To explore more about this sustainable coating, let us first discuss some important aspects of powder coatings. Unlike conventional coatings like paints, which are films that are formed via the evaporation of a solvent, powder coatings typically are dry powders that are applied electrostatically and cured via temperature or with ultraviolet light and require no volatile components. Nowadays, these coatings are intensively used in industry to provide protection against aggressive environmental conditions and/or for decorative purposes. Some examples of powder-coated products can be seen in Figure 1. The binder or resin is the main constituent of a typical thermoset powder coating (TPC) and is the film-forming element of the product. It provides adhesion to a substrate, binds pigments and other additives together, and determines important properties such as durability, flexibility, and hardness. In addition, colors, additives, and fillers can be added to modify certain properties of the coating like gloss, opacity, and stability.

Figure 1: Examples of powder-coated applications which are applied for decorative and protective purposes, such as parts for the automotive industry and powder-coated metal objects like pipelines.

Several types of thermoset powders, derived from epoxies, acrylics, hydroxyls (polyester), and carboxyl(polyurethane) groups can be used in the synthesis of TPCs. Some of these types suffer from poor exterior durability or moderate chemical resistance. Therefore, an alternative could be a polycarbonate-based resin which is typically amorphous, and usually exhibits properties like high transparency and low UV absorption, particularly suitable for outdoor use. However, the downside of commercially synthesized polycarbonate is the use of phosgene (Cl₂C=O), which is a highly toxic gas that requires serious environmental and safety considerations. The co-monomer bisphenol A (BPA) is also debated for its potential adverse health effects.

Limonene oxide is a potential biobased epoxide derived from limonene and could be a good alternative to phosgene / BPA. Limonene is a major component that can be found in the oil of citrus peels, like oranges. It is a colorless liquid that is often used as a flavoring agent in food manufacturing. Its abundance and its multiple functionalities make it an attractive, renewable building block for polymer synthesis. Via a chemical reaction that involves carbon dioxide (CO₂), a fully recyclable poly(limonene carbonate) (PLC) can be synthesized, carrying functional groups that can be modified or crosslinked to introduce new functionalities such as antibacterial activity, hydrophilicity, and water solubility. This makes CO₂, also known as the primary driver of climate change, a useful molecule that can be used as a monomer to create a sustainable polycarbonate powder coating. This pathway is shown schematically in Figure 2. As a result, this fully limonene-derived PLC has great potential as a TPC binder, which can deliver good exterior durability and chemical resistance. These two properties make this type of renewable binder a great alternative for the manufacturing of powder coatings, avoiding any concerning reactants.

Figure 2: Simplified overview that involves the reaction mechanism of a limonene-based coating. Here, first limonene is epoxidized to limonene oxide. The latter is used for the synthesis of poly(limonene carbonate) (PLC) in the presence of carbon dioxide. With the use of a crosslinking molecule (thiol-based) and radical initiator, under the influence of ultraviolet light, a crosslinked network (TEN) is formed via a thiol-ene reaction with the pendant isoprenyl groups of PLC and results in the formation of a thin layer on a particular surface.

Whether you’re looking to enhance material sustainability, develop new materials, or material research, our team has the knowledge, expertise, and state-of-the-art infrastructure to help you achieve your goals. And, with a large network within the TU/e, we’re able to tap into a wealth of knowledge and resources. Contact us to learn more about how we can help you!

For additional technical details about this topic, feel free to visit the main article via the following link: Limonene-derived polycarbonates as biobased UV-curable (powder) coating resins

Reaching the unreachable!
Confocal Raman spectroscopy is a highly suitable technique for this, as the laser beam can be focused on a particular spot beneath a material surface, shown in the schematic. We discuss the capabilities of this technique here in 2 demonstration examples.

1. Polyethylene bag
As a first example we have placed a closed polyethylene (LDPE) bag containing poly(ethylene terephthalate) (PET) granules directly under the confocal Raman apparatus. We performed a depth analysis through the bag into the granules, while continuously analyzing the material composition. A clear transition can be seen going from LDPE towards PET in the spectra below. This example also demonstrates another use case for this technique, in which a bag of unknown material could be analyzed without needing to risk opening the bag, as confocal Raman spectroscopy can be used to analyze the material right through the packaging.

2. Glass vial with acetone
The same principle applies to unknown liquids inside a glass vial. In this example we placed a glass vial with acetone directly underneath the Raman microscope. The measurements can be performed through the glass barrier, while continuously analyzing the chemical composition of both the glass vial and the acetone. The spectra below clearly show the transition between the different materials

Confocal Raman spectroscopy can be used to identify unknown substances, particularly when very detailed and local sample analysis is required. With this technique the chemical composition of particles with a particle size down to 1 μm can be analyzed. Moreover, these particles can be analyzed even if they are fully enclosed inside a matrix, as we have demonstrated in the examples.

Have you ever encountered small particulate matter trapped in your product without knowing its origin? Confocal Raman spectroscopy may be the answer. Please feel free to contact us to discuss the possibilities!