Conference Program

One of the multifunctional surfactants used for the physical and chemical characteristics improvement of polymer films, papers, and cosmetics is surfactant cation copolymer containing hydroxyethylcellulose and dimethydiallyl-amonium chloride (Polyquaternium-4; PQ4). However, the concentration of the salts on the film is very low and it has become a challenge for scientists to develop a practical and rapid method for the determination of the coating. In this study, the Pyrolysis-GC/MS is used for such analysis. The method requires very little sample preparation. The multi-mode micro-furnace pyrolyzer with different modes of operations including evolve gas analysis (EGA), flash pyrolysis, thermal desorption, heart cutting allows users to choose among the techniques for their analysis purposes. The first step is to perform an EGA using temperature programs. Based on EGA thermogram, Heart cutting is then utilized for the trace determination of PQ4 surfactant on the film. The result obtained proves the reproducibility of the technique.

Non-Isocyanate Polyurethane (NIPU) coatings are increasingly important due to their low toxicity and sustainable attributes. While several alternative routes for the synthesis of NIPU have been established, their successful exploitation in advanced water-based, UV-cure, or high-solid coating technologies requires customization of their polymer structure, morphology, and crosslinking functionalities. Building on our previous work on NIPUs derived from cyclic carbonate/amine route, this presentation will discuss how NIPUs are selectively functionalized for UV-curable (-acrylate), moisture-curable (-silane), and ambient temperature curable (-acetoacetate – click-chemistry) coating systems. By optimizing chemical structures and functionalities of NIPU and incorporating dual-cure mechanisms, coatings with an outstanding balance of application and performance properties have been achieved. Such coatings have the potential to replace conventional PU coatings for many end-use industrial applications.  .

TiO2 pigments are known to have several effects on paint durability.  As a strong UV light absorber, TiO2 protects underlying resin from direct interactions with the UV component of sunlight.  However, TiO2 can convert some of the UV light energy into chemical energy in the form of radicals, which can then attack the binder.  In addition to the inherent photoactivity of the TiO2 pigment, which can be partially modified through a surface coating, the degree of TiO2 dispersion can also affect paint durability.  While it would be very useful to the formulator to understand the relative importance of these two effects on paint durability, they are typically quite difficult to identify/separate.  Here we present a technique to make this separation and show how this information can be used to optimize paint durability.

Bisphenol-A based materials are getting phased-out in various applications including in metal packaging coatings. Simultaneously, steel packaging manufacturer, can makers, and coating formulators are wrestling with simultaneous challenge coming from shifting regulatory pressures driving substrate replacement towards Chromium-free passivation alternative (CFPA) to comply with legislative moves in various territories. Eastman Chemical is actively participating in the development of next generation polyester Bisphenol-A non-intent (BPA-NI) resins technology that can deliver improved resistance to food sterilization, long-term shelf stability, with balanced flexibility and toughness critical to withstanding aggressive canning process while adapting to this new challenge associated with substrate development. Here, we employ accelerated pack test, electrochemical impedance spectroscopy (EIS), and fitness-for-use testing to understand and analyze suitability and performances of several BPA-NI solutions on conventional substrate and new CFPA substrate. This work will provide understanding of compatibility, benefits and limitations of various BPA-NI solutions.

Traditional material design methodologies focus on performance. While these methods can produce new materials with interesting functionalities, the serviceable life of these materials is usually an afterthought. Advances in applied artificial intelligence and machine learning methods are enabling a new class of material design methodologies. These approaches utilize genetic algorithms and evolutionary programming, along with principles of autonomous science, to automatically and efficiently design new materials that fulfill specified performance functions. However, these methods still focus on initial, optimal, or “time zero” performance, and do not incorporate knowledge of service life, outdoor exposure effects, or performance deterioration with time. This work proposes a new methodology, which incorporates service life prediction concepts into autonomous material design cycles. The objective is to create computer programs that can design new, functional polymeric coating materials that can also meet rigorous serviceable life requirements common to many industrial applications.

