoxy resin.Styrene-butadiene latex commercialized for paper coatingsUV curing ink, Inmont, US patent 24068781947Dupont introduces the pentarythritol type alkyd paint, which is introduced two years laterin UK [Standeven].1948First use of styrene-butadiene latexes in architectural paints – Glidden‟s „Spred Satin ‟.Verwey and Overbeek publish their contribution to what became DLVO theory [E. J. W.Verwey and J. Th. G. Overbeek, Theory of Stability of Lyophobic Colloids, Elsevier,Amsterdam, 1948]1947 – 1950Epoxy resins commercialized [1].1949Kienle publishes on alkyd resins that dry much faster [R. H. Kienle, Ind. Eng. Chem. 41,p.726 (1949) ].1950Hildebrand, in the third edition of his book coins the term „solubility parameter‟[Hildebrand, J. H., and Scott, R. L., “The Solubility of Nonelectrolytes,” Chap. XI(Reinhold Publ. Corp., New York, N.Y., 1950)]M. Van der Waarden begins to understand steric stabilization of colloids in “Stabilizationof carbon black dispersions in hydrocarbons”, Journal of Colloid Science, 5 317-25(1950)Unsaturated polyester resins appear [1], probably following Carothers‟ work.Natrosol registered as trademark for alkali soluble cellulose ethers, and enters themarket for thickeners.Research into epoxy coatings at Devoe and Raynolds Inc.1951 – 1955.Epoxy-polyamide resin systems are introduced[1].1951Acrylic polymers for emulsion paints under development.DuPont introduces the chloride process for refining TiO2 at its Edgemoor plant.1952Powder coatings invented in Germany for fluidized bed use.Thixotropic alkyds (in some ways the forerunner for hydrocarbon environments ofassociative thickeners for aqueous systems).Stuart Croll200910NDSU

1953First all-acrylic latex introduced commercially: Rhoplex AC-33 in USA, ( PrimalTMAC-33 in Europe).1954Thixotropic alkyd resins introduced [1].1955Water soluble/dispersible thermosetting resins introduced, e.g. alkyds and acrylics [1].1956G. L. Brown‟s research into latex film formation [“Formation of Films from PolymerDispersions,” J. Polym. Sci., Vol. 22, pp. 423 – 434 (1956).Commercial production of isophthalic acid [Alkyd Resins by C. R. Martens, ReinholdPublishing Corporation NY 1961. (Chapman and Hall Ltd. London)].Shell introduces amine and polyamide cured epoxy resins.1956 – 1960General Motors uses acrylics and acrylic-melamine resins in place of some of thecellulose nitrate and alkyd coatings for automotive finishes.Urethane Oils and alkyds, thermoplastic acrylics for lacquers, thermosetting acrylics forenamels, silicone copolymers [1].Crosslinking latexes are introduced [17].1957George Brewer develops anodic electrophoretic coatings at Ford Motor Company. Seeintroduction in 1964.1960US patent 2930775, composition of a dispersing aid for pigments etc., maleic aciddiisobutylene copolymer 1:1, corresponds to Tamol 731.1961 – 1965Fluoropolymers first introduced [look up Teflon].1962Texanol registered as trademark by Eastman Chemicals and found use as a coalescingaid for latex paints by Eastman together with several customers and other resin suppliers[Del Rector, Eastman Chemical Company, private communication]. The discovery of thecompound was somewhat accidental.1960s- early 1970First polyurethane dispersions (in water) were patented [D. Dieterich, “AqueousEmulsions, Dispersions And Solutions Of Polyurethanes; Synthesis And Properties,”Progress in Organic Coatings, 9 p. 281 – 340, (1981); Dr. R. Roesler, Bayer Chemicals,private Communication]Stuart Croll200911NDSU

