Dr. Mark D. Soucek

Research Areas

• UV-Curable Coatings
• Ureas, Urethanes, Polyesters
• Waterborne Coatings
• Space Coatings
• Powder Coatings Center
• Dry Oils and Ceramer Coatings

Drying Oils, Alkyds & Ceramer Coatings

In the field of paints and coatings, seed oils have been traditional used as drying oils as a component of class of paints known as alkyds. The term drying oil is used to describe oils in which the unsaturated fatty acid residues or glycerides crosslink via auto-oxidative process to form a varnish. In order for a seed oil to be classified as a "drying oil", the drying index [drying index= % linoleic acid + 2(% linolenic acid)] has to be >70, and for a semi-drying oil the drying index is in the 65-70 range. Sunflower and linseed oils are categorized as a semi-drying and a drying oil, respectively. Metal catalysts known as driers are usually added to semi-dryings oil like sunflower oil to accelerate the drying process.

Vegetable oil and its derivatives have traditionally been a major ingredient in commercial coatings and the ink industry. In fact, vegetable oil derivatives such as alkyds, uralkyds, and epoxy esters are widely used as low cost coatings To reduce the dependence on petroleum as a chemical feedstock for coatings, there has been a push to derive new classes of coating resins and reactive diluents from renewable resources. Epoxidized vegetable oils, in particular, can be photopolymerized and are used in UV-curable coatings and inks. While cost effective, commercial epoxidized oils have suffered from a low glass transition temperature and a sluggish reaction rate. As a consequence, it would be very interesting to design new derivatives of epoxy vegetable oils with enhanced polymerization rate and more stiffness built into the polymer backbone.

Researchers at Cargill have chemically modified linseed oil using a Diels-Alder reaction of cyclopentadiene at high temperature and pressure to form norbornene groups on the chain known as Dilulin. Typically, only 2 – 5% of the double bonds are modified via these processes. Although the first report of the epoxidiation of Dilulin can be found in the patent literature, Soucek and coworkers have recently reported the first detailed investigation of the epoxidation chemistry for Dilulin. They found that the epoxidation of the mixed norbornene and acyclic double bond could be optimized using a phase-transfer process with H 2O 2 and tungstate epoxidation catalyst. However, the degree of norbornylization was not varied and the effect of the reactive diluent (vinyl ether) and non-reactive diluent was not investigated.

The strategy for the preparation of ENLO is shown in Scheme 1. The ENLO was prepared using two steps from linseed oil. In the first step the norbornene linseed oil (NLO) was prepared by the Diels-Alder reaction of dicyclopentadiene with linseed oil at 250 oC in the pressure of 0.76 - 0.90 Mpa. The ENLO was subsequently epoxidized NLO with hydrogen peroxide catalyzed by the tungstate phosphate. Based on a fatty acid assay, the triglyceride consisted of a mixture of 10% saturated fatty acid and 90% unsaturated fatty acid (22% oleic, 16% linoleic, and 52% linolenic acid). The average carbon-carbon double bond is 6.30 mol per mol linseed oil, mole ratio (1.05/1.0) of dicyclopentadiene to the carbon-carbon double bond is employed to norbornylize linseed oil (NLO-100). Similarly, molar ratio of 0.5/1.0 and 0.25/1.0 (dicyclopentadiene / oil carbon-carbon double bond) were also prepared.

New inorganic/organic hybrid coatings have been prepared utilizing linseed oil, ENLO, soybean, and sunflower oil as an organic phase and two sol-gel precursors [Ti(Oi-Pr) 4, Ti(Oi-Pr) 2(acac) 2]. Continuous single phase films have been prepared with a range of sol-gel precursor to drying oil ratios up to 50 % of the sol-gel component. Various coatings properties such as adhesion, hardness, impact resistance and flexibility were obtained as a function of sol-gel precursor content. In addition, tensile properties and thermo-oxidative stability were also investigated. The sol-gel precursor appears to accelerate the drying process of the drying oil. Higher sol-gel precursor content increased both tensile strength and tensile modulus and decreased flexibility and strain-at-break. The thermo-oxidative stability was relatively constant throughout the hybrid samples and comparable to drying oils films with driers.

The development of drying oil and alkyd based ceramer coatings as low VOC, environmentally benign, corrosion resistant coatings for metal substrate is an area of ongoing research. In addition to metal substrates, leather and mineral substrates are also being pursued. Our ceramers approach zero VOC as coating, using environmentally benign starting materials. As shown in our studies, the new hybrid coatings have superior adhesion to the substrate, are self-drying (the inorganic metal-oxo clusters catalyzes the auto-oxidative crosslinking process of the organic phase), and have better barrier properties than drying oils. Due to their excellent barrier properties, these coatings also have potential as electrical insulating coatings and in the microelectronic industry. Moreover, the mixed metal ceramers have corrosion resistance which is competitive with the presently used epoxide-based primers. In addition to the inherent environmental advantages, the coatings are also very inexpensive.

Pertinent Publications

1. Soucek, M.D.; Tuman, S. J. (1995) "Novel Organic/Inorganic Materials Based Drying Oils with Sol-Gel Precursors" Polymer Preprints vol. 36(2), 336.

Novel Inorganic/Organic Hybrid Materials Based on Drying Oils with Sol-Gel Precursors

Scott J. Tuman and Mark D. Soucek

Department of Polymers & Coatings

North Dakota State University, Fargo, ND 58105

New inorganic/organic hybrid materials have been prepared utilizing linseed oil and sunflower oil as an organic phase and two sol-gel precursors [Ti(Oi-Pr) 4 and Ti(Oi-Pr) 2(acac) 2] as an inorganic phase. The overall objective of this study was to improve the mechanical properties of drying oil thin films without substantially decreasing their thermo-oxidative stability. The method employed involves an in situ polycondensation of metal alkoxides in organic polymer matrices via the sol-gel process. During processing, the metal sol-gel precursors appear to accelerate the autoxidative cross-linking process of the organic phase. Materials with a range [0-25 wt %] of sol-gel precursor to drying oil ratios have been studied. The tensile properties, fracture toughness and thermo-oxidative stability were observed as a function of sol-gel precursor content. Higher sol-gel precursor content increased both tensile strength and tensile modulus but decreased strain-at-break. The thermo-oxidative stability was similar to drying oil thin films cured with driers.