Developing new molecules capable of improving coating performance is technically challenging; doing so while also ensuring that they can be successfully globally registered can seem impossible. However, there are strategies that can enable companies to improve their innovation efforts by shortening product development time, lowering overall R&D costs, and improving the odds of commercial success.
This paper will describe how a “benign-by-design” approach was used in the development of new molecules unable to meet the US EPA definition of low-risk polymers. By using predictive models to estimate molecules’ physical/chemical and environmental fate behavior, EH&S criteria could be introduced at the beginning of the molecular design phase; therefore, potential issues were identified before performing any synthesis. Chemical structure-toxicity/biodegradability relationships were built around families of molecules with the best environmental profiles, and that information was combined with traditional structure-property relationships to arrive at new molecules that met both performance and regulatory targets.

Sophisticated algorithms enabled by big data analytics and machine learning (ML) have untapped potential to improve the accuracy of formulation optimization and performance prediction. A case study exploring broad formulations typical of the European market  was conducted using a novel matting resin that provides an engineered surface with controlled topology and functionality. An optimal design-of-experiments strategy combined with high-throughput methodology were utilized to evaluate about 1000 paint formulations, covering a design space of greater than 38000 combinations.  Modeling of paint properties was carried out by applying a range of methods to compare the accuracy of the models. Applied methodologies were Taylor Series Expansion involving main effect and higher order interaction terms, Partial Least Square, Bootstrap Forest, and Neural Network. Predictive models were further utilized to optimize performance and simulate preferred compositional spaces for a targeted balance of properties. Optimal formulations were validated using benchtop formulation and characterization.

Over 75% of coating formulations require multiple reformulations, accelerated laboratory and outdoor durability testing.  Rational Coating Formulation differs from conventional approaches in that it relies on the established material properties of coating ingredients-entropy and enthalpy- and assesses potential interactions/reactions among ingredients prior to formulation. The approach is similar to material and product reliability, practiced in aeronautic and electronics industries to develop and produce reliable and high-performance products. This paper will discuss and demonstrate methodologies used in Rational Formulation approaches. Intrinsic and extrinsic properties of raw materials in most common coating technologies will be demonstrated and the clear justification of materials choice will be presented. In addition, the effects of materials' attributes on coating performance, durability and overall cost are

For manufacturing environments, painting is the most expensive process in the plant.  The most expensive to build and operate, it accounts for more rework and scrap than any other department.
Programming a new part or color is tedious.  Simulation programs help, but checking the result requires painting, curing, then inspecting each part.  Each defect can require hours or even days to resolve…
SprayVision is an innovative approach to process analysis.  Voted “2020 Idea of the Year”, it allows painters to analyze the results of the painting process “in the wet” in minutes – eliminating the curing process.  This can cut hours, even days, from the setup process.  Moreover, it establishes baselines for atomizer performance and spray patterns which can be checked periodically to eliminate defects, increase FPY and reduce the overall cost of coating parts. 
This represents a “game changer” in the painting industry.

In recent studies comparing the outdoor weathering of poly(vinylidene fluoride) (PVDF)-based coatings against several accelerated weathering test cycles, including ASTM D7869-13, we found all the cycles accurately reproduced Florida rank order gloss and color retention trends for PVDF-based coatings made with single (non-TiO2) pigments. However, none of cycles accurately predicted the rank order of rutile TiO2 grades for Florida gloss retention, nor the magnitude and direction of color fade in organic pigment/inorganic pigment blends. This paper follows up on that study to address the question of whether the D7869 cycle, or other accelerated weathering cycles, might nevertheless have some utility for industry standard or specification purposes, across resin lines, especially if the test is limited to specific reference colors or more ideally to specific reference pigments. This approach with reference colors was recently adopted by the SSPC C.1.8 committee for the new SSPC Paint 47 fluoropolymer topcoat standard.

Michelman is developing a series of unique hybrid additives that enable exterior wood decking and fencing coatings to maintain their initial color, appearance, and structural properties even after prolonged environmental exposure.
 Through accelerated and exterior weathering exposure testing and real-life application testing, we have been able to verify that these experimental products provide superior water and abrasion resistance and may be compatible with a variety of resin systems. In addition, some of these materials exhibit improved dirt-pick-up resistance on Southern Yellow Pine wood species as measured by an internal Michelman test method.

