trength. Scientists understand how forces, stress and strain combine to make strong materials, but they understand less about how to create the materials in the first place.
Pearls of wisdom
"The standard view is that the crystal front moves too fast for the inclusions to move out of the way, like a wave washing over a rock," said De Yoreo.
That idea's drawback is that it lacks the details needed to explain where the strain within the material comes from. The new results from De Yoreo and colleagues do, however.
"We've found a completely different mechanism," he said.
To find out how calcium carbonate incorporates proteins or other strength-building components, the team turned to atomic force microscopy, also known as AFM, at the Molecular Foundry, a DOE Office of Science User Facility at Lawrence Berkeley National Laboratory. In AFM, the microscope tip delicately runs over the surface of a sample like a needle running over the grooves in a vinyl record. This creates a three-dimensional image of a specimen under the scope.
The team used a high concentration of calcium carbonate that naturally forms a crystalline mineral known as calcite. The calcite builds up in layers, creating uneven surfaces during growth, like steps and terraces on a mountainside. Or, imagine a staircase. A terrace is the flat landing at the bottom; the stair steps have vertical edges from which calcite grows out, eventually turning into terraces too.
For their inclusions, the team created spheres out of organic molecules and added them to the mix. These spheres called micelles are molecules that roll up like roly-poly bugs based on the chemistry along their bodies - pointing outwards are the parts of their molecules that play well chemically with both the surrounding water and the calcite, while tucked inside are the parts that don't get along with the watery environment.
Better composites through chemistry
"The step edge has chemistry that the terrace doesn't," said De Yoreo. "There are these extra dangling bonds that the micelles can interact with."
The edges hold onto the micelles as the calcium carbonate steps close around them, one after another. The team watched as the growing steps squeezed the micelles. As the step closed around the top of the micelle, first a cavity formed and then it disappeared altogether under the surface of the growing crystal.
To verify that the micelles were in fact buried within the crystals, the team dissolved the crystal and looked again. Like running a movie backwards, the team saw micelles appear as the layers of crystal disappeared.
Finally, the team recreated the process in a mathematical simulation. This showed them that the micelles - or any spherical inclusions - are compressed like springs as the steps close around them.
These compressed springs then create strain in the crystal lattice between the micelles, leading to enhanced mechanical strength. This strain likely accounts for the added strength seen in seashells, pearls and similar biominerals.
"The steps capture the micelles for a chemical reason, not a mechanical one, and the resulting compression of the micelles by the steps then leads to forces that explain where the strength comes from," said De Yoreo.
Kang Rae Cho, Yi-Yeoun Kim, Pengcheng Yang, Wei Cai, Haihua Pan, Alexander N. Kulak, Jolene L. Lau, Prashant Kulshreshtha, Steven P. Armes, Fiona C. Meldrum and James J. De Yoreo. Direct observation of mineral-organic composite formation reveals occlusion mechanism, Nature Communications January 6, 2016, doi:10.1038/NCOMMS10187.
Pacific Northwest National Laboratory
Space Technology News - Applications and Research
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