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2. Tuman, S. J.; Fouquette, D. J.; Soucek, M.D. (1995) “Structure-Property Behavior of Inorganic /Organic Materials with Acid Catalyzed Sol-Gel Reactions” Polymer Preprints vol. 36(2), 338.

Structure-Property Behavior of Inorganic/Organic Hybrid Materials with Acid Catalyzed Sol-Gel Reactions

Scott J. Tuman, David Fouquette and Mark D. Soucek

Department of Polymers & Coatings

North Dakota State University, Fargo, ND 58105

The study investigates the structure-property behavior of hybrid materials in order to determine the effect of the acid catalyst to sol-gel precursor ratio. New inorganic/organic hybrid materials have been prepared utilizing linseed oil and sunflower oil as an organic phase and a sol-gel precursor [Si(OEt) 4] (TEOS) as an inorganic phase. Our approach involves an in situ polycondensation of metal alkoxides in organic polymer matrices via the sol-gel process. Since TEOS volatilizes below the cure temperature of these hybrid materials, it is necessary to build-up the sol-gel clusters at ambient conditions before curing. The tensile properties, thermo-oxidative stability and phase morphology were observed as a function of sol-gel precursor content. Higher acid catalyst content increased both tensile strength and tensile modulus up to a limiting value. The thermo-oxidative stability was relatively unaffected by the inclusion of an acid catalyst. Electron micrographs showed an increase in phase separation with increased acid catalyst content.

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3. Tuman, S. J.; Chamberlain, D.; Scholsky, K. M.; Soucek, M.D. (1995) “Differential Scanning Calorimetry Study of Linseed Oil Cured with Metal Catalysts” Polymer Preprints vol. 36(2), 380.

Department of Polymers & Coatings

North Dakota State University, Fargo, ND 58105

‡Department of Chemistry

Winona State University, Winona, MN 55987

Differential Scanning Calorimetry (DSC) has been used to study the reaction of linseed oil catalyzed by conventional metal driers and two metal sol-gel precursors, Ti(Oi-Pr) 2(acac) 2 and Ti(Oi-Pr) 4. The reaction kinetics of the curing process of these hybrid materials have been studied in order to understand the reaction mechanisms involved. In this study, materials with a range (0 to 4.0 wt %) of metal catalyst to drying oil ratios have been prepared. The onset temperature and peak temperature of the reaction exotherm were observed as a function of metal catalyst content. In addition, the Borchardt and Daniels kinetics software package was used to investigate the heat of reaction. Higher metal catalyst content caused the onset temperature and peak temperature to decrease. The inclusion of metal catalysts decreased the heat of reaction.

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4. Soucek, M.D.; Tuman, S. J. (1996) "Novel Organic/Inorganic Coatings Based on Linseed and Sunflower Oil with Sol-Gel Precursors" J. Coat. Technol. vol. 68(854), 73.

Novel Inorganic/Organic Coatings Based on Linseed Oil and Sunflower Oil with Sol-Gel Precursors

Scott J. Tuman and Mark D. Soucek*

Department of Polymers & Coatings

North Dakota State University, Fargo, ND 58105

*Person to whom correspondence should be sent

Abstract

New inorganic/organic hybrid coatings have been prepared utilizing linseed oil and sunflower oil as an organic phase and two sol-gel precursors [Titanium (IV) i-propoxide, Titanium (di-i-propoxide) bis(acetyl-acetonate)] as an inorganic phase. The ultimate goal is to develop a primer that will provide better adhesion and corrosion protection for metal substrates with minimal environmental impact. Coatings with a range of sol-gel precursor to drying oil ratios have been studied. Various coatings properties such as adhesion, hardness, impact resistance and flexibility were observed as a function of sol-gel precursor content. In addition, the tensile properties and thermo-oxidative stabilities were also investigated. During processing, the sol-gel precursors appear to accelerate the drying of the coatings. Higher sol-gel precursor content increased both tensile strength and tensile modulus but decreased flexibility and strain-at-break. The thermo-oxidative stability was similar to drying oil coatings cured with driers.

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5. Tuman, S. J.; Chamberlain, D.; Scholsky, K. M.; Soucek, M.D. (1996) “Differential Scanning Calorimetry Study of Linseed Oil Cured with Metal Catalysts” Prog. Org. Coat. vol. 28, 251.

S. J. Tuman, D. Chamberlain, K. M. Scholsky ‡ and M. D. Soucek*

Department of Polymers & Coatings

North Dakota State University, Fargo, ND 58105

‡Department of Chemistry

Winona State University, Winona, MN 55987

Abstract

Differential Scanning Calorimetry (DSC) has been used to study the autoxidative curing process of linseed oil catalyzed by conventional metal driers and two metal sol-gel precursors, Ti(Oi-Pr) 2(acac) 2 and Ti(Oi-Pr) 4, at elevated temperatures. Linseed oil resins with a range of 0 to 5.0 wt % metal sol-gel precursor and 0 to 9.0 wt % zirconium drier have been investigated by both dynamic and isothermal methods. The onset, peak, and end temperatures of the reaction exotherms were observed as a function of metal catalyst type and content. The Borchardt and Daniels kinetics method was used to quantify the heat of reaction of the dynamic DSC scans. The indention hardness of the resultant coatings in the DSC sample pans was measured as an indication of cross-link density. The inclusion of small quantities of metal catalyst (0 to 5.0 wt % titanium alkoxide, 0 to 2.0 wt % zirconium drier) caused the reaction exotherm to broaden and shift to lower temperatures. At higher metal catalyst content ( > 5.0 wt % Ti(Oi-Pr) 2(acac) 2 or 5.0 wt % Ti(Oi-Pr) 4) the reaction exotherms became imperceptible. Overall, as the metal catalyst content was increased, the heat of reaction decreased while indention hardness increased. The effects of the two sol-gel precursors on the reaction exotherms were similar to the effects of conventional driers. Combinations of conventional driers were also studied.

