May 4, 2024

Counterintuitive Surprise! Weaker Bonds Can Make Polymers 10x Stronger

Chemists from MIT and Duke University have actually innovatively increased the strength of polymers significantly by incorporating weaker bonds into their structure, a discovery that does not modify other physical homes of the materials. This advancement could have a considerable impact on increasing the life-span of rubber tires and minimizing microplastic waste, among other applications.
By including weak linkers to a polymer network, chemists drastically boosted the products resistance to tearing.
A team of chemists from MIT and Duke University has found a counterproductive method to make polymers more powerful: introduce a few weaker bonds into the material.
Working with a type of polymer called polyacrylate elastomers, the scientists discovered that they could increase the products resistance to tearing up to tenfold, merely by utilizing a weaker kind of crosslinker to sign up with a few of the polymer building blocks.

One architecture typically utilized for these polymers is a star polymer network. These polymers are made from 2 types of building blocks: one, a star with 4 identical arms, and the other a chain that acts as a linker. As they anticipated, they found that when weaker end-linkers were utilized to hold the polymer strands together, the product ended up being weaker. This takes place, the researchers believe, because the weaker bonds are arbitrarily distributed as junctions in between otherwise strong strands throughout the material, rather of being part of the ultimate strands themselves. When this material is stretched to the breaking point, any cracks propagating through the product attempt to prevent the more powerful bonds and go through the weaker bonds rather.

These rubber-like polymers are typically used in automobile parts, and they are also typically utilized as the “ink” for 3D-printed things. The scientists are now exploring the possible growth of this approach to other types of products, such as rubber tires.
” If you could make a rubber tire 10 times more resistant to tearing, that could have a dramatic effect on the life time of the tire and on the quantity of microplastic waste that breaks off,” states Jeremiah Johnson, a teacher of chemistry at MIT and among the senior authors of the study, which was published on June 22 in the journal Science.
As this polymer network is stretched, weaker crosslinking bonds (blue) break more quickly than any of the strong polymer strands, making it harder for a crack to propagate through the material. Credit: Courtesy of the researchers, modified by MIT News
A substantial advantage of this approach is that it does not appear to alter any of the other physical residential or commercial properties of the polymers.
” Polymer engineers understand how to make products harder, however it inevitably involves altering some other property of the material that you do not wish to alter. Here, the durability improvement comes without any other significant change in physical homes– a minimum of that we can measure– and it is brought about through the replacement of only a small fraction of the general material,” says Stephen Craig, a professor of chemistry at Duke University who is likewise a senior author of the paper.
This job grew out of a longstanding cooperation in between Johnson, Craig, and Duke University Professor Michael Rubinstein, who is also a senior author of the paper. The papers lead author is Shu Wang, an MIT postdoc who made his PhD at Duke.
The weakest link
Polyacrylate elastomers are polymer networks made from strands of acrylate held together by linking particles. These structure blocks can be joined together in various methods to produce materials with various properties.
One architecture typically utilized for these polymers is a star polymer network. These polymers are made from 2 kinds of foundation: one, a star with four similar arms, and the other a chain that functions as a linker. These linkers bind to the end of each arm of the stars, developing a network that looks like a volley ball net.
In a 2021 study, Craig, Rubinstein, and MIT Professor Bradley Olsen teamed up to measure the strength of these polymers. As they anticipated, they discovered that when weaker end-linkers were used to hold the polymer strands together, the material ended up being weaker. Those weaker linkers, which consist of cyclic molecules understood as cyclobutane, can be braked with much less force than the linkers that are typically used to sign up with these foundation.
As a follow-up to that research study, the researchers chose to investigate a different kind of polymer network in which polymer hairs are cross-linked to other strands in random locations, rather of being signed up with at the ends.
This time, when the researchers utilized weaker linkers to join the acrylate building blocks together, they found that the material became far more resistant to tearing.
This takes place, the scientists think, due to the fact that the weaker bonds are arbitrarily distributed as junctions in between otherwise strong strands throughout the product, instead of being part of the ultimate strands themselves. When this material is stretched to the breaking point, any cracks propagating through the material try to prevent the more powerful bonds and go through the weaker bonds rather. If all of the bonds were the very same strength, this means the fracture has to break more bonds than it would.
” Even though those bonds are weaker, more of them end up needing to be broken, due to the fact that the crack takes a course through the weakest bonds, which ends up being a longer course,” Johnson says.
Difficult products
Utilizing this method, the scientists revealed that polyacrylates that integrated some weaker linkers were 9 to 10 times harder to tear than polyacrylates made with stronger crosslinking molecules. This effect was accomplished even when the weak crosslinkers comprised only about 2 percent of the total structure of the material.
The scientists likewise showed that this altered structure did not modify any of the other homes of the product, such as resistance to breaking down when heated up.
” For two materials to have the exact same structure and same properties at the network level, however have an almost order of magnitude distinction in tearing, is rather rare,” Johnson says.
The scientists are now investigating whether this approach might be utilized to improve the toughness of other products, consisting of rubber.
” Theres a lot to explore here about what level of enhancement can be gotten in other kinds of materials and how best to benefit from it,” Craig states.
Referral: “Facile mechanochemical cycloreversion of polymer cross-linkers enhances tear resistance” by Shu Wang, Yixin Hu, Tatiana B. Kouznetsova, Liel Sapir, Danyang Chen, Abraham Herzog-Arbeitman, Jeremiah A. Johnson, Michael Rubinstein and Stephen L. Craig, 22 June 2023, Science.DOI: 10.1126/ science.adg3229.
The groups deal with polymer strength is part of a National Science Foundation-funded center called the Center for the Chemistry of Molecularly Optimized Networks. The mission of this center, directed by Craig, is to study how the residential or commercial properties of the molecular parts of polymer networks affect the physical habits of the networks.