An extended Poster Session was held on the first day of the conference from 5:30 pm to 7:30 pm, concurrent with a Networking Reception. Poster contributors discussed their research results with interested attendees.
Formulating for a New Era: Using New VOC-Exempt and VOC-Compliant Solvents
Dave Pasin, TBF Environmental Technology
The purpose of this presentation is to discuss and detail advances in VOC compliant solvents. The presentation will outline a variety of new VOC compliant solvents, their efficacy, how they may perform and where they may be used in coatings and adhesive formulation applications. The presentation will also discuss formulating to lower the VOCs of paint and coatings and the effect of these new solvents on the phsyiochemcial characterisitics of the coatings.
The presentation will also discuss the development of a new VOC exempt, low toxicity replacement for Glycol Ether and a new VOC exempt replacement for film forming coalescents such as Texanol and Film Former.
4 Learning Objectives
i) Novel VOC compliant solvent options available for low VOC formulation
ii) Using VOC compliant solvents effectively
iii) New VOC solvents to replace glycol ethers and film forming coalescents
iv) Decreasing toxicity in formulation by using a new generation of VOC compliant replacements
Radiation-Curable Non-Isocyanate Polyurethane Green Coatings: Synthesis, Characterization and properties
Forough Zareanshahraki, Eastern Michigan University
Radiation curable coatings have become one of the fast developing eco-friendly coating systems, thanks to their low VOC and HAPs emission and exceptional rapid curing. Since its inception, the UV-curing technology has mainly been used for flat surfaces, controlled in-factory application, and curing systems. But recent innovations in UV curing equipment have made it possible to use these systems in with on-site coating applications. Therefore, this study proposes to use this crosslinking chemistry as a novel approach for designing green polyurethane coatings for military applications such as radomes, antennas, gun shields, wing leading edges and helicopter blades coatings.
Synthesis of novel UV-curable Non-Isocyanate (UV-NIIPU) Oligomers was carried out in three steps: First, Multi-functional cyclic carbonates (MFCC) were prepared by Carbonation of aliphatic epoxy compounds under mild temperature and pressure conditions in the presence of a catalyst. Epoxy content tracking and FTIR spectroscopy showed more than 95 percent of epoxy conversion into cyclic carbonate. Then, Amine functional NIPUs (NIPU-PA) were synthesized through reaction of MFCCs with excess amount of aliphatic amines. Reaction progress was monitored by amine value titration according to ASTM D2074 and FTIR spectroscopy by following the cyclic carbonate peak (~1800 cm-1). Finally, to develop a UV-curable system, (meth) acrylate functionality was introduced by reacting amine groups at chain ends with Glycidyl methacrylate (GMA) in acetonitrile, in the presence of an inhibitor to avoid free-radical induced gelation. Epoxy content monitoring, using a revised epoxy titration method and FTIR spectroscopy showed about 90 percent yield.
UV-curable NIPU coatings were formulated by using UV-NIPU oligomer, a conventional photo initiator and reactive diluents and evaluated for military critical performance properties such as low temperature flexibility, resistance to aromatic fuels and lubricating and hydraulic fluids, etc.
The study shows that high performance UV-curable NIPU coatings for military applications can successfully be developed by proper design of UV-NIPU oligomers and selection of appropriate reactive diluents.
Low Temperatures Curing Powder Coatings System for New Applications
Cal EzeAgu, Allnex
allnex has developed a series of high reactive powder coatings polyester systems offering innovative solutions to low temperatures cure for new applications and reduced bake cycles. The binders based on these technologies can be cured at peak metal temperatures as low as 130oC for 10 minutes. This reduction in cure temperatures is bringing new innovative approach to novel applications and optimized process efficiency while keeping high performance. The objective of this paper is to present allnex’s findings that demonstrate this achievement
Novel Two-Component Non-Isocyanate Polyurethanes for Sustainable Coatings
Hamidreza Asemani, Eastern Michigan University
The coating systems used on aircraft and transportation surfaces have stringent performance requirements such as rain erosion resistance, low temperature flexibility, good barrier and exterior durability properties and resistance to aromatic and hydraulic fluids. The solvent-borne two-component polyurethane (PU) coatings are currently the undisputed systems of choice to meet the on-site application/curing and performance requirements. However, current polyurethane chemistry contains isocyanate compounds, which are hazardous and may be prohibited for use in the near future. Considering the serious challenges like high usage of volatile organic compounds (VOCs) or hazardous air pollutants (HAPs) and curing limitations, this study has focused on design and development of environmentally benign two component high solid Non-Isocyanate Polyurethane (2K-HS-NIPU) systems through a novel route based on cyclic carbonate/amine chemistry.