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6. Wold, C R.; Soucek, M.D. (1996) “Novel Inorganic/Organic Ceramer Coatings” Polym. Prepr., vol. 37(2), 309.

Novel Inorganic/Organic Ceramer Coatings.

Chad R. Wold and Mark D. Soucek *,

Department of Polymers and Coatings,

North Dakota State University, Fargo, North Dakota 58105

Abstract

Mixed metal oxide hybrid ceramer coatings were developed using linseed oil as the organic phase with titanium i-propoxide, titanium (di-i-propoxide) bis(acetylacetonate), and Zirconium n-propoxide as the inorganic sol-gel precursors. The overall goal of this study is to develop a primer that will provide better adhesion and corrosion protection for metal substrates with minimal environmental impact. Zinc acetate dihydrate was introduced to the system as an anticorrosive agent. Various coatings properties such as adhesion, hardness, impact resistance and flexibility were observed as a function of sol-gel precursor type and content. In addition, electrochemical impedance spectroscopy (EIS) was used to evaluate the corrosion properties in which low concentrations of sol-gel precursor content demonstrated excellent electrical barrier properties.

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7. Wold, C R.; Soucek, M.D. “Mixed Metal Oxide Inorganic/Organic Ceramer Coatings” Polym. Prepr., 1997, vol. 38(1) , 205.

Mixed Metal Oxide Inorganic/Organic Ceramer Coatings

Chad R. Wold and Mark D. Soucek *,

Department of Polymers and Coatings,

North Dakota State University, Fargo, North Dakota 58105

Abstract

Mixed metal oxide hybrid ceramer coatings were developed using linseed oil as the organic phase with titanium i-propoxide, titanium (di-i-propoxide) bis(acetylacetonate), and Zirconium n-propoxide as the inorganic sol-gel precursors. The overall goal of this study is to develop a primer that will provide better adhesion and corrosion protection for metal substrates with minimal environmental impact. Zinc acetate dihydrate was introduced to the system as an anticorrosive agent. Various coatings properties such as adhesion, hardness, impact resistance and flexibility were observed as a function of sol-gel precursor type and content. In addition, electrochemical impedance spectroscopy (EIS) was used to evaluate the corrosion properties in which low concentrations of sol-gel precursor content demonstrated excellent electrical barrier properties.

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8. Wold, C R.; Soucek, M.D. “Mechanical Properties of Mixed Metal Oxide/Linseed Oil-Based Ceramer Coatings” Polym. Mat. Sci. Eng.,1998, vol. 78(1) , 29.

Mechanical Properties Of Mixed Metal Oxide/Linseed Oil-Based Ceramer Coatings.

Chad R. Wold and Mark D. Soucek *,

Department of Polymers and Coatings,

North Dakota State University, Fargo, North Dakota 58105

Mixed metal oxide ceramer coatings were developed utilizing linseed oil as the organic phase with titanium i-propoxide, and zirconium n-propoxide as the inorganic sol-gel precursors. Zinc acetate dihydrate was introduced to the system as an anticorrosive agent. The presence of two sol-gel precursors was found to substantially increase the tensile properties of the final coatings. In addition, small concentrations of zinc acetate dihydrate further increased the tensile properties. The tensile strength, tensile stress, and tensile modulus of these coatings are reported as a function of metal alkoxide content.

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9. Wold, C R.; Soucek, M.D. “Mixed Metal Oxide/Linseed Oil-Based Coatings”J. Coat. Tech.,1998, vol. 70 , No. 882, 43.

Mixed Metal Oxide Inorganic/Organic Coatings.

Chad R. Wold and Mark D. Soucek *,

Department of Polymers and Coatings,

North Dakota State University, Fargo, North Dakota 58105

Abstract

Mixed metal oxide ceramer coatings were developed using linseed oil as the organic phase with titanium i-propoxide, and zirconium n-propoxide as the inorganic sol-gel precursors. The overall goal of this study was to develop a primer that will provide corrosion protection and better adhesion to metal substrates with minimal environmental impact. Zinc acetate dihydrate was introduced to the system as an anticorrosive agent. Various coatings properties such as adhesion, hardness, impact resistance, flexibility, and tensile properties were investigated as a function of sol-gel precursor type and content. In addition, electrochemical impedance spectroscopy (EIS) was used to evaluate the corrosion properties of these mixed metal oxide inorganic/organic coatings.

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10. Wold, C. R.; Soucek, M. D. “Rheological Properties of Linseed Oil-Based Ceramer Coatings”Polym. Mat. Sci. Eng., 1998, vol. 81 , 134.

Rheological Properties of Linseed Oil-Based Ceramer Coatings

Chad R. Wold and Mark D. Soucek

Department of Polymers and Coatings

North Dakota State University

Fargo, ND 58105

Abstract

Dynamic mechanical thermal analysis was used to determine the crosslink density and glass transition of various ceramer coatings. The metal-oxide ceramer coatings were developed using linseed oil as the organic phase with titanium i-propoxide, and zirconium n-propoxide as the inorganic sol-gel precursors. The viscoelastic characteristics and tensile properties were investigated as a function of sol-gel precursor type and content. The sol-gel precursor type and content were found to effect the crosslink density, glass transition temperature, and tensile modulus. In addition, phase morphology, of these ceramer coatings were evaluated using small-angle X-ray scattering. The morphology of these ceramer coatings was found to primarily depend on sol-gel precursor concentration.