1964Epoxy, acrylic and other resins used for anodic electrophoretic primers – pioneered byFord Motor Company (Brewer, 1964). First electrophoretic (otherwise known aselectrodeposition) paint tank filled at Ford Wixom works by PPG.Eastman built the first plant producing Texanol as a commercial chemical. Thiscoalescing additive made the application of latex paints possible over a much broaderrange of environmental conditions.[Del Rector, Eastman Chemical Company, privatecommunication]1966 – 1970Ultraviolet and electron-beam cured polymer coatings appear for very fast curerequirements with low solvent emissions.Non-aqueous dispersions of acrylics are developed.1967Los Angeles County invoked EPA Rule 66(5) that regulated the use of potentiallyharmful solvents in industrial coatings. This was to restrict photochemically (helped byUV) reactive solvents that combine with nitric oxide from automobiles and industrialprocesses to produce the well-known „smog‟. Calculations quickly showed that „highsolids‟ coatings would be necessary. The world changed for coatings in the US. HighSolids means 60% solids by weight or higher.UV wood coatings (Bayer) (see 1946).1969Commercialization of UV curing printing ink.1970sStart of serious work on thermoplastic and thermosetting polyester powder coatings andrapid development of UV curing compounds.1970Clean Air Act passed in US.1971Cathodic electrophoretic paints for automotive use introduced by PPG.First non-mercurial mildewcide introduced: Skane M-8.Acrylic polyelectrolyte thickeners introduced.1973-75Arab oil embargo, shortages of petrochemical feedstock puts more impetus behindchemistries that avoid use of lots of organic solvents and so attention turned to waterborne or high solids types.1976Stuart Croll200912NDSU

Cathodic electrocoat primer released by PPG.Acrylic, polyester and urethane oligomers developed for high solids coatings.1980sThe modern „High Solids‟ age starts here. One might compare it to the Iron Age.1981Modified polyelectrolyte thickeners introduced, HASE (hydrophobically modified alkaliswellable emulsions) and HEUR (hydrophobically modified urethane block copolymers).1982Epoxy water borne dispersions introduced.Hard latex with hollow core introduced as opacifier.1983Group transfer polymerization [U.S. Patent, 4417034, November 22, 1983, DuPont Co.;S. N. Lewis., Letter to the Editor, Chem. Eng. News, 61, No. 48, 3 (1983)]. New methodof tailoring very specific designs of polymers.1983 – 86Acceptance of powder coatings in several niche markets, based on polyesters combinedwith epoxies, triglycidyl isocyanurate etc.1987ISO 9000 is born from BS 5750. ISO 9000 is essentially a standard for organizations tocreate their own standards; requires strict adherence, follow-up and improvement.Analytical InstrumentationMethods such as IR, FTIR, UV, NMR, XRD, Raman, TGA, DTA, DSC, ESCA-XPS,Auger, SEM, TEM, DMTA (torsional braid analysis), Rheometers, MS, Chromatography,are all techniques that have made a major contribution to the science and technology ofpolymers and coatings. This section is very incomplete, and additions are welcome sinceit represents major enablers in the 2nd chemical revolution. A good starting reference tothe history of instrumentation is “The History and Preservation of ChemicalInstrumentation,” Eds John T. Stock and Mary Virginia Orna, D. Reidel Publishing Co.(Springer), 2008Mass Spec history is available at nd see also S. Borman, H. Russell, G. Siuzdak, “ Mass Spec Timeline” TODAY‟SCHEMIST AT WORK, September, 47-49. (2003)Crystallography and X-ray diffraction started with von Laue and Bragg in 1912 and auseful history can be found in J.-L. Hodeau, R. Guinebretiere, “Crystallography: past andpresent,” Appl. Phys. A 89, 819 -823 (2007).Stuart Croll200913NDSU

1881Infrared absorption first studied in by Abney and Festing.1903Russian botanist Mikhail Semenovich Tswett, coined „chromatography‟ from Latin forcolor writing, reports column adsorption chromatography. He passed extracts of planttissue through a chalk column to separate pigments by differential adsorption. [M. S.Lesney, “Chromatography, A brief history of "color writing”, Today's Chemist at Work,1998, 7 (8), 67-68, 71-72].1931Richard Kuhn and others use chromatography to separate isomers of polyene pigments,showing that this was a more widely useful technique [M. S. Lesney, “Chromatography,A brief history of "color writing”, Today's Chemist at Work, 1998, 7 (8), 67-68, 71-72].1920-1930sFurther research done in universities on infrared spectroscopy.1934Don Brookfield sells the first dial viscometer.1941Beckman makes the first commercial infrared spectrometer.Vitamin A is discovered to absorb in ultraviolet part of spectrum which is then used inUS to check that military rations had vitamins.1946Purcell, Torrey, and Pound at Harvard (Purcell et al., 1946) and Bloch, Hansen, andPackard at Stanford (Bloch et al., 1946) independently found that they could detectcharacteristic magnetic moments of spinning atomic nuclei, i.e. nuclear magneticresonance, NMR.1953First NMR spectrometer made by Varian Associates, HR-30.Stuart Croll200914NDSU