Multi-functional cyclic carbonates (MFCC) were prepared as primary building blocks by carbonation of aliphatic epoxy compounds under mild temperature and pressure conditions, in the presence of a catalyst. Degree of carbonation of >95% was confirmed by FTIR spectroscopy by following epoxy peaks. Amine functional NIPUs (NIPU-PA) were synthesized by reaction of aliphatic and cycloaliphatic amines and MFCCs. Two-component coating compositions were prepared by using stoichiometric proportions of NIPU-PAs and aliphatic epoxy compounds as crosslinkers and their film properties were studied. The results revealed that by proper design of NIPU oligomers -their functional group content , backbone structure and molecular weight- high solid 2K-coatings with acceptable performance such as low temperature flexibility and resistance to chemicals and solvents could be obtained.
Elimination of isocyanates, substantially reduced VOCs and HAPs as well as fast ambient curing, make these polyurethane coatings a promising alternative for various industrial applications. Further study on formulation and structural performance of such coatings is in progress.
Novel Fluorocarbon Resin ZenduraTM C100 Introduction and Application
Jeffrey Han, Honeywell
Zendura C100 is a novel fluorocarbon resin developed by Performance material & technology of Honeywell. After 4 years of outstanding research and development, Zendura C100 has been commercialized and are applied as heavy-duty anti-corrosion and protective coating successfully. Zeudura C100 are the only fluoropolymer with novel molecular structure in the past 40 years, which is a copolymer of Honeywell’s fluoromonomer and vinyl ether/ester monomers. Since the unique molecular structure of fluoromonomer, C100 show differentiated features from current FEVE resin including higher solid content but lower viscosity, meanwhile, excellent weatherability and durability are provided by Zendura as traditional fluorocarbon resin. Besides, Zendura c100 also show good solubility and compatibility with pigment/fillers which provide flexibility on paint formulation development. In summary, Zendura C100 provide possibility to develop paint with lower VOC content, which are applicable as protective coating of bridge and architectures.
Thermal Barrier Coatings on Paper Substrate
Mohammed Mustafees Khan, University of Mississippi
Thermal resistive coatings are applied some material surfaces that are subjected to external heat sources. These coatings aim to increase the operating temperatures of the original material without affecting the base properties. Thermal barrier coatings are employed in Aerospace industry, steel structures, kitchen laminates, railways and electronics amongst others. The current study focuses on the application of these coatings onto paper substrates with possible application in the packaging industry. The thermal behaviour of paper substrates is studied under transient application of heat loads for varying time periods and humidity. Hydrophobicity of the paper substrates has also been studied.
An in-house apparatus was developed to conduct thermal barrier experiments. Whatman filter paper with grade-1 specification was used as the substrate, and the coating formulation was maintained at 55:45 solids to water ratio. It consisted of pigment (CaCO3), binder (Acronal® S728 na) and dispersant (Dispex® N40 V) suspended in an aqueous medium. Four different additives have been identified, namely Cellulose nanocrystals (CNCs), Silica Aerogel, Nano-TiO2 and Nano clay because of their thermal resistive properties and biodegradability. Initial thermal barrier studies indicated that 2% addition of Silica-based aerogels provided the highest thermal barrier once conditions reached equilibrium, with an average temperature gradient (before and after the sample) of 55.3oF. This is a 14oF improvement over coated paper samples without additives and 7oF improvement over 2% CNC addition to the coating formulation. Hydrophobic measurements were also conducted on prepared samples, and a 4% Aerogel addition provided a contact angle of 138.5o, clearly indicating good hydrophobicity. Thermal Gravimetric Analysis (TGA) was conducted to determine the material degradation at very high temperatures, while SEM and Keyence VH-Z250R microscope studies are being conducted to determine topology, morphology, particle shape and surface smoothness of the coatings.
Future work will focus on using Nano-TiO2 and Nano clay as additives in the coating formulation, development of CNC aerogels, measurement of thermal barrier performance at different humidities and calculation of thermal conductivity of coated paper.
High-Performance Polyamide Powders for Coating Applications
Biao Liu, Wanhua Chemical
Although thermoplastic polyamides exhibit excellent mechanical properties when used in powder coatings, they still have evident problems in the grinding and powder spray coating process. In this work, a series of polyamide-epoxy compounds were developed by melt blending of structure-designed carboxyl terminated polyamides and epoxy components. The prepolymer compounds were expected to convert to tough and high-molecular-weight polymer coatings after the baking process. Different polymer structures and component ratios were investigated in detail to determine the best combination and condition to produce high performance coatings. The results demonstrated that the compounds can be easily ground into fine powders at room temperature and have good melt flowability at the baking temperatures. The ultimate coatings exhibited smooth surface, excellent abrasion resistance and impact strength, as well as good adhesion to metals. These materials will have competitive advantages in producing tough and high performance coatings at low cost via classical powder spray coating process.
The Stabilization of UV-Curable & Waterborne Formulations with Novel HALS
Mervin Wood, BASF Corporation
The light stabilization of coatings has been a challenge for many years in the paint industry. More than four decades ago, it was discovered that Hindered Amine Light Stabilizers (HALS) play an important role in the light stabilization of polymers and resin binders. Typically, these compounds are derivatives of 2, 2’, 6, 6’-tetramethylpiperidine and when exposed to peroxy radicals are oxidized to produce stable nitroxides. This reaction, in addition to the scavenging of alkyl radicals by the nitroxides, forms a cycle describing HALS as a class of excellent polymer and resin binder stabilizers. Novel hindered amine light stabilizers, which can be utilized in UV-curable and waterborne coatings that provide excellent protection from the deleterious effects of UV light, will be discussed.
