SELF-HEALING PLASTICS

TERNA COLEGE OF ENGINEERING, OSMANABAD. Presented by: HASHMI MD ABDUL RASHEED. rush4hashmi@gmail.com DIMARI KAMLESH B. kamnon_kamal@yahoo.co.in Cell no.9969569367 Abstract: Plastic over time naturally gets weaker, no matter how well made it is, because over time microscopic cracks form in the plastic that become weak points in the structure that will only degrade into ever larger cracks. It becomes important to heal these microscopic cracks before they can grow larger and become an actual problem. A new kind of plastic is being developed that contains very small balloons filled with liquid. The liquid contains monomer molecules, the building material of plastic. A new solid plastic that contains a special chemical has been already developed. This chemical is used as catalyst. The new plastic still cracks like common plastic. But, when it does, the monomer liquid is released and flows into the crack. The catalyst in the solid plastic then reacts with the liquid monomer. The chemical reaction between the liquid monomer and the catalyst creates polymer molecules that repair the break. The repaired plastic has seventy-five percent of the strength of undamaged plastic. Overall the embedded small balloons provide two independent effects: the increase in virgin fracture toughness from general toughening and the ability to self-heal the virgin fracture event. Introduction: Microencapsulated dicyclopentadiene (DCPD) healing agent and Grubbs’Ru catalyst are incorporated into an epoxy matrix to produce a polymer composite capable of SELF-HEALING. Healing is achieved by incorporating a microencapsulated healing agent and a catalytic chemical trigger within a polymer matrix. A propagating crack ruptures the microcapsules and exposes catalyst particles. Crack opening draws the healing agent into the crack plane, where contact with the catalyst phase initiates polymerization. The polymerized healing agent reestablishes structural integrity across the crack plane.

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Chemicals in use: DICYCLOPENTADIENE: Dicyclopentadiene, abbreviated DCPD, is the chemical compound with the formula C10H12. At room temperature, it is a white crystalline solid with a camphor-like odor. Dicyclopentadiene is coproduced in large quantities in the steam cracking of naphtha and gas oils to ethylene. The major use is resins, particularly unsaturated polyester resins. When heated above 100 °C, dicyclopentadiene undergoes a reaction to yield cyclopentadiene, a compound important in both organic and inorganic chemistry. The reaction is reversible and at room temperature cyclopentadiene slowly dimerizes to reform dicyclopentadiene.Dicyclopentadiene is a monomer in polymerization reactions. PRICE:High, $0.30 per pound & low, $0.28

IUPAC name Other names Molecular formula Molar mass Density Melting point Boiling point

3a,4,7,7a-Tetrahydro-4,7-methano-1H-indene 1,3-Dicyclopentadiene C10H12 132.20 g/mol 0.98 g/cm3 32.5 °C 170 °C

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The product should find use as an intermediate for UPR (unsaturated polyester resins ) and petroleum resins, but higher end uses are targeted. In marine use, DCPD has been increasingly substituted for unsaturated polyesters. The C10 structure has an alcohol group and a double bond which may be used in innovative ways. EPOXY MATRIX: In chemistry, epoxy or polyepoxide is a thermosetting epoxide polymer that cures (polymerizes and crosslinks) when mixed with a catalyzing agent or "hardener". Most common epoxy resins are produced from a reaction between epichlorohydrin and bisphenol-A. The chemistry of epoxies and the range of commercially available variations allow cure polymers to be produced with a very broad range of properties. In general, epoxies are known for their excellent adhesion, chemical and heat resistance, good-to-excellent mechanical properties.

Fig. Structure of unmodified epoxy prepolymer. n denotes the number of polymerized subunits and is in the range from 0 to about 25 When epoxies are mixed with the appropriate catalyst, the resulting reaction is exothermic, and the oxygen on the epoxy monomers is "flipped." This occurs throughout the epoxy, and a matrix with a high stress tolerance is formed, and "glues" the materials together.

GRUBB’S CATALYST: Ruthenium carbene complex was invented by chemistry professor Robert H. Grubbs. The Grubbs' catalyst is ideal because it remains active even on exposure to air, moisture, or most organic functional groups.

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Fig: Structure of Grubb’s Catalyst, ruthenium carbium. Molecular formula Molar mass Appearance CAS number Melting point C43H72Cl2P2Ru 822.96 g/mol Purple Solid [172222-30-9] 153 °C (426 K)

Grubbs' Catalyst is a transition metal carbene complex named after the chemist by whom it was first synthesized, Robert H. Grubbs. In contrast to other olefin metathesis catalysts, Grubbs' Catalysts tolerate other functional groups in the alkene and are compatible with a wide range of solvents. For these reasons, Grubbs' Catalysts are extraordinarily versatile. Process: The microcapsules could be produced by high-speed stirring of an aqueous mixture of urea and formaldehyde, dicyclopentadiene, resorcinol acid catalyst, and ethylene-maleic anhydride resin emulsifying agent. The product is microcapsules of ureaformaldehyde resin containing dicyclopentadiene liquid. To make their composite system, stir 10% by weight of resin microcapsules 100 microm in diameter into the epoxy formulation. They cure the molded epoxy for 24 hours at room temperature followed by a 24-hour bake at 40 ºC. The polymerization catalyst dispersed throughout is a ruthenium carbene complex invented by chemistry professor Robert H. Grubbs of California Institute of Technology. The Grubbs catalyst remains active even on exposure to air, moisture, or most organic functional groups.

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Self-healing of cracks:

HEAL THYSELF Video images show a crack rupturing a microcapsule, which releases dicyclopentadiene. The capsule’s contents were dyed red to aid visualization of the flow. Conclusion: 1) The addition of microcapsules produced a transition of the fracture plane morphology to hackle markings. 2) Addition of DCPD-filled urea-formaldehyde (UF) microcapsules yields up to 12.7% increase in fracture toughness and induces a change in the fracture plane morphology to hackle markings. 3) Overall the embedded microcapsules provide the independent effect to self-heal the virgin fracture event. Future scope: On large scale production, it has several uses. 1) One could be for things that are impractical to fix on a regular basis, like parts deep inside air plane wings or space ships. 2) It can be used in manufacturing automobile parts like bonnet, hood etc.. which won’t get scratched or crack. 3) And it could be used in people, to replace bone joints that have become broken or damaged. These include knees or hips.

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