Synthetic PigmentsN.B. At present, most of the entries for TiO2 are above.Egyptian Antiquity (4th Dynasty 2500)Egyptian blue, a glass really, (Cuprorivaite) CaO.CuO.4SiO2Cobalt used to colour materials, such as glass (and ground to make a pigment in medievaltimes, “smalt”), and pottery glazes – probably occurred around whole of Middle East.Chinese Antiquity ( 800 B.C.)Chinese Blue and Purple, similar compositions to Eqyptian blue but with barium insteadof calcium.Mayan Antiquity, 4th - 8th (?) Century A.D.Maya Blue, indigo intercalated into palygorskite clay [G. Chiari et al.]. This is anexample of what has become a very modern approach to nanocomposites!1704 (approx)Prussian blue introduced, i.e. Fe4[Fe(CN)6]3.14 – 16 H2O. First synthetic pigment of themodern(?) era.1828 (approx)Ultramarine blue.1905Red -naphthol [“Industrial Organic Pigments,” W. Herbst, K. Hunger, 2nd. Ed. 1997,VCH-Wiley]1907Toluidine red (PR 3) [“Industrial Organic Pigments,” W. Herbst, K. Hunger, 2nd. Ed.1997, VCH-Wiley]1909Hansa yellow (PY 1) first made in Germany – monoazo pigment that is usefully lightstable [“Industrial Organic Pigments,” W. Herbst, K. Hunger, 2nd. Ed. 1997, VCH-Wiley]1916First type of titanium dioxide pigment made. Farup and Jebsen in Norway invent thesulphate process for industrial production.1919First production of TiO2 pigment (anatase mixed with barium sulphate) Frederikstad bythe Titan Company.1920Stuart Croll200915NDSU

First synthesis of diffraction effect pigments materials using HgCl2 platelets (Note use ofmaterial from fish scales dates back to 17th. Century).1923Anatase pigments were introduced in France [Napier et al.], but rutile pigments did notappear until the early 1940s1930 approxInterference pigments made with other heavy metals, lead, arsenic and bismuth salts asplatelets. Note that in 1959 Merck makes basic lead carbonate (white lead) as aninterference (platelet shaped particles) pigment.Fluorescent paints made from anthracene dyes in shellac, by Robert and Joseph Switzerof Berkeley, California [Pinchin and Tsang].1932ICI in England introduce alkyd paint, based on technology from DuPont in USA.1935Commercialization of diarylide yellows (patented in 1911)Phthaloblue appeared, a synthetic, organic pigment that is very light stable.1938Phthalogreen is commercialised [“Industrial Organic Pigments,” W. Herbst, K. Hunger,2nd. Ed. 1997, VCH-Wiley].1948DuPont commercialise the chloride process for making rutile TiO2 pigments.1954Disazo condensation pigments [“Industrial Organic Pigments,” W. Herbst, K. Hunger, 2nd.Ed. 1997, VCH-Wiley]1955Quinacridones - intense, stable organic red pigments [“Industrial Organic Pigments,” W.Herbst, K. Hunger, 2nd. Ed. 1997, VCH-Wiley]1956Perylene chemistry pigments, versatile chemistry that produces cheaper, but less stablered pigments than quinacridones.1960Benzimidazoline series of pigments appear [“Industrial Organic Pigments,” W. Herbst, K.Hunger, 2nd. Ed. 1997, VCH-Wiley]1963Stuart Croll200916NDSU