Cleaning, Fractionating, and Solvating Lignin for Materials Applications
Graham Tindall, Clemson University
Thies and co-workers [1,2] have discovered that when raw lignins are combined with hot acetic acid–water (AA/H2O) mixtures, two liquid phases are formed: a solvent phase into which are extracted the metal salts and other impurities and an ultrapure, solvated lignin phase that is the desired product. Purities of less than 20 ppm Na and <100 ppm total metals can be achieved in this liquefied lignin phase, as the metal salts readily diffuse out of the solvated lignin and into the solvent. Furthermore, the AA/H2O solvent composition can be “tuned” to partition the raw lignin feed between the solvent and lignin phases according to molecular weight (MW). Finally, because the ultrapure lignin phase is solvated, it has the potential to be directly processed into useful products. No other lignin-treatment method reported in the literature exhibit the ability to simultaneously clean, fractionate, and solvate lignins without washing. We call the process ALPHA, which stands for Aqueous Lignin Purification using Hot Acids. A low-ash, raw Kraft lignin has been purified via ALPHA, dry-spun from the solvated form into lignin fibers, and then processed into the desired final carbon fibers. As a reference and first step, the raw lignin was solvated by ALPHA but was not fractionated or cleaned before conversion into carbon fibers. In succeeding experiments, 50/50, 65/35, and 67/33 AA/H2O solvent mixtures were used to clean, solvate, and fractionate the raw lignin so that a highest 50% MW cut, a highest 25% MW cut, and a highest 10% MW cut were isolated. Conversion of these cuts into carbon fibers showed consistent improvements in fiber properties with increasing number average molecular weight of the lignin.
Klett, A. S.; Payne, A. M.; Thies, M. C. Continuous-Flow Process for the Purification and Fractionation of Alkali and Organosolv Lignins. ACS Sustainable Chem. Eng., 2016, 4, 6689-6694.
Klett, A. S.; Chappell, P. V.; Thies, M. C. Recovering ultraclean lignins of controlled molecular weight from Kraft black-liquor lignins. Chem. Comm. 2015, 51, 12855-12858.
Synthesis and Application of Cationic PUD with High-Temperature Resistance
Junying Deng, Wanhua Chemical Group
Cationic polyurethane dispersion (PUD), which carries positive charges, has particular applications in spinning, glass fiber, metal pretreatment, etc. For current preparation technology, N-alkyl diethanolamines are widely used as hydrophilic chain extenders to provide hydrophilicity to the hydrophobic PU chain. However, the hydrophilic functional group, quaternized tertiary amine, is located in the main chain of the polymer, which limits its hydrophilicity. So, a massive dose of chain extender with tertiary amine should be used to well disperse the system, which further leads to softness, clamminess and yellowing of the film. In addition, tertiary amine can catalyze the reaction between –NCO and –OH, which leads to great difficulty in reaction control. In this work, polyamines containing tertiary amine in the side chain were used as hydrophilic chain extenders. Through proper selection of amines, process regulating, screening of soft or hard monomers and additives, a series of cationic PUD with solid content 38%~45% and pH 4~6 were prepared. By using polyamines instead of N-alkyl diethanolamines as chain extenders, stable emulsions could be prepared with better reaction control and lower extender dosages. The high-temperature-yellowing test was performed at 240 ˚C, lasted for 20 min. Compared with cationic PUDs using N-alkyl diethanolamines as extenders, our cationic PUD with much fewer extenders had better performance in high-temperature-yellowing resistance. Our cationic PUD also had excellent storage stability, which showed no significant changes about viscosity after storage at 50 ˚C for 20 days.
Crosslink Density: A Model to Predict Performance of Automotive Clear Coats
Raviteja Kommineni, Eastern Michigan University
Automotive interior coatings for flexible and rigid substrate represent an important segment within automotive coating space. These coatings are used to protect plastic substrates from mechanical and chemical damage, besides providing color and aesthetics. Coatings undergo a lot of mechanical and chemical abuse from surrounding environment during their long service life. These coatings are expected to resist aggressive chemicals, fluids, and stains while maintaining their long-term physical appearance and mechanical integrity. Designing such coatings poses significant challenges to formulators in effectively balancing these properties.
