Mood ring materials offer a new way to detect damage in failing infrastructure

The team’s initial studies, published last April in the Proceedings of the SPIE Conference on Sensors and Smart Structures Technologies for Civil, Mechanical and Aerospace Systems, have determined that adding a tiny concentration of special nanoparticles (1 to 5 percent by weight) to an optically clear polymer matrix produces a distinctive light signature that changes as the material is subjected to a broad range of compressive and tensile loads.

The Vanderbilt group is not the only research team using nanoparticles to create smart materials, but they have a special advantage. They are using a particular type of nanoparticle called a white light quantum dot. These quantum dots are unique because they emit white light where other quantum dots only emit light at specific wavelengths.

These special quantum dots were accidentally discovered in 2005 in the laboratory of Sandra Rosenthal, Jack and Pamela Egan Professor of Chemistry at Vanderbilt. “We were trying to make the smallest cadmium selenide quantum dots possible and, when we did, we were astonished to discover that they emit in a broad spectrum,” she recalled.

“White light quantum dots have very unique optical properties compared with other nanoparticles,” said Talitha Frecker, a chemistry graduate student who is participating in the study. “The white light fluorescence is a surface phenomenon.”

Fast forward to 2013 when Adams moved to Vanderbilt. When he learned about Rosenthal’s discovery, he realized that her quantum dots were tailor made for creating smart materials: “When we put these nanoparticles into a material, they observe and react to what is going on around them.”

Now Adam’s expectation has been confirmed by the series of preliminary tests that Brubaker and his colleagues have conducted. They have coated fiberglass and aluminum strips with a polymer coating containing white light quantum dots and subjected them to varying degrees of external load. They have determined that the intensity of the emission spectrum produced by the quantum dots decreases as the load increases. The drop-off is largest with the initial loading and gradually decreases at higher levels of load.

“The mechanism is still a bit unclear, but we have demonstrated that entrapping these quantum dots in ultra-thin polymer films on metal surfaces can provide advance warning when the underlying metal is about to sustain physical or chemical damage,” said Professor of Chemical and Biomolecular Engineering Kane Jennings, who is participating in the project along with doctoral student Ian Njoroge.

The researchers theorize that the quantum dots emit light in a broad spectrum because more than 80 percent of the atoms lie on the surface. They also know that the bonds between the surface atoms and molecules surrounding them plays a critical role.

“The end result is that the strength of the quantum dot emissions gives us a permanent record of the level of stress that a material has experienced,” said Brubaker.

In this fashion, the researchers have verified that the material can act as a new kind of strain gauge that permanently records the cumulative amount of stress that the material to which it is applied experiences.

In their initial experiments, the engineers have kept the loads relatively modest, under 1,250 pounds, well within the elastic limits that the materials can withstand without permanent damage. This has provided them a baseline that they can use to compare to the results they get as they move to higher loads that cause the materials to begin failing.

The researchers know that things will get more complicated as they ramp up the stresses they are applying.

For example, in a set of tests they ran with epoxy cylinders, which deformed into a barrel shape under compression, they found that the emission spectrum actually increased, instead of decreasing. They hypothesize that this increase in emission occurred because the deformation actually squeezed the nanoparticles closer together so there were more of them within the small area where they were measuring the emission.

Vanderbilt notes that the researchers have already encountered one of these complications when they tested surface coated fiberglass samples. When these samples were loaded under tensile stress, the emissions spectrum decreased much as it did with the aluminum samples until the load reached about 350 pounds. But then it began to climb.

By the popping and cracking coming from the samples, they realized this was the point when individual fibers in the sample began breaking. They hypothesize that the emission increased because quantum dots that were previously hidden within the fiberglass matrix were exposed when fibers began to fail. This again increased the number of quantum dots within a given area, causing the overall emission level to rise.

The LASIR team also realizes there is another problem that they will have to solve to make a practical damage detection system. The quantum dots suffer from photo-bleaching. That is, when they are exposed to light they gradually lose their fluorescence over time. As a result, the material must be shielded from external light.

“There is a lot we have to learn before we can create a smart material that is ready for real world applications, but all the signs are positive,” said Adams. “Some of our commercial partners are very interested so there is a good chance that it will be adopted if it performs as well as we think it will.”

— Read more in Cole D. Brubaker et al., “In-situ material state monitoring using embedded CdSe quantum dots,” Sensors and Smart Structures Technologies for Civil, Mechanical, and Aerospace Systems (20 April 2016) (DOI: 10.1117/12.2218351)