Accelerated outdoor weathering with linear Fresnel-reflecting concentrators, which track the course of the sun throughout the day to maximize and concentrate solar radiation onto test specimens, is a well established and mature technology.  The use of concentrated solar radiation often results in degradation processes that are similar to those observed in natural end use applications.
When using traditional mirrors, the entire solar spectrum is concentrated onto the specimens.  This is not ideal for testing materials with poor thermal conductivity, such as plastics or composites, since they can easily overheat and thermally decompose.  A recent development in accelerated outdoor weathering is the use of newer “cool mirror” technology, instead of, or in combination with, traditional mirrors.  These new mirrors are designed to reflect UV and short-wave visible, but not infrared, radiation.  This results in lower specimen temperatures.  The new technology enables researchers  to test temperature-sensitive materials using solar concentrating exposures.

A long recognized need in the coatings industry is a rapid and accurate assessment of paint durability.  Testing under conditions identical to the end-use application would require excessive exposure times, since exterior paints are expected to last for many years if not decades.  Various techniques have been developed to shorten exposure times by increase exposure intensity, typically by increasing intensity or energy of UV light directed at the film.  However, these techniques can have serious shortcomings because they do not accelerate all degradation pathways proportionally, and in general the shorter the exposure time, the poorer the correlation with actual end-use performance.  We have found that early chalking results for panels exposed to ambient (Florida) conditions are excellent predictors of long term performance, allowing for an accurate assessment of chalk resistance to be made in a matter of months rather than years.  We will review this technique and results.

Coatings formulators can spend a great deal of time and resources screening various additives to remedy defects on cured surface coatings. However, in some cases, the processing parameters prior to spray application may be the cause of significant changes in surface defects for powder coating systems. We compared various preparation methods to changes in surface appearance and physical performance for FEVE resin-based powder systems over metallic substrates. This study will utilize accelerated corrosion testing that includes accelerated exposure testing (QUV and Prohesion) along with electrochemical impedance spectroscopy (EIS) to evaluate how a powder system’s preparation can influence the topcoat’s overall performance.

Ponding water coating damage is one of the least understood problems of the roofing industry. Two model acrylic coatings on TPO substrate were put under lab-controlled accelerated growth of algae in ponding water to learn about coating damage before and after subsequent wet-dry cycles. Three distinct damage features in sequence were observed: (1) the pit formation on the coating surfaces, (2) the algae biofilm mud-cracking induced surface damage, and (3) erosion of coating in the mud-cracked region over the wet-dry cycles. Adhesion of the algae biofilm with the coating surface and drying the biofilm were found to be the critical factors that govern the erosion on the coating surface and pit formation, respectively. The mechanisms of biofilm-induced erosion during the wet-dry cycling were postulated based on the mechanics and experimental observations. A new accelerated testing methodology for evaluating long-term roof coating performance is proposed.

Aqueous hybrid dispersions of poly(vinylidene fluoride) (PVDF) and acrylic resins offer a way to achieve highly weatherable topcoats while meeting stringent VOC requirements. This paper describes new studies of PVDF hybrid binders in 1-k and 2-k protective topcoat formulations, with stay-clean surface properties that are of interest for chemical storage tanks. The 2-k PVDF hybrid topcoats in particular, with standard urethane crosslinking, show chemical and abrasion resistance comparable to commercial 2-k acrylic-urethane coatings. In cyclic corrosion tests of full 2-coat and 3-coat systems, the performance with these waterborne topcoats is comparable to systems with commercial solvent-based topcoats. Moreover, 1-k and 2-k hybrid topcoats demonstrate excellent gloss and color retention in both Florida and accelerated weathering testing, and in line with the requirements of the new SSPC Paint 47 standard for fluoropolymer topcoats. Stay-clean properties depended on multiple factors: polymer Tg, crosslink density, surface energy and other surface properties.

Hexigone was created after a discovery at Swansea University, where the research team had been looking for a high performance corrosion inhibitor to replace the highly toxic, carcinogenic and mutagenic, hexavalent chromate.
The challenge was time dependant as European legislation was enforcing a ban on the use of hexavalent chromate across Europe.  The initial sunset date was in 2017, with this pushing back to January 2019.  
By utilising ‘Chemical Intelligence’, the team developed a highly effective smart additive that out-performed hexavalent chromate in laboratory testing.  With support from The RSC, InnovateUK, The Royal Society, The Royal Academy of Engineering and some very understanding investors, Hexigone has moved from a UK lab discovery to an export company.
The highs and lows of the journey, from the nano level discovery and electrochemical fundamentals of corrosion, through to a commercially produced product will be discussed.’

