This article needs additional citations for verification .(February 2015) |
Reactive compatibilization is the process of modifying a mixed immiscible blend of polymers to arrest phase separation and allow for the formation of a stable, long-term continuous phase. It is done via the addition of a reactive polymer, miscible with one blend component and reactive towards functional groups on the second component, which result in the "in-situ" formation of block or grafted copolymers. [1]
A large number of commercial polymeric products are derived from the blending of two or more polymers to achieve a favorable balance of physical properties. However, since most polymer blends are immiscible, it is rare to find a pair of polymers that both are miscible and have desired characteristics. An example of such pair is the miscible resin NORYL™, a mix of poly(phenylene oxide) and polystyrene. [2] Immiscible blends will phase separate and form a dispersed phase, which may improve physical properties (figure 1). DuPont’s rubber toughened Nylon consists of small particles of poly(cis-isoprene) (natural rubber) in a Nylon matrix that toughen the material by arresting crack propagation.
The Gibbs free energy of mixing, , must be negative for a blend to be miscible. According to Flory-Huggins theory, a revision of regular solution theory, the entropy change per mole of lattice sites of blending polymer 1 and polymer 2 is
, where ΔS is the change in entropy of mixing, R is the gas constant, Φ is the volume fraction of each polymer, and x is the number of segments of each polymer. [3] x1 and x2 increase with higher degrees of polymerization and thus molecular weight. Since most useful polymers are high in molecular weight, the change in entropy experienced from the mixing of two large polymer chains is very low, and typically does not bring the Gibbs free energy low enough to constitute miscibility.
Most processed polymer mixes consist of a dispersed phase in a more continuous matrix of the other component. The formation, size, and concentration of this disperse phase are typically optimized for specific mechanical properties. If the morphology is not stabilized, the dispersed phase may coalesce under heat or stress from the environment or further processing. [4] This coalescence may result in diminished properties (brittleness and discoloration) due to the induced phase separation. These morphologies can be stabilized by sufficient interfacial adhesion or lowered interfacial tension between the two phases.
A common technique involves functionalizing one monomer. For example, Nylon-rubber bands are polymerized with functionalized rubber to produce graft or block copolymers. The added structures make it no longer favorable to coalesce and/or increase the steric hindrance in the interfacial area where phase separation would occur.
Dynamic mechanical analysis is a technique used to study and characterize materials. It is most useful for studying the viscoelastic behavior of polymers. A sinusoidal stress is applied and the strain in the material is measured, allowing one to determine the complex modulus. The temperature of the sample or the frequency of the stress are often varied, leading to variations in the complex modulus; this approach can be used to locate the glass transition temperature of the material, as well as to identify transitions corresponding to other molecular motions.
In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are sometimes called bipolymers. Those obtained from three and four monomers are called terpolymers and quaterpolymers, respectively. Copolymers can be characterized by a variety of techniques such as NMR spectroscopy and size-exclusion chromatography to determine the molecular size, weight, properties, and composition of the material.
Gas mixtures can be effectively separated by synthetic membranes made from polymers such as polyamide or cellulose acetate, or from ceramic materials.
Flory–Huggins solution theory is a lattice model of the thermodynamics of polymer solutions which takes account of the great dissimilarity in molecular sizes in adapting the usual expression for the entropy of mixing. The result is an equation for the Gibbs free energy change for mixing a polymer with a solvent. Although it makes simplifying assumptions, it generates useful results for interpreting experiments.
In thermodynamics, the entropy of mixing is the increase in the total entropy when several initially separate systems of different composition, each in a thermodynamic state of internal equilibrium, are mixed without chemical reaction by the thermodynamic operation of removal of impermeable partition(s) between them, followed by a time for establishment of a new thermodynamic state of internal equilibrium in the new unpartitioned closed system.
Coacervate is an aqueous phase rich in macromolecules such as synthetic polymers, proteins or nucleic acids. It forms through liquid-liquid phase separation (LLPS), leading to a dense phase in thermodynamic equilibrium with a dilute phase. The dispersed droplets of dense phase are also called coacervates, micro-coacervates or coacervate droplets. These structures draw a lot of interest because they form spontaneously from aqueous mixtures and provide stable compartmentalization without the need of a membrane—they are protocell candidates.
In chemistry, a regular solution is a solution whose entropy of mixing is equal to that of an ideal solution with the same composition, but is non-ideal due to a nonzero enthalpy of mixing. Such a solution is formed by random mixing of components of similar molar volume and without strong specific interactions, and its behavior diverges from that of an ideal solution by showing phase separation at intermediate compositions and temperatures. Its entropy of mixing is equal to that of an ideal solution with the same composition, due to random mixing without strong specific interactions. For two components
In materials science, a polymer blend, or polymer mixture, is a member of a class of materials analogous to metal alloys, in which at least two polymers are blended together to create a new material with different physical properties.