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11. Wold, C.R.; Ni, H.; Soucek, M.D. “Model Compound Study of Sol-Gel Precursor Interaction with Free Fatty Acids” Polym. Prepr., 1999 , vol. 40(2), 793.

Model Compound Study of Sol-Gel Precursor Interactions with Drying Oils

Chad R. Wold and Mark D. Soucek

Department of Polymers and Coatings

North Dakota State University, Fargo, ND 58105

This study was used to determine whether a metal carboxylate containing unsaturated fatty acids could be used in conjunction with a drying oil to form a homogeneous inorganic/organic coating. To investigate this proposed interaction, Ti(Oi-Pr) 4 was reacted with linoleic, oleic, and stearic acids. Nuclear magnetic resonance, Fourier-transform infrared spectroscopy, and Fourier-transform Raman spectroscopy were used to study the interaction between Ti(Oi-Pr) 4 and free fatty acids. The data obtained revealed a bidentate chelating metal carboxylate.

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12. Ballard, R. L.; Tuman, S. J.; Fouquette, D. J.; Stegmiller, W.; Soucek, M.D. “Effects of an Acid Catalyst on the Inorganic Domain of Inorganic-Organic Hybrid Materials” Chem. Mater.1999, vol. 11, 726.

Effects of an Acid Catalyst on the Inorganic Domain of Inorganic-Organic Hybrid Materials

R.L. Ballard, S.J. Tuman, D.J. Fouquette, W. Stegmiller, and M.D. Soucek *

Department of Polymers & Coatings

North Dakota State University

Fargo, North Dakota 58105

Abstract

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.13. Wold, C.R.; Soucek, M.D. “Viscoelastic and Thermal Properties of Linseed Oil-Based Ceramer Coatings” Macromol. Chem. Phys. 2000 , 201(3), 382.

Viscoelastic and Thermal Properties of Linseed Oil-Based Ceramer Coatings

Chad R. Wold and Mark D. Soucek *

Department of Polymers and Coatings

North Dakota State University, Fargo, ND 58105

Abstract

Dynamic mechanical thermal analysis (DMTA) was used to determine the crosslink density and glass transition temperature of various ceramer coatings. The metal-oxide ceramer coatings were developed using linseed oil as the organic phase with titanium i-propoxide, and zirconium n-propoxide as the inorganic sol-gel precursors. The viscoelastic characteristics and tensile properties were investigated as a function of sol-gel precursor type and content. The phase morphology, and thermal decomposition of these ceramer coatings were evaluated using small-angle X-ray scattering (SAXS), and thermal gravimetric analysis (TGA), respectively. The sol-gel precursor type and content were found to effect the crosslink density, glass transition temperature, and tensile modulus. The morphology of these ceramer coatings was found to primarily depend on sol-gel precursor concentration. Thermal gravimetric analysis (TGA) revealed that the thermal history of the ceramer coatings also depended on sol-gel precursor concentration.

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14. Teng, G.; Soucek, M. D. “ Synthesis, Characterization, and Application of Blown Oil for Ceramer Coatings” Polym. Mater. Sci. Eng. 2000 , 83, 489-490.

Synthesis, Characterization, and Application of Blown Oil for Ceramer Coatings

Ganghua Teng,, and Mark D. Soucek

North Dakota State University, Polymers and Coatings Department

Fargo, ND 58105

Abstract

New ceramer coatings based on blown soybean oil with sol-gel precursors were prepared and evaluated as a function of the blowing process and sol-gel precursors content. Soybean oils were blown at three different rates in order to optimize the blowing process. Three sol-gel precursors, titanium (IV) i-propoxide, titanium (IV) di-i-propoxide bis-acetoacetonate, and zirconium n-propoxide were then used with the blown oil to investigate the affect of sol-gel precursors content on film properties. Both tensile properties and general coatings properties (including adhesion, hardness, impact resistance, and flexibility) were investigated as a function of sol-gel precursor content. In general, higher sol-gel precursor content increased hardness, tensile strength and modulus, and corrosion resistance, but decreased impact resistance.

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15. Ballard, R. L.; Tuman, S. J.; Fouquette, D. J.; Stegmiller, W.; Soucek, M.D. (2001) “Inorganic-Organic Hybrid Coatings with Mixed Metal-Oxides” European Polymer Journal. 37, 381.

Inorganic-Organic Hybrid Coatings with Mixed Metal Oxides

R. L. Ballard, J. P. Williams, J. M. Njus, B. R. Kiland, and M. D. Soucek *

Department of Polymers & Coatings

North Dakota State University

Fargo, North Dakota 58105

Abstract

Ceramer coatings were developed using soybean oil as the organic phase with mixtures of titanium(IV) isopropoxide (TIP) and zirconium(IV) propoxide (ZRP) as the inorganic phase. TIP was also used in combination with zinc acetate dihydrate and zinc phosphate, with the zinc serving as an anticorrosive agent. The properties of the coatings were evaluated to determine whether a beneficial synergistic effect is obtained by using mixed metal oxides as the inorganic phase. Hardness, adhesion, flexibility, impact resistance, fracture toughness, tensile properties, and dynamic mechanical properties were investigated. Ultraviolet spectroscopy revealed that the zinc acetate dihydrate and the zinc phosphate react with the sol–gel precursor of the inorganic phase. Beneficial synergistic effects were observed in tensile modulus, fracture toughness, and the energy release rate at fracture for equal-weight-percent mixtures of TIP and ZRP.

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16. Wold, C.R.; Ballard, R.; Soucek, M.D. “Corrosion Resistant Linseed Oil-Based Ceramer Coatings” Proceedings of the 58 th Flax Institute of the United States, March 23-25, 2000; Fargo, ND, 129.