Many surface defects, such as fisheyes, edge pull, and retraction are caused when the liquid film dewets after application. Application of the coating by brush, roller or spray may effectively force wet and spread the film across the substrate, but defects may form soon after application. There is competition between the hydrodynamic inertia of the applied film and the interfacial tension forces that can cause the coating to dewet or retract.
Additives can be used to prevent these defects by reducing the interfacial forces that drive retraction. However, with many different additives to choose from, that may also cause unwanted side effects, the formulator can find additive selection difficult. This paper will compare the advantages and disadvantages of different additive chemistries used to prevent defects caused by dewetting. It will also introduce a new, highly versatile, and effective siloxane wetting agent suitable for many different coating applications and substrates.

Although protective coatings are frequently used to improve the durability and aesthetics of concrete/masonry substrates, robust adhesion is difficult to achieve and typically requires labor-intensive surface preparations (e.g., acid etching and sand blasting) prior to coating applications. Analytical characterization indicates that the cohesive failure in concrete skin is the main root cause for poor adhesion. Guided by this mechanistic understanding, we developed a waterborne hybrid technology capable of penetrating and fortifying the loosely bonded concrete surface layer. The hybrid technology can be subsequently formulated into a clear bonding primer (basecoat), enabling waterborne topcoats to provide robust adhesion on a wide range of minimally prepared and challenging concrete and inorganic substrates. 

Some may say it would be easier to get oil and water to form a homogeneous mixture than ultra-low gloss high-performance 100% solids UV coating at an applicable viscosity (<2,000cP at 25o).  The high crosslink density that makes UV so attractive for high scratch, abrasion, and high gloss application make 100% UV a liability for matte finishes. Formulators routinely have to choose between oligomer content and crosslink density to achieve desired visual appearance (matte appearance plus clarity) and application viscosity.   Another tool formulators, jobbers, and finishers use to achieve matte finish is Excimer curing.  Excimer uses a unique curing process to achieve a matte finish by creating a wrinkled and roughened surface.  The importance of resin selection is crucial to the efficiency or consistency of the wrinkling.  This paper will explore resin design to achieve a high-performance matte finish and resin selection for maximizing Excimer curing.

Energy efficient curing is an extremely relevant area of development for current and future coatings applications. Energy efficient curing can be achieved using thermal sources such as ovens or infrared (IR) lights; or can be achieved using non-thermal sources such as ultraviolet (UV) or visible light. Energy efficient curing reduces the energy consumption associated with producing high performance coatings. We have developed new, high performance cycloaliphatic epoxy coating systems capable of curing between 120 °C - 150 °C or using visible (405 nm) LED systems. Depending on the desired application, these systems can be used as clear coats or heavily pigmented systems additionally, we can tailor our coating systems for powder or solvent spray applications.  Herein, we will describe our resin systems and will provide example formulations as well as curing and performance data.

Matting of clear wood coatings is a critical aspect in capturing the natural beauty of the substrate and appealing to consumer demands.  Maintaining this visual appearance is vital to coating and product lifespan and with deep matte finishes, resistance to burnish and polishing is of particular concern.  Recent work has identified interesting synergies of matting technology that pair the efficiency and clarity of silica matting agents with the physical durability and protective ability of organic particles.   The plastic deformation and energy dissipation of these particles resist polishing forces and protect the matting structure of the silica.  This combination has shown excellent synergy and allows formulation of durable deep-matte finishes with excellent burnish resistance.  There are also significant benefits in reduced viscosity build at high matting agent levels, stability to settling, and chemical resistance.  This presentation will review the technical details of the synergy and characteristics in different wood coating systems.

For many years, waterbased UV has been limited in these industries because of limited tools in the toolbox due to the fact that water and UV curable chemistry are more like oil and water when combined.  This poor compatibility left a lot to be desired in terms of gloss, clarity, and overall coating performance.  For wood and flooring applications, these aesthetic issues were acceptable because the substrate covered up a multitude of sins.  Today, water-based UV has come a long way where aesthetics and performance  can be equal to that of 100% solids and solventborne UV curable coatings allowing formulators, jobbers, and finishers to embrace a more conscientious approached to the environment.  This paper will examine novel waterborne UV technologies that expand the product toolbox that addresses needs such as faster water release, exterior durability, and high gloss making waterborne UV advantageous for wood and beyond.