Title: Self Healing Polymeric Materials for Glove Application.

Outcome: To produce a prototype glove that is able to self-heal surface cracks

under ambient/ non extreme conditions.

Self-healing in polymers requires restoration of mechanical properties by bonding

across interfaces created by fracture, cracking, or cutting. These healing polymers are
categorized as “non-autonomic” and “autonomic” on the basis of the presence or
absence of human intervention. Non-autonomic healing polymers require external
stimuli such as heat, UV light, or an organic solvent, while autonomic self-healing
polymers spontaneously repair their wounds under ambient conditions. Autonomic self-
healing polymers are undoubtedly valuable in difficult-to-access environments (e.g.,
aerospace, deep sea, inside the body, and inside devices). Autonomic self-healing
polymers have been achieved using two seminal approaches, namely the extrinsic
method through microencapsulation and the intrinsic method that uses a variety of
dynamic chemistries. Most intrinsic examples are based on the reversible covalent
bonds (e.g., Diels−Alder reaction, disulfide metathesis and imine bonds), physical
interactions (e.g., hydrogen-bonding interactions and metal−ligand interactions), or a
combination of the two (e.g., dynamic imine bonds with hydrogen-bonding interactions
and disulfide metathesis with hydrogen-bonding interactions).

In the first approach, covalent bonds are reshuffled upon application of an

external stimulus such as light or heat: cracks in the material will be bridged by newly
formed bonds. The network linkages are recycled to achieve healing via a metathesis
mechanism of the cross linking groups (Figure 1a). In the second approach, pioneered
by White, Sottos, and co-workers, microcapsules containing unreacted monomer are
embedded in a polymeric material. When a crack appears, the skin of the capsules
ruptures; the monomer is released and cured by a catalyst dispersed in the matrix
(Figure 1b). Both approaches have advantages and disadvantages, and the employed
self-healing technique has to be chosen judiciously with respect to the targeted
application of the material. For example, embedded microcapsule networks display
autonomous self-healing only for a limited number of times, whereas adaptable
networks can theoretically be healed infinitely. On the other hand, and in contrast to the
microcapsule approach adaptable networks require external triggering of a stimulus for
inducing the healing process. In an effort to tune and tailor the existing approaches for
the desired applications, variable healing agents, encapsulated network systems,
reversible cross-linking reactions, and stimuli are being considered.

Self-recovering materials can be described widely into three conceptual ap-

proaches: capsule embedment based self-mending material; vascular self-
recuperating material and intrinsic based self-mending material (Figure 2). Each
approach differs by the instrument used to sequester the mending usefulness until
initiated by split. The sort of sequestration coordinates the harm volume that can be
recovered, the repeatability of mending, and the recovery rate for each approach. This
present segment displays an idea of the techniques that have been used to set self-
repairing materials and of a substantial number of the vital appropriations for each
approach.
Extrinsic Self-Healing Mechanisms
Capsule Embedment Based Self-Healing Material
One of the most remarkable embedded microcapsule network systems was published
by White et al. who reported autonomous self-healing via the ring opening metathesis
polymerization of encapsulated dicyclopentadiene which was released into an epoxy
based network loaded with a Grubbs I catalyst. The same authors later described refined
networks with incorporated vascular systems, which permanently supply the network
with the encapsulated healing agent, enabling the network to self-heal an unlimited
number of times. Besides, Lehn and co-workers designed a double dynamic bisimino
carbohydrazide polymer infused with acid catalyst that healed at room temperature in
bulk. Similarly, disulfide metathesis can also cause healing at room temperature with
the aid of an aliphatic phosphine catalyst. Catalyst-free approaches comprise an even
smaller subset of strategies to achieve bulk healing at room temperature. Preliminary
investigations qualitatively suggest room-temperature self-healing can occur through
tailor-made Diels-Alder moieties.

Intrinsic Self-Healing Mechanisms

Characteristic self-recovering materials don't have a sequestered repairing operator yet
have a idle without moving self-patching functionality that is actuated by harmed or by
an external shock. These materials rely upon chain movability and catch, reversible
polymerizations, softening of thermoplastic stages, hydrogen holding, to begin self-
recovering. Since each of these reactions is reversible, various repairing events are
possible.
 The earliest thermally responsive systems were based on furan−maleimide
Diels−Alder chemistry with temperatures greater than 115 °C needed for healing.
However, exposure to high temperatures is often not feasible or desirable for many
applications, which has led to other approaches being explored to induce healing. For
example, Klumperman and co-workers developed a healing process based on a
thiol−disulfide exchange mechanism at 60 °C. Although this approach proved highly
successful for the preparation of healable materials, the concentration of thiols was
observed to decrease over time under an ambient atmosphere because of continuous
oxidization of thiols to disulfides. Alkoxyamines have also been considered as
thermoreversible dynamic-covalent bonds that can bring about self-healing behavior.
However, the radical products of alkoxyamine dissociation are also sensitive to oxygen
and high temperatures (90−130 °C), which are typically required to induce dissociation
of the labile O−C bond.

Although other successful healing systems triggered by variable stimuli such as

light, pH value, redox agents or various heat triggered approaches have been reported,
Diels–Alder (DA) adaptable networks have become one of the most studied systems in
the field of self-healing materials. Among its advantages for establishing industrial
products is the tolerance of the Diels–Alder/retro Diels–Alder process to oxygen and
moisture, as well as its hysteresis-free cycling between the bonded and debonded state.
However, the number of suitable DA pairings which have proven to be cycled in a
reasonable temperature range (i.e. below the materials’ degradation temperature) are
scarce. To date, only a few DA systems are used in self-healing materials offering
cyclability at mild temperatures in a reasonable timeframe. The most prominent system
is by far the N-maleimide/ furane DA pair pioneered by Wudl and coworkers in their
aforementioned work.

Shape memory assisted self-healing

While the presence of stable reactive groups during self-healing reactions is one aspect
of self-healing, another aspect is physical network remodeling. If there are polymer
network components that ‘‘remember’’ their shape before damage, their presence may
be advantageous in designing self-healing networks. The shape memory polymers
(SMPs) represent this group of mechanically responsive materials that have the ability
to return from a temporarily altered physical state to its original shape. Induced by an
external stimulus, such as temperature, electrical or magnetic fields, solution or light,
they may offer a number of unique advantages.

The primary advantage of using shape memory polymers in self-healing

materials is driven by an opportunity to close a crack, thus enhance healing efficiency.
Upon stimulus leading to self-healing, shape memory components can exert a recovery
force to minimize the size of the crack, and aid the repair process via self-healing
agents blended into the network. Embedding shape-memory alloy (SMA) wires into
self-healing epoxy with manually injected or microencapsulated healing agent also
offered certain advantages. If aligned correctly, the wires contract at or above the shape
change transformation temperature, thus physically decreasing the crack dimension. If
alignment is not correct, the effect will be counterproductive. Perhaps most pragmatic
examples include blending of shape memory thermosetting polymers with small
amounts of thermoplastics, where the former force the crack to close, and the latter
repair the damage by diffusion, entanglements and/or polymerization.

Proposal (2pg)
Introduction:
Advantages
Objectives
Literature review MVQ elastomer, properties,molecular structure
Methodology-Chemicals properties (carcinogenic?)
Characterization
Gantt Chart:
First 3 month: Purchase, setup experimental
Glove synthesis +elastomer, vary parameter (phr, other elastomer, temperature)