Among many factors affecting these properties, the cross-link density (XLD) of these coatings is the most predominant factor. In general, the higher the XLD, meaning more the number of cross-links between the polymeric chain per unit volume, the lower will be its permeability to the diffusion of solvents and chemicals at a given film thickness. XLD also affects various mechanical properties like flexibility, hardness, toughness etc., and hence coatings with optimum XLD are desirable. Coating formulators often use time-consuming trial and error studies to determine formulation with optimum XLD. We have formulated a range of 2K-polyurethane automotive clear coats with varying XLDs, applied onto the widely used automotive plastic substrate at varying dry-film thickness (DFT). The XLD of these coatings has been determined by using Equilibrium Swelling technique using various solvents. These coatings have been tested for chemical, physical and mechanical properties as per standard test protocols. Analysis of the results has provided useful insight into the effect of XLD on various coating properties. Using these results we have developed a model to predict the effect of XLD on various coating properties as a function of their DFTs. This model is very useful for both formulators (Optimization of XLD) as well as the coating applicators (optimization of DFT). Besides, the scope of this model can be extended to estimate the solubility parameter of the different solvents and fluids. Application of this model in solving a real-world industry problem has been successfully demonstrated.
Initiator Influence on the Encapsulation and Leaching of Ag Nanoparticles
Gabrielle Boivin, Université Laval
Translucent coatings on wood in exterior applications often fail due to photodegradation and colonization by black-stain fungi and require frequent refinishing. This limits competitiveness with alternative materials. In previous work, functionalized silver nanoparticles were incorporated in acrylic polymer particles by miniemulsion polymerization in order to synthesize black-stain resistant latexes. It was found that latexes containing silver nanoparticles show antifungal activity against Aureobasidium pullulans, Sclerophoma pityophila and Epicoccum nigrum at low silver concentration (0.1% m/m) (Boivin, Ritcey, Morris, Landry, 2017). One of the main concerns of the use of nanocomposite materials is the leaching of nanoparticles and their long-term effect on humans and the environment. The present work summarizes the influence of a hydrophobic initiator (benzoyl peroxide) versus a hydrophilic initiator (potassium persulfate) on the encapsulation and leaching of the silver nanoparticles in miniemulsion polymerization. The cryo-TEM analyses show that the positioning of the silver nanoparticles in the polymer particles is influenced by the nature of the initiator. Moreover, leaching tests were performed and the influence of the silver nanoparticles size on leaching was also evaluated.
Study on H12MDA Modified by Propylene Oxide
Eric Liu, Wanhua Chemical Group
4,4′-Diaminodicyclohexyl methane(H12MDA) is cycloaliphatic amine obtained by hydrogenation of 4,4-Diaminodiphenyl methane（MDA）. Epoxy resin cured by H12MDA has excellent weather resistance, dielectric properties and mechanical properties, so it is widely used in flooring coating, electronic packaging, adhesives and other fields. As the H12MDA usually crystallizes at low temperature, so it should be modified before using in the winter. The traditional modifier is the long chain monofunctional glycidyl ether, such as butyl glycidyl ether(501), phenyl glycidyl ether (690), glycidyl 2-methylphenyl ether (691) and benzyl glycidylether(692). However, the high molecular weight of the modifier result in the problems of high viscosity and low reactivity of the modified H12MDA, low hardness and glass transition temperature of the cured resin. In this paper, we choose low molecular weight Propylene oxide （PO）as the modifier, and the results showed that PO modified H12MDA has lower viscosity and higher reactivity, and its cured resin has higher hardness and glass transition temperature. It is confirmed that PO modification is a promising way for cycloaliphatic amine.
Waterborne Alkyd Resin — An Approach to Address a Chronic Technical Challenge
Nihal Pandrapragada, Eastern Michigan University
Water-borne Alkyd Resin: An approach for addressing a chronic technical challenge
Paint and coating industry has transitioned from solvent-based coatings to water-based, in response to the environmental concerns and regulatory pressure. While alkyd resin based paints are among very high-volume products, there has been much less progress in their transition to water borne coatings. This is primarily due to a technical challenge – alkyd resins being essentially polyesters, are not hydrolytically stable.
In order to address this challenge, acrylic grafting has been found to be a promising approach and many products based on this approach are commercially available. However, in this approach involving addition of acrylic monomers onto the alkyd, substantial fraction of acrylic copolymer that is not bonded to alkyd, is formed. This results into poor storage stability and often poor gloss and appearance of their films. Furthermore, the carboxylic acid functionalization may serve as catalyst for hydrolysis, severely affecting hydrolytic stability of such system.
We have used an innovative approach for preparation of alkyd emulsion that does not use carboxylic acid functionalization for water dispersibility. In this approach a mixture of alkyd resin, monomers and initiator is first emulsified in water using external emulsifier. This emulsion is then heated at appropriate temperature to initiate radical polymerization within the droplets. We hypothesize that due to the proximity of alkyd resin to the monomers, grafting efficiency would be higher, resulting into more stable emulsion with good film properties. The absence of carboxylic functionality is expected to improve hydrolytic stability. Emulsions will be characterized for particle size, hydrolytic stability and grafting efficiency. Film properties of both fresh and incubated samples will be studied and compared with conventional solvent based alkyd, as a control.