Chad R. Wold, Ron Ballard, and Mark D. Soucek*

Department of Polymers and Coatings

North Dakota State University, Fargo, ND 58105

Electrochemical impedance measurements were conducted on linseed oil-based ceramer coatings on aluminum panels immersed in 3% NaCl solution for 180 days. Electrochemical impedance spectroscopy was used to evaluate the corrosion resistance of the ceramer coatings as a function of sol-gel precursor content. The ceramer coatings were developed using linseed oil as the organic phase and titanium i-propoxide and zirconium n-propoxide as the sol-gel precursors. The ceramer coatings containing 5 wt% titanium i-propoxide or zirconium n-propoxide provided excellent barrier protection and maintained a resistance greater than 1 x 10 9 ohms in the low frequency range (f = 0.01 Hz) throughout the study. As an extension to this study, 0.5-1 wt% zinc acetate dihydrate was added as an anticorrosive agent to linseed oil with 5 and 10 wt% titanium i-propoxide. The incorporation of zinc acetate dihydrate dramatically increased the impact resistance while maintaining flexibility. Surprisingly, the incorporation of zinc acetate dihydrate initially decreased the modulus but maintained an initial resistance of 1 x 10 8 ohms for 180 days.

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17. Teng, G.; Soucek, M.D. “Epoxidized Soybean Oil-Based Ceramer Coatings” J. Am. Oil Chem. Soc. 2000 , Vol. 77(4), 381.

Epoxidized Soybean Oil - Based Ceramer Coatings

Ganghua Teng, and Mark D. Soucek*

Department of Polymers & Coatings

Abstract

New inorganic/organic hybrid coatings containing epoxidized soybean oil were prepared. Three sol-gel precursors [titanium (IV) i-propoxide, titanium (IV) di-i-propoxide bis-acetoacetonate, and zirconium n-propoxide] were utilized as the inorganic phase. Various coatings properties, including adhesion, hardness, impact resistance, flexibility, and tensile properties, were investigated as a function of sol-gel precursor type and concentration. All ceramer coatings exhibited excellent flexibility and hardness. Tensile strength and hardness increased with sol-gel precursor concentration. A slight decrease in adhesion and impact resistance was observed with increasing precursor content.

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18. Ni, H.; Simonsick, Jr., W.J.; Skaja, A.D.; Williams, J. P.; Soucek, M.D. (2000) “Polyurea/Polysiloxane Ceramer Coatings” Prog. Org. Coat. 38 (2), 97.

† Polymers and Coatings Department, North Dakota State University, Fargo, ND 58105, USA

* To whom correspondence should be addressed.

Abstract

Tetraethylorthosilicate (TEOS) oligomers were prepared through the hydrolysis and condensation of TEOS with water. The mixture of TEOS oligomers was characterized by FT-IR, 29Si NMR and Electrospray Ionization-Mass Spectrometry (ESI-MS). The ESI-MS and 29Si NMR data show molecular weight ranges from 400-2000 g/mole and many cyclic species exist in addition to linear oligomers. The mechanical and tensile properties were evaluated as functions of TEOS oligomer concentration and silane-functionalized isocyanurate concentration. In addition, viscoelastic properties, thermal properties and morphology of the ceramer coatings were investigated using Dynamical Mechanical Thermal Analysis (DMTA), Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) with Energy Dispersion X-ray Analysis (EDAX). The data showed that ceramer coating properties were affected by both TEOS oligomer content and silane-functionalized isocyanurate content. Also, the adhesion was enhanced by incorporating the TEOS oligomers into the polyurea/polysiloxane coatings.

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19. Ni, H.; Skaja, A.D.; Soucek, M.D. (2000) “Acid-Catalyzed Moisture-Curing Polyurea/Polysiloxane Ceramer Coatings” Prog. Org. Coat. 40, 175.

Acid-catalyzed moisture-curing polyurea/polysiloxane ceramer coatings

Hai Ni, Allen D. Skaja, Jonathan P. Williams and Mark D. Soucek *

Polymers and Coatings Department, North Dakota State University, Fargo, ND 58105, USA

Abstract

The para-toluene sulfonic acid (p-TSA) was used to catalyze the moisture curing of an organic/inorganic hybrid coating system. The organic phase was based on the isocyanurate of 1,6-hexamethylene of diisocyanate (HDI). The inorganic phase was based on the prepolymerized oligomers of tetraethyl orthosilicate (TEOS). An alkoxysilane-functionalized HDI isocyanate was added into the coating formulation to aid in phase miscibility. The general coating and tensile properties were evaluated as a function of the acid catalyst concentration. In addition, the films were analyzed using differential scanning calorimetry (DSC) and dynamical mechanical thermal analysis (DMTA). The results indicated that the acid catalyst enhanced the adhesive properties of the hybrid coatings. The addition of the acid catalyst increased the changed crosslink density of films and decreased the crystallinity of the organic phase.

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20. Ballard, R. L.; Sailer, R. A.; Larson, B.; Soucek, M. D. (2001) “Fracture Toughness of Inorganic-Organic Hybrid Coatings” J. Coat. Technol. Vol. 73(913), 107.

R. L. Ballard, R. A. Sailer, B. Larson, and M. D. Soucek *

Department of Polymers & Coatings

North Dakota State University

Fargo, North Dakota 58105

Abstract

The concepts of fracture toughness and the energy release rate at fracture for thin polymeric films are introduced. Fracture toughness and energy release rate data for ceramer films based on a linseed oil alkyd, a sunflower oil alkyd, and a commercial alkyd with titanium diisopropoxide bis(acetylacetonate), titanium(IV) isopropoxide, and zirconium(IV) propoxide are presented and compared to previously reported tensile data. Differences between the fracture data and the tensile data demonstrate the usefulness of fracture toughness testing. The energy release rate at fracture may be the one property to maximize in order to optimize all of the other coating properties. It may therefore be a great aid in the optimization of coating formulations. Data from dynamic mechanical thermal analysis indicate that there may be a correlation between fracture properties and secondary relaxation processes in the films.