DuPont patents metal oxide (TiO2) coated mica flakes as interference effect pigments,closely followed by patents from Mearl in 1964.1971Use of aluminium flake pigments in metallic effect coatings for Lincolns. The flakepigments were made by Avery [G. P. Bierwagen, NDSU, private communication].1972Dupont, then others, supply titanium dioxide pigments in slurry form to the US paintindustry.1978White lead pigments banned in US.1984Use of interference effect pigments in automotive use [VCH Interference Pigment book].Stuart Croll200917NDSU

Bibliography1. J. A. Prane, “Introduction to Polymers and Resins,” Federation Series on coatingsTechnology, Federation of Societies for Coatings Technology, Philadelphia PA (1986).2. “Organic Coatings: Their Origin and Development” Proc. of the InternationalSymposium on the History of Organic Coatings, held September 11 – 15, 1989, in MiamiBeach, FL. Eds. R. B. Seymour and H. E. Mark, Elsevier Science Publishing Co. Inc,New York, NY (1990)3. T. R. Bullett, “Paint: A Changing Spectrum,” Rev. Prog. Coloration, Vol. 14, pp. 78 –83 (1984)4. Sheldon Hochheiser, “Rohm and Haas: History of a Chemical Company,” Univ. ofPennsylvania Press, Baltimore, MD (1986)5. Keith Hammond, “A brief history of paint,” series in Polymers Paint Colour JournalFeb-July 2003.6. C. R. Martens, “Alkyd Resins,” Reinhold Publishing Corporation NY 1961. (Chapmanand Hall Ltd. London)7. E. Napier, J. G. Balfour, “A radiant history, The changing face of titanium dioxide,”Surface Coatings Int., Vol. 81(11), 533-537 (1998)8. “Industrial Inorganic Pigments,” Ed. G. Buxbaum, VCH-Wiley 19939. “Industrial Organic Pigments,” W. Herbst, K. Hunger, 2nd. Ed. 1997, VCH-Wiley.10. Temple C. Patten, “Paint Flow and Pigment Dispersion,” Interscience Publishers,John Wiley and Sons Ltd., New York, NY, 1st edition 1964.11. G. E. F. Brewer, “History of Painting: 75 Years,” Plating and Surface Finishing, Vol.71 (June), pp. 57 – 60 (1984)12. J. Boxall, “A history of paint technology Part II: mid-19th century to 20th century,”Paintindia, pp. 6 – 12 (July 1982)13. P. Nylén and E. Sunderland, “Modern Surface Coatings,” Interscience Publishers,John Wiley and Sons Ltd., New York, NY 196514. “Treatise on Coatings,” Volumes 1 – 5, Eds. R. R. Myers, J. S. Long, Marcel Dekker,New York NY, 1965.Stuart Croll200918NDSU

15. Harriet Standeven, “Cover the World: A History of the Manufacture of HouseholdGloss Paints in Britain and the United States from the 1930s to the 1950s,” ModernPaints Uncovered, Tate Modern, 16-19th May 2006.16. Sarah Eleni Pinchin and Jia-sun Tsang, “Daylight Fluorescent Pigments,” ModernPaints Uncovered, Tate Modern, 16-19th May 2006.17. J. W. Taylor, M. A. Winnik, “Functional Latex and Thermoset Latex Films,” JCTResearch, Vol 1(3), 163 – 190 (2004).18. G. Chiari, R. Giustetto, J. Druik, E. Doehne, G. Ricchiardi, “Pre-columbiannanotechnology: reconciling the mysteries of the maya blue pigment,” Appl. Phys. A., 90,3 – 7 (2008)19. H. Berke, “The invention of blue and purple pigments in ancient times,” Chem. Soc.Rev., 36(1), 15 – 30 (2007)20. Reference for paint cleaning techniques and their history:Helmut Ruhemann, "The Cleaning of Paints," Pub. Frederick A. Prager, New York 1968Stuart Croll200919NDSU

P. Castan (Switzerland) and S. Greenlee (USA) patent epoxy resins. Triton surfactants invented by Herman Bruson (for Rohm and Haas?). 1933 National Grid for supplying electricity was established in the United Kingdom by interconnecting regional grid