Self-Dispersing and Stimuli-Responsive Polyurethane Dispersions
Harshit Gupta, Eastern Michigan University
Free-energy driven dispersion formation is of intense interest, because microscopic to nanoscopic phase separation from macroscopic phases of chemical components involves an intriguing balance of chemical forces that results in apparent thermodynamic stability. We report a single-pot approach to synthesizing polyurethanes (PUs) in solvent, wherein aqueous compatibility is induced by using imidazolium hydroxide salts (ionic liquids) as chain terminating groups. Effects of various diisocyanates, diols, crosslinking agents, and chain terminators on the creation of PUDs (polyurethane dispersions) are described with respect to impact on spontaneous self-dispersing when such PUs are dried (of solvent) and placed in water. The size evolution of such (self) dispersion is examined by videography and by dynamic light scattering, and size reduction from more strenuous activation by sonication is studied. Effects of indifferent salt on aqueous stability are measured, and anion-dependent stimuli-responsiveness is characterized. This stimuli-responsiveness appears based on tuning imidazolium-anion pair solubility by anion exchange. Film formation is also examined. Water-sensitive films with weak mechanical properties, but promising for hydrogel delivery applications, as well as mechanically robust and water-resistant films for protective coatings are formulated, depending on diisocyanate and diol selections.
Synthesis of Bio-Acrylics Monomers & Polymers from Renewable Resources
Parijat Ray, Monash University
Dihydro-5-hydroxyl furan-2-one (2H-HBO), a renewable-sourced chemical containing the hydroxyl functionality is converted into its acrylic counterpart for the first time through a green chemical procedure. This newly-synthesized acrylic monomer is able to be polymerized using different techniques such as bulk, solution and emulsion polymerization. To check the capability of this monomer to polymerize with different other commercially-available acrylates, copolymerizations are studied based on emulsion techniques. The pendent lactone ring remains unopened during the polymerization and makes the polymer highly polar to be polymerized in a polar solvent like dimethyl sulfoxide (DMSO). This monomer is suitable to copolymerize with other commercially available acrylic monomers such as methyl methacrylate (MMA), hydroxyethyl methacrylate (HEMA), styrene, etc. RAFT emulsion polymerization is also studied with the same monomer in a simple way which gives a steady conversion (~60%) with a low dispersity of 1.06. The homopolymer produced from emulsion polymerization shows higher molecular weight from all the methods, with a glass transition temperature of around 108°C which is showing the potentiality of this monomer as an interesting, green replacement for methyl methacrylate in certain field of applications. Along with this study, few other bio-based acrylates will be introduced and discussed.
Application of 3 types of hydroxyl acrylic monomers in waterborne 2K acrylic coatings
Rick Lu, Wanhua Chemical Group
This paper studies the application of 4-HBA in waterborne hydroxyl acrylic emulsion, by using different hydroxyl acrylate monomer, HEA, HEMA, 4-HBA respectively to synthesize waterborne hydroxyl acrylic polyol, and aqueous polyisocyanate curing agent matching test, found that compared to the traditional HEA, HEMA hydroxy monomers. 4-HBA synthesis of waterborne hydroxyl acrylic polyol, cross-linking can be obtained faster, more excellent flexibility, to enhance the film chemical resistance and weather resistance are of great help.
Organic-Inorganic Hybrid Coating System Using UV-Initiated Click Chemistry
Himanshu Manchanda, Eastern Michigan University
The coatings industry is teeming with new inventions each year, with minimal exposure to hazardous chemicals and waste as one of its goals. The idea of reducing the harmful emissions from paints while improving upon their existing performance, has led to the exploitation of plenty of new chemistries and chemicals in the recent past. One such promising area lies in the development of an Organic-Inorganic hybrid (OIH) coating system by leveraging the dual-cure chemistry involving Michael-Addition (MA) of acetoacetate and acrylate moieties as well as UV-initiated moisture curing of silane functional groups.
The focus of this research is to exploit the MA reaction for applications such as replacement of harmful acrylic monomers with acetoacetate-based resins synthesised in our labs as well as a prospective coating system for additive manufacturing. A photo base generator (PBG) has been used that generates, in-situ, a super base that is capable of instantly kicking off MA reaction resulting in rapid curing. The super base is also expected to catalyse moisture-curing reaction of the silane functional groups also present in the system. Coatings have been formulated using uniquely designed acrylic oligomers (MA-acceptor), acetoacetate functional reactive diluents (MA-donors) and organo-silanes (sol-gel precursors), besides super PBG. The study highlights many technical and environmental benefits of these OIH coatings with great potential for commercial exploitation. An overall assessment of the film properties obtained using the acrylate-based reactive diluents and the acetoacetate-based reactive diluents has been made. The research also involves an in-depth analysis of the UV-initiated process mechanisms and the structure property relationships for the various results obtained.
Additionally, an effort is being made to further extend this concept in the field of additive manufacturing as a plausible replacement for the currently used adhesives. The idea is to leverage upon the existing limitations of slower production rates and weaker mechanical properties of 3-D printed materials in comparison to their counterparts developed using the conventional injection moulding techniques. While the concept is still in the preliminary stages, suitable additions to the existing chemistry can prove to be a game changer in the additive manufacturing industry.