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21. Deffar, D.; Teng, G.; Soucek, M.D. (2001) “Inorganic-Organic Hybrid Coatings Based on Bodied Soybean Oil” Sur. Coat. Int.: Part B Vol. 84( B2), 147.

Inorganic-Organic Hybrid Coatings Based on Bodied Soybean Oil

Department of Polymers and Coatings

North Dakota State University, Fargo, ND, 58105

* To whom all correspondence should be addressed.

Inorganic-organic hybrid coatings were prepared using bodied soybean oil with sol-gel precursors. Three sol-gel precursors, titanium tetra-i-propoxide (TIP), titanium (di-i-propoxide) bis (acetylacetonate) (TIA) and zirconium tetra-n-propoxide (ZrP) were evaluated at three different concentrations (wt %). Coating properties of hardness, cross-hatch adhesion, reverse impact resistance and flexibility were obtained as a function of sol-gel precursor. In addition glass transition temperature and elastic modulus were also determined. The addition of different types of sol-gel at 5, 10, and 15 wt % concentrations imparted hardness without critically affecting flexibility. The optimum hardness and flexibility coating properties were obtained at a 10 wt % sol-gel concentration. The reverse impact resistance however, decreased at a 15 wt % sol-gel concentration. The system containing sol-gel precursor, TIP (10 wt %) exhibited the best coating properties in comparison with TIA and ZrPsystems.

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22. Deffar, D.; Teng, G.; Soucek, M. D. (2001) “Comparison of Titanium-Oxo-Clusters Derived from Sol-Gel Precursors with TiO 2 Nanoparticles in Drying Oil Based Ceramer Coatings” Macromol.Mater.Eng. 286, 204.

Comparison of Titanium-Oxo-Clusters Derived from Sol-Gel Precursors with TiO 2 Nanoparticles in Drying Oil Based Ceramer Coatings

Department of Polymers and Coatings

North Dakota State University, Fargo, ND, 58105

* To whom all correspondence should be addressed.

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23. Teng, G.; Wegner, J.R.; Hurtt, G. J.; Soucek, M. D. (2001) “Novel Inorganic/Organic Hybrid Materials Based on Blown Soybean Oil with Sol-Gel Precursors” Prog. Org. Coat. 42(1-2), 29.

Novel Inorganic/Organic Hybrid Materials Based on Blown Soybean Oil with Sol-Gel Precursors

Abstract

New ceramer coatings based on blown soybean oil with sol-gel precursors were prepared and evaluated as a function of the blowing process and sol-gel precursors content. Soybean oils were blown at three different rates in order to optimize the blowing process. Three sol-gel precursors, titanium (IV) i-propoxide, titanium (IV) di-i-propoxide bis-acetoacetonate, and zirconium n-propoxide were then used with the blown oil to investigate the affect of sol-gel precursors content on film properties. The gelation and film properties of ceramer coatings were dependent on chemical composition, which was a function of blowing time and blowing rate. Both tensile properties and general coatings properties (including adhesion, hardness, impact resistance, and flexibility) were investigated as a function of sol-gel precursor content. In general, higher sol-gel precursor content increased tensile strength and modulus, but decreased impact resistance.

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24. Deffar, D.; Soucek, M. D. (2001) “Synergistic Effect of Driers on Soybean Oil-Based Ceramer Coatings” J. Coat. Technol. Vol. 73(919), 95.

Synergistic Effect of Driers on Soybean Oil-Based Ceramer Coatings

David Deffar and Mark D. Soucek*

Department of Polymers and Coatings

North Dakota State University, Fargo, ND, 58105

* To whom all correspondence should be addressed.

Inorganic-organic hybrid coatings were prepared using blown soybean oil with sol-gel precursors. Three sol-gel precursors, titanium tetra-i-propoxide (TIP), titanium (di-i-propoxide) bis (acetylacetonate) (TIA) and zirconium tetra-n-propoxide (ZrP) were used in conjunction with cobalt, manganese and zirconium driers. The goal of this study was to investigate if synergy exists between the drier and sol-gel precursors with respect to the autoxidation process. Various coating properties such as hardness, adhesion, reverse impact resistance and flexibility were evaluated as a function of sol-gel precursor and drier content. Viscoelastic and tensile properties were also investigated.

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25. Wold, C.R.; Ni, H.; Soucek, M.D. (2001) “Model Reaction Study on the Interaction between the Inorganic and Organic Phases in Drying Oil Based Ceramer Coatings” Chem. Mater. , 13(9), 3032.

Model Reaction Study on the Interaction between the Inorganic and Organic Phases in Drying Oil Based Ceramer Coatings

Chad R. Wold, Hai Ni, and Mark D. Soucek*

Department of Polymers and Coatings, North Dakota State University, Fargo, North Dakota 58105

Abstract

Metal-oxo carboxylates containing unsaturated fatty acids were used to model the interaction between drying oils and sol-gel precursors in inorganic/organic coatings. The metal carboxylates were prepared by reacting titanium isopropoxide [Ti(O-i-Pr) 4] with linolenic and oleic acids. Nuclear magnetic resonance spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, and Fourier transform Raman (FT-Raman) spectroscopy were used to investigate the bond formation between Ti(O-i-Pr) 4 and free fatty acids. The 13C NMR and FT-IR spectra indicate the metal carboxylates are complex mixtures of bidentate chelating, bridging, and metal-oxo bridging clusters. The incorporation of unsaturated metal carboxylates in linseed oil coatings increased the glass transition temperature to 49 C and increased the cross-link density to 1.41 × 10 -3 mol/cm 3.

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26. Chen, J.; Soucek, M.D.; Simonsick, W.J.; Celikay, R.W. (2002) “Preparation and Photopolymerization of Norbornyl Epoxidized Linseed Oil” Polymer, 40(20), 5379.