Miscibility is the property of two substances to mix in all proportions, forming a homogeneous mixture. Such substances are said to be miscible. The term is most often applied to liquids but also applies to solids and gases. An example in liquids is the miscibility of water and ethanol as they mix in all proportions.
In polymer chemistry, gradient copolymers are copolymers in which the change in monomer composition is gradual from predominantly one species to predominantly the other, unlike with block copolymers, which have an abrupt change in composition, and random copolymers, which have no continuous change in composition . In the gradient copolymer, as a result of the gradual compositional change along the length of the polymer chain less intrachain and interchain repulsion are observed.
Short Fiber Reinforced Blends are partial case of ternary composites, i.e. composites prepared of three ingredients. In particular they can be considered as a combination of an immiscible polymer blend and a short fiber reinforced composite. These blends have the potential to integrate the easy processing solutions available for short fiber reinforced composites with the high mechanical performance of continuous fiber reinforced composites. The performance of these complex, ternary systems is controlled by their morphology.
Rubber toughening is a process in which rubber nanoparticles are interspersed within a polymer matrix to increase the mechanical robustness, or toughness, of the material. By "toughening" a polymer it is meant that the ability of the polymeric substance to absorb energy and plastically deform without fracture is increased. Considering the significant advantages in mechanical properties that rubber toughening offers, most major thermoplastics are available in rubber-toughened versions; for many engineering applications, material toughness is a deciding factor in final material selection.
Temperature-responsive polymers or thermoresponsive polymers are polymers that exhibit drastic and discontinuous changes in their physical properties with temperature. The term is commonly used when the property concerned is solubility in a given solvent, but it may also be used when other properties are affected. Thermoresponsive polymers belong to the class of stimuli-responsive materials, in contrast to temperature-sensitive materials, which change their properties continuously with environmental conditions. In a stricter sense, thermoresponsive polymers display a miscibility gap in their temperature-composition diagram. Depending on whether the miscibility gap is found at high or low temperatures, either an upper critical solution temperature (UCST) or a lower critical solution temperature (LCST) exists.
The lower critical solution temperature (LCST) or lower consolute temperature is the critical temperature below which the components of a mixture are miscible in all proportions. The word lower indicates that the LCST is a lower bound to a temperature interval of partial miscibility, or miscibility for certain compositions only.
An emulsion dispersion is thermoplastics or elastomers suspended in a liquid state by means of emulsifiers.
In electrochemistry, ITIES is an electrochemical interface that is either polarisable or polarised. An ITIES is polarisable if one can change the Galvani potential difference, or in other words the difference of inner potentials between the two adjacent phases, without noticeably changing the chemical composition of the respective phases. An ITIES system is polarised if the distribution of the different charges and redox species between the two phases determines the Galvani potential difference.
Adsorption is the adhesion of ions or molecules onto the surface of another phase. Adsorption may occur via physisorption and chemisorption. Ions and molecules can adsorb to many types of surfaces including polymer surfaces. A polymer is a large molecule composed of repeating subunits bound together by covalent bonds. In dilute solution, polymers form globule structures. When a polymer adsorbs to a surface that it interacts favorably with, the globule is essentially squashed, and the polymer has a pancake structure.
Macroemulsions are dispersed liquid-liquid, thermodynamically unstable systems with particle sizes ranging from 1 to 100 μm, which, most often, do not form spontaneously. Macroemulsions scatter light effectively and therefore appear milky, because their droplets are greater than a wavelength of light. They are part of a larger family of emulsions along with miniemulsions. As with all emulsions, one phase serves as the dispersing agent. It is often called the continuous or outer phase. The remaining phase(s) are disperse or inner phase(s), because the liquid droplets are finely distributed amongst the larger continuous phase droplets. This type of emulsion is thermodynamically unstable, but can be stabilized for a period of time with applications of kinetic energy. Surfactants are used to reduce the interfacial tension between the two phases, and induce macroemulsion stability for a useful amount of time. Emulsions can be stabilized otherwise with polymers, solid particles or proteins.
In colloidal chemistry, the critical micelle concentration (CMC) of a surfactant is one of the parameters in the Gibbs free energy of micellization. The concentration at which the monomeric surfactants self-assemble into thermodynamically stable aggregates is the CMC. The Krafft temperature of a surfactant is the lowest temperature required for micellization to take place. There are many parameters that affect the CMC. The interaction between the hydrophilic heads and the hydrophobic tails play a part, as well as the concentration of salt within the solution and surfactants.
In polymer chemistry, compatibilization is the addition of a substance to an immiscible blend of polymers that will increase their stability. Polymer blends are typically described by coarse, unstable phase morphologies; this results in poor mechanical properties. Compatibilizing the system will make a more stable and better blended phase morphology by creating interactions between the two previously immiscible polymers. Not only does this enhance the mechanical properties of the blend, but it often yields properties that are generally not attainable in either single pure component.