Waterproofing Low-Slope Roofing Using a Unique Elastomeric System
John Dockery, Trinseo
Waterborne elastomeric coatings are used extensively in cool white roofing systems, but several deficiencies remain. A number of coating manufacturers have seen market share shift to other technologies due to those deficiencies. Performance challenges have been water ponding, asphalt bleed through and adhesion to low energy substrates. Trinseo has developed an alternative cost-effective elastomeric system to address these paucities without the use and added cost of functional additives when compared to existing acrylic products on the market.
Color and Light: Advancements in Curing Colored and Special-Effect Pigments
Sidney Hutter, Sidney Hutter Glass & Light
My proposed American Coatings Conference presentation will cover the research and use of colored and special effect pigment technology with UV adhesives and suspension agents and other additives in my glass sculptures. In previous presentations to groups including RadTech NA, The Glass Art Society, and other scientific, cultural institutions, I submitted research based on my use of UV adhesives, dyes, effect pigments, stabilizers and photo initiators as they applied to my studio practices.
I will discuss the above topics as they relate to recent advances in colored and special effect pigment technology to solve fading, stabilization and other UV curing issues. In addition I will detail the use of dispersing and suspension agents used to create my unique UV adhesive recipes, as well as, using the latest LED photo curing initiators
Overall, my presentation will be a discussion of how I have adapted the use of technology (adhesives, dyes, pigments and additives) to my studio practice of creating original fine art pieces and commercially available lighting products. My presentation will be verbally engaging and visually stimulating featuring images of my production processes, examples of my research successes and failures, as well as examples of my completed artwork.
My website (www.sidneyhutter.com) features numerous images of my artwork utilizing pigments and colorants. In addition, a recent UVEB Tech magazine article (with cover image) about my process using colored and effect pigments is available for viewing. If you need more elaboration on the presentation feel free to contact me . Thank you! I look forward to the opportunity to share my research with the community.
Effective Low-VOC Epoxy Solution in Practice — A Case Study from Hypothesis to Practice to Field Study
Christian Piechocki, Olin Epoxy
Effective Low VOC Epoxy Solution in Practice – A Case Study from Hypothesis to Practice to Field Study
Within the chemical and petrochemical industries, solvent-borne Epoxy primers and mid coats act as the initial barrier against corrosion due to their ease of application and proven track record of excellent protection. Increasing demand to control emissions of volatile organic compounds (VOC), has led the industries to move to lower VOC solutions. While high solids, low VOC Epoxy solutions are the leading incumbent, they typically have undesired characteristics including high viscosity, poor sprayability, and reduced corrosion resistance, resulting in slower adoption of low VOC solutions by contractors and asset owners.
In this paper Olin Epoxy will share the key learnings of the successful progression of a novel low VOC, low viscosity Epoxy from performance hypothesis to field application. The specific trials were conducted in a region regulated by the Texas Commission on Environmental Quality, where limitations on allowable emissions from the coating process are enforced. VOC emissions are calculated daily thus limiting the quantity of paint that can be applied and thereby impacting maintenance scheduling, cost, and timing.
Author: Christian Piechocki
Note Not to be included in abstract but for your information: This paper was presented at ECS April 2017. We will augment this paper with 1 year performance data and information in relation to the relevance to Asset Owners operating in the region regulated by Texas Commission on Environmental Quality.
Evaluation of Thin-Film Drying Profiles Using Non-Invasive Optical Analysis
Matt Vanden Eynden, Formulaction
Development of stable emulsions is critical for formulation chemists who desire to have a stable, well-dispersed product that can also exhibit a desired shelf-life and avoid destabilization phenomena that will inhibit transfers between storage vessels. New materials and regulations are leading chemists to develop new formulas to meet these criteria. Visual analysis of these emulsions can be time-consuming and objective causing extensive project times and qualitative results, and other optical techniques involve disturbing or diluting the samples.
We present here a technique based on Multiple Light Scattering (MLS) to fulfill this purpose. Destabilization phenomena such as sedimentation, creaming, clarification and flocculation can be identified and quantified much fast than standard visual analysis. Such data can accelerate project timelines and provide critical data in order to optimize a formulation. It has proven to be a useful technique to characterize the dispersion state of colloidal samples and the mean diameter of particles in concentrated dispersions. Where other optical techniques ask a very high dilution and risk to denature the sample, this technique has the advantage to analyze in one click, without sample preparation or dilution, concentrated suspensions
Application of the Vinyltrimethoxy Silane as Moisture Scavenger for the High Reactive 2K Polyurethane Coatings
Ahmed Eessa, El-Mohandes
The 2k polyurethane coating can be formed by a simple addition reaction between hydroxyl group containing materials and isocyanate group containing materials. The high reactivity of the aromatic diisocyanate results in absorption of moisture at room temperature and liberation of carbon dioxide bubbles which in turn led to undesired defects of the applied coatings. In this work we investigated the use of vinyltrimethoxy silane (VTMS) as moisture scavenger in the polyurethane coatings and studied its chemical reactivity towards water and diisocyanate. The kinetic characterization of the polyurethane formation in the presence and absence of the VTMS were successfully described by different techniques (FTIR-ATR measurements of diisocyanate transmittance at wavenumber 2272 cm-1). The activation energies were 19.04 and 17.38 kJ/mol in the presence and absence of the VTMS, respectively, so, using the VTMS led to fast and safe reaction even under high temperature and high relative humidity conditions. The final results concluded that the VTMS is capable of undergoing chain reactions with both humidity and diisocyanate and participate in the final polyurethane network which improved the final coating properties like gloss and hardness.