Synthesis and Photopolymerization of Norbornyl Epoxidized Linseed Oil

Jianxia Chen and Mark D. Soucek

Polymers and Coatings Department

North Dakota State University, Fargo, ND 58105

William J. Simonsick and Recep W. Celikay

Marshall R & D Laboratory

DuPont Automotive, Philadelphia, PA 19146

Abstract

Norbornyl epoxidized linseed oil was synthesized via Diels-Alder reaction of cyclopentadiene with linseed oil at high pressure (~ 200 Psi) and high temperature (240 ° C), followed by an epoxidation using hydrogen peroxide with a quaternary ammonium tetrakis(diperoxotungsto) phosphate(3-) epoxidation catalyst.The products were characterized using 1H and 13C NMR, FT-IR, and electrospray ionization (ESI) mass spectroscopy. Photo-induced curing kinetics of norbornyl epoxidized linseed oil coatings was investigated using real-time FT-IR spectroscopy with a fiber optic UV-curing system. The norbornyl epoxidized linseed oil was formulated with three different divinyl ether reactive diluent. The effect of divinyl ether concentration and types of divinyl ether on the curing reaction was investigated. It was found that the curing rate of norbornyl epoxidized linseed oil was lower than that of cycloaliphatic epoxide, but higher than epoxidized linseed oil. The incorporation of divinyl ethers increased the curing rate and overall conversion of the epoxide groups. Of the three divinyl ether used, coating with triethyleneglycol divinyl ether (TEGDE) showed the highest curing rate and coating with cyclohexane dimethanol divinyl ether (CHDMDE) showed the lowest curing rate.

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27. Chen, J.; Soucek, M.D. (2002) “Epoxidation of Partially Norbornylized Linseed Oil” Macromol. Chem. Phys. 203 , 2042.

Epoxidation of Partially Norbornylized Linseed Oil

Jianxia Chen and Mark D. Soucek

Polymers and Coatings Department, North Dakota State University, Fargo, ND 58105

William J. Simonsick, Jr and Recep W. Celikay

Marshall R & D Laboratory, DuPont Automotive, Philadelphia, PA 19146

Abstract

A new cycloaliphatic epoxide functionalized monomer was prepared from partially norbornylized linseed oil (Dilulin Ò ). Epoxidation was accomplished using three different approaches: peracetic acid, dioxirane and hydrogen peroxide. Dioxirane was generated from potassium peroxomonosulfate and acetone. Hydrogen peroxide was used with a quaternary ammonium tetrakis(diperoxotungsto) phosphate(3-) as a epoxidation catalyst.The epoxidation reactions were monitored by FT-IR and the products were characterized using [ 1H, 13C] NMR, FT-IR, FT-Raman, and electrospray ionization (ESI) mass spectroscopy. For all three approaches, the effect of reaction time, temperature, catalyst concentration, and pH was investigated. Out of the three approaches, the hydrogen peroxide epoxidation was preferred on the basis of yield and ease of purification. The kinetic data were obtained only for the hydrogen peroxide approach. The reaction was found to be first-order with respect to the alkene double bond and 1.4 th –order with respect to the catalyst.

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28. Teng, G.; Soucek, M.D.; Vick, B.A.; Simonsick, W.J.; Sen, A. (2003) “Spectroscopic investigation of the Blowing Process of Soybean Oil” Surf. Coat. Inter. Part B, vol. 86, 221.

Spectroscopic Investigation of the Blowing Process

Department of Polymers & Coatings, North Dakota State University, Fargo, ND 58105

USDA-ARS, Fargo, ND 58105

William J. Simonsick Jr. and Atish Sen

Marshall Research and Development Laboratory, DuPont Automotive, Philadelphia, PA 19146

Abstract

Blown soybean oil was characterized by gas chromatography (GC), nuclear magnetic resonance spectroscopy (NMR), ultraviolet visible spectroscopy (UV-Vis), infrared spectroscopy (IR), electrospray ionization-Fourier transfer mass spectrometry (ESI-FTMS), and gel permeation chromatography (GPC). During the blowing process, transition of cis to trans and conjugation of double bonds, crosslinking, and degradation of oils occurred concurrently. The disappearance of unsaturated fatty esters followed first order kinetics. The formation of carbon-carbon and ether linkages was observed with NMR. It was proposed that the formation of ether linkage occurred via three routes: 1) combination of radicals, 2) homopolymerization of epoxide, and 3) hydroxyl addition to oxirane. Furthermore, the effect of the blowing process on the rheological behavior of the oils was also observed, and blown oil exhibited a higher viscosity than bodied oil.

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29. Teng, G.; Soucek, M.D. (2003) “Blown Soybean Oil Ceramer Coatings for Corrosion Protection” Macromol.Mater. Eng., 288, 844.

Ganghua Teng and Mark D. Soucek

Department of Polymer Engineering, University of Akron, Akron, Ohio 44325

Abstract

A series of ceramer coatings were formulated using blown soybean oil as the organic phase, and sol-gel precursors [titanium (IV) i-propoxide, titanium (IV) di-i-propoxide bis-acetoacetonate, and zirconium n-propoxide] as the inorganic phase. The corrosion resistance of the ceramer coatings was evaluated using failure-at-scribe and electrochemical impedance spectroscopy (EIS) on aluminum after exposure in a Prohesion Chamber. Scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDXA) were also used to evaluate the coatings after exposure. The ceramer coatings demonstrated higher pull-off adhesion, impedance modulus (after exposure), and lower failure-at-scribe than the blown soybean oil film. It was surmised that the addition of sol-gel precursor enhanced the corrosion protective properties of the ceramer coatings via a self-assembling layer of metal-oxo clusters at the film substrate (aluminum) interface.

Key words: Ceramer; Organic coatings; Titanium; Zirconium; EIS

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30. Zong, Z.; Soucek, M.D.; Liu, Y.; Hu, J. (2003) “Cationic Photopolymerization of Epoxynorborane Linseed Oils: The Effect of Diluents” J. Poly. Sci:. Part A41, 3440.

Zhengang Zong and Mark D. Soucek*

Department of Polymer Engineering, The University of Akron, Akron, OH 44325

Yubiao Liu and Jun Hu

Department of Chemistry, The University of Akron, Akron, OH 44325

Abstract

New epoxynorbornene linseed oils (ENLO) were prepared as a function of norbornene content. The cationic photopolymerization of the ENLOs was investigated using real-time infrared spectroscopy and photo-DSC. The effect of reactive diluent and non-reactive diluents on the polymerization rate was also studied. The diluents were found to decrease the viscosity of formulation and accelerate markedly the rate of polymerization of ENLO and increase their final conversion. The effected reactive diluent was compared for ENLO and epoxidized linseed oil (ELO). It was observed that the relative reactivity of oxiranes was not as important as the viscosity of the reacting system and proposed that the cationic photopolymerization of ENLO was controlled by diffusion.

Keywords: epoxynorbornene linseed oil (ENLO); photoinitiated cationic polymerization; photopolymerization; kinetics (poly); diluents

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31. Zou, K; Soucek, M.D. (2004) “UV-Curable Organic-Inorganic Hybrid film Coatings Based on Epoxidized Cyclohexene Derivatized Linseed Oil” Macro. Chem. Phys., 204(15), 2032.

UV-Curable Organic-Inorganic Hybrid Films Coatings Based on Epoxidized Cyclohexene Derivitized Linseed Oil

Kunrong Zou, Mark D Soucek *

Department of Polymer Engineering, The University of Akron, Akron, OH, 44304

Abstract

Organic-inorganic hybrid films based on epoxidized cyclohexene derivitized linseed oil (ECLO) and TEOS oligomers were prepared via a UV-curing process. The kinetics of the hybrid materials were studied by Photo-DSC. The tensile properties, pencil hardness, pull-off adhesion, reverse impact resistance, solvent resistance and abrasion resistance of the hybrid coatings were evaluated. A dynamic mechanical thermal analysis(DMTA) and thermogravimetric analysis (TGA) were used to investigate the viscoelastic and thermal properties of the hybrid films. The morphology of the hybrid film was characterized by atomic force microscope (AFM). The hybrid films exhibited higher pencil hardness, tensile strength and tensile modulus, fracture toughness, abrasion resistance, cross-link density, and thermal stability compared to the ECLO organic film. The Photo-DSC data showed that photo-curing speed of the hybrid materials increased with TEOS oligomers content. It was postulated that the TEOS oligomers were reactive diluents.

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32. Soucek, M.D.; Johnson, A.H.; Wegner, J.M. (2004) “Ternary Evaluation of UV-Curable Seed Oil Inorganic/Organic Hybrid Coatings Using Experimental Design” Prog. Org. Coat. Vol. 5(4), 300.

Ternary Evaluation of UV-Curable Seed Oil Inorganic/Organic Hybrid Coatings Using Experimental Design

Mark D. Soucek, 1* Aaron H. Johnson, 2 Jonathan M. Wegner 2

1Department of Polymer Engineering, University of Akron, Akron, OH 44325

2Department of Polymers & Coatings, North Dakota State University, Fargo, ND 58105

Abstract

Inorganic/organic hybrid coatings were prepared using epoxidized linseed oil with combinations of the two sol-gel precursors (titanium (IV) isopropoxide, tetraethyl orthosilicate), and a telechelic silicate based on a modified oligomeric caprolactone. The coatings were UV-cured with sulfonium initiators which concomitantly cured the epoxy functional organic phase and the sol-gel inorganic phase to form a co-continuous inorganic/organic system. A ternary experimental design was employed to elucidate the influence of inorganic modifier on the mechanical properties of the inorganic/organic hybrid coatings. Small angle X-ray scattering (SAXS) was used to evaluate radius of gyration of the metal-oxo-cluster. Various coating properties, such as hardness, impact resistance, adhesion, solvent resistance, and surface energy were investigated as a function of sol-gel precursors. Inorganic/organic hybrid coatings containing both tetraethyl orthosilicate and the modified caprolactone resulted in improved hardness and solvent resistance with no loss of impact strength. The inclusion of titanium (IV) isopropoxide in to the systems resulted in a systematic reduction in the coatings properties. This was attributed to inhibition of the organic crosslinking process as a consequence of absorption of ultraviolet light by the titanium-oxo-clusters.

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33. Soucek, M.D.; Johnson, A.J. (2005) “Preparation of Nano-sized UV-Absorbing Titanium-Oxo-Clusters via a Photo-Curing Ceramer Process” 16(2-3), 257.

Preparation of Nanosized UV-absorbing Titanium-oxo-clusters via a Photo-curing Ceramer Process

Mark D. Soucek, * Aaron H. Johnson, Leon E. Meemken, Jonathan M. Wegner

Department of Polymer Engineering, University of Akron, Akron, OH 44325

Abstract

A titanium sol-gel precursor, titanium (IV) isopropoxide (TIP), was mixed with an epoxidized linseed oil (ELO). Using a cationic super-acid photoinitiator, ttriarylsulfonium hexafluoroantimonate, both the organic phase (ELO) and the inorganic phase (TIP) were concomitantly cured. The exposure to moisture was strictly controlled before and during the UV-curing process. The UV-Visible spectra, SAXs (small angle X-ray), DMA (dynamic mechanical properties), and contact angle were investigated as a function of sol-gel precursor. The UV-Visible spectra revealed that the inorganic/organic hybrid materials were more effective at blocking the UV-light than nanoparticulate titanium dioxide while maintaining complete transparency in the visible region. The contact angle data indicated that the inorganic phase preferentially was concentrated at the film-surface interface. The SAXs data was indicative of a 2-5 nm titanium-oxo-cluster size, and the DMA data suggests a well distributed system.

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