Low Surfactant Waterborne Acrylics for Concrete Applications
Terri Carson, Alberdingk Boley
Concrete is a versatile substrate used in many applications ranging from residential environments to commercial infrastructures. As with most substrates, it has higher durability when coated since exposure to water, chemicals, abrasion and UV can lead to faster degradation. In the floor coatings market, two-component epoxies and polyurethanes are commonly used due to their high durability and abrasion resistance. However, there have been increasing new developments of high performing water-based acrylics designed to meet performance criteria as well. A new family of acrylics will be presented that are suitable for concrete applications. These acrylics are characterized by very low surfactant levels and multi-phase morphology providing formulation latitude to meet low VOC regulations with high end performance. The performance of these products has been evaluated as one component systems, but the option to cure with crosslinkers has also been investigated to determine any potential benefits. Comparisons have been made with other commercial water based products available on the market. The results have shown the new polymers have excellent durability, very good chemical and water resistance and adhesion. The formulations also have the advantage of long pot life, exterior durability and environmentally friendly compared to traditional resin technologies. Further work has also proven these products have excellent performance on other substrates such as wood. Robust products have been developed for multiple substrates offering multi-purpose performance equivalents compared to traditional products.
Alkoxysilane Sol-Gel Consolidants for Calcareous Stone
Alison Rohly, North Dakota State University
Novel Synthesis of Acetoacetate Resin Derived from Kraft Lignin
Eric Krall, North Dakota State University
Poly (Urea-Formaldehyde) Microcapsules Containing Epoxy Ester for Self-Healing Coatings
Cheng Zhang, The University of Akron
Assessment of the Viability of Coating Open-Time Determination through Rheological Methods
Arlen Prosser, California Polytechnic State University
Latex, Associative Thickener, and Surfactant Interactions and their Effects on Coating Film Properties
David Chisholm, California Polytechnic State University
Enhanced Detection of Coating Aging Mechanisms Using Quantum Dots
William Thompson, California Polytechnic State University
Real-time Film Formation Investigation of Polymeric Coatings
R.F. Bouscher, The University of Akron
Synthesis and Characterization of Non-Isocyanate Urethane-Acrylic Hybrid Latexes
Anise Cobaj, The University of Akron
Encapsulation of Alkyd Toward Self-Healing Corrosion Resistant Coatings
Brittany Pellegrene, The University of Akron
Self-healing coatings have been proposed as a method to slow the corrosion process and delay recoating needs. A self-healing coating can mend microcracks and other surface defects. Some of these systems require exposure to external stimuli to initiate the curing process and others can autonomously cure after a damage event. The problem with many of the current self-healing coating systems is the presence of excess monomer that can be volatilized during the drying process. Additionally, many of these systems utilize poly(urea-formaldehyde) in the nano/microcapsule shell, which could release formaldehyde from the coating upon cracking of the capsule.
To improve upon the current systems, encapsulation of alkyd resin in a silica microcapsule is shown here. The encapsulation of alkyd using a shell material that does not contain formaldehyde is an important step toward commercial use of these capsules. Future research will involve the incorporation of these capsules into a coating system and evaluation of their self-healing ability.
The Effect of Unsaturation in Plant Oil-Based Monomers on Properties of High Bio-based Content Latexes Synthesized in Mini-emulsion Polymerization
Zoriana Demchuk, North Dakota State University
The Effect of Unsaturation in Plant Oil-Based Monomers on Properties of High Bio-based Content Latexes Synthesized in Mini-emulsion Polymerization
ABSTRACT: Recently, a range of acrylic latexes from plant oil-based acrylic monomers (POM’s) and styrene was successfully synthesized using miniemulsion copolymerization which gives a prospect to polymerize highly hydrophobic monomers.
The number-average molecular weight and glass transition temperature of latex copolymers depend on biobased content in the monomer feed and the unsaturation amount of POM’s (the amount of double bonds in fatty acid fragments). Using 1H NMR spectroscopy it was confirmed that double bonds of fatty acid fragments persist mostly unaffected during the polymerization and can be further used for post-polymerization reactions (e.g. crosslinking). The latex free films were cured at elevated temperature and further characterized using DSC, DMA, tensile and pendulum hardness testing.
It was determined that the amount of unsaturation in POM’s has impact on mechanical properties of the resulting latex films. By establishing the linear dependence of the crosslink density on monomer feed unsaturation, the latex network formation and thermomechanical properties can be adjusted by simply mixing various plant oil-based monomers at certain ratios in the monomer feed. The POM’s fragments in latex copolymer act as an internal plasticizer, enhance the toughness of latex films and convert brittle polymers into flexible film-forming materials which can be potentially used for coatings and adhesive applications.
Emulsion Copolymerization of Plant Oil-based Monomers for Latex Coating
Kyle Kingsley, North Dakota State University
Novel Organic-Inorganic Sol-gel Coatings: A promising replacement for Chromate Pretreatment
Swapnil Shukla, Eastern Michigan University
In a protective coating system, pre-treatments which are directly applied on the metal substrate prior to primer play a key role in protection of the substrate in corrosive environment as well as providing adhesion to the subsequently applied layers. Hexavalent chromium based conversion coatings have long been considered as the undisputable pre-treatment due to its excellent anti-corrosion properties. However, extensive efforts have been in progress in recent years to establish suitable replacements for conventional chromate based pretreatments, mainly driven by their serious health risk to users, negative environmental impacts and strong regulations against its usage. Among various options, Organic-Inorganic Hybrid (OIH) pretreatments based on sol-gel chemistry offer environmental advantages as well as strong interactions with both the substrate and the topcoat which can lead to desirable corrosion protection and inter-layer adhesion.
In this study, series of novel OIH precursors based on the reaction of aliphatic and aromatic epoxies with aminosilanes and thiosilanes have been synthesized and applied on aluminum 2024 substrates via dipping method. Applied coatings were cured in oven at elevated temperatures to complete the crosslinking and form a uniform film. The chemical structure of sol-gel precursors and the deposited OIH films were characterized by FTIR analysis and the corrosion resistance performance was assessed by quantitative techniques such as Electrochemical Impedance Spectroscopy (EIS), D.C. Polarization along with Accelerated Salt Spray Corrosion Test (ASTM B117). A modified technique of Oxirane Oxygen Content measurement derived from ASTM 1652 standard was also used to quantify the exact conversion of precursor reactants.
Synthesis of Cardanol-Based Polyols via Thiol-ene/epoxy Click Reactions for Polyurethane Coatings Application
Haoran Wang, The University of Akron
Considering the increasing of petroleum oil prices and the environmental problems caused by petroleum industry, developing bio-based polymers from renewable resources has received great attention both in academia and industry. Cardanol is extracted from cashew nut shell, a byproduct of cashew food industry. It is a cost-effective renewable resource. The unsaturated alkyl phenolic structure makes cardanol be a unique and valuable building block for polymer materials
In this study, three bio-based polyols with different functionality are synthesized from cardanol. 1H NMR, 13C NMR, are used to characterize and identify the synthesized polyols. Then, the polyols are formulated with hexamethylene diisocyanate trimer to prepare polyurethane coatings. Finally, the thermal stability, mechanical properties, and UV durability of the polyurethane coatings are studied.
Flexible Smart Anticorrosive Coating with Applications in Aerospace
Masoud Sobani, The University of Akron
Extreme enhancement of thermally activated curing
Robert Fortebaugh, Penn State University
The Effect of Surface Modifying Additives in Fouling-Release Siloxane-Polyurethane Coatings
Jackson Benda, Dakota State University
Marine biofouling is considered the undesirable accumulation of marine organisms ranging from microorganisms, algae, and larger animals such as barnacles and mussels on structures submerged in seawater. Over 4000 species of marine foulants are involved and cause problems with marine vessels such as increased fuel consumption and carbon emissions, decreased speed, and the spread of non-native species. Traditionally, anti-fouling (AF) paints that contain inorganic/organic biocides are used to prevent the settlement and attachment of foulants on ship’s hulls, but some paints, especially containing tri-organotin, are highly toxic and poison marine environments. Thus, fouling-release (FR) coatings have been developed, which are relatively non-toxic and rely on low surface energy components to allow weak adhesion of marine foulants which can be cleaned off easily. Prior research at NDSU has resulted in a self-stratifying, hydrophobic, siloxane-polyurethane (SiPU) coating formulation which showed comparable FR properties to commercial standards. To improve upon the FR properties of this SiPU system, the use of surface modifying additive amphiphiles is being explored. A series of amphiphiles were synthesized by hydrosilylation between polyhydromethylsiloxanes and allyl polyethylene glycol monomethyl ethers under Karstedt’s catalyst. These co-polymers formed comb-like structures and were analyzed using proton Nuclear Magnetic Resonance Spectroscopy and Fourier Transform Infrared Spectroscopy to confirm their structure. The amphiphiles were incorporated into the standard SiPU formulation at different amounts. Surface analysis techniques were used to observe the change in surface properties before and after water immersion. Laboratory biological assays using C. lytica and N. incerta (marine bacterium and diatoms) were carried out to assess the AF/FR properties.