In polymer chemistry, the gel point is an abrupt change in the viscosity of a solution containing polymerizable components. At the gel point, a solution undergoes gelation, as reflected in a loss in fluidity. After the monomer/polymer solution has passed the gel point, internal stress builds up in the gel phase, which can lead to volume shrinkage. Gelation is characteristic of polymerizations that include crosslinkers that can form 2- or 3-dimensional networks. For example, the condensation of a dicarboxylic acid and a triol will give rise to a gel whereas the same dicarboxylic acid and a diol will not. The gel is often a small percentage of the mixture, even though it greatly influences the properties of the bulk. [1]
An infinite polymer network appears at the gel point. Assuming that it is possible to measure the extent of reaction, , defined as the fraction of monomers that appear in cross-links, the gel point can be determined. [2] The critical extent of reaction for the gel point to be formed is given by:
For example, a polymer with N≈200 is able to reach the gel point with only 0.5% of monomers reacting. This shows the ease at which polymers are able to form infinite networks. The critical extent of reaction for gelation can be determined as a function of the properties of the monomer mixture, , , and : [3]
A gel is a semi-solid that can have properties ranging from soft and weak to hard and tough. Gels are defined as a substantially dilute cross-linked system, which exhibits no flow when in the steady state, although the liquid phase may still diffuse through this system.
Polymer physics is the field of physics that studies polymers, their fluctuations, mechanical properties, as well as the kinetics of reactions involving degradation and polymerisation of polymers and monomers respectively.
In chemical thermodynamics, activity is a measure of the "effective concentration" of a species in a mixture, in the sense that the species' chemical potential depends on the activity of a real solution in the same way that it would depend on concentration for an ideal solution. The term "activity" in this sense was coined by the American chemist Gilbert N. Lewis in 1907.
In polymer chemistry, ring-opening polymerization (ROP) is a form of chain-growth polymerization in which the terminus of a polymer chain attacks cyclic monomers to form a longer polymer. The reactive center can be radical, anionic or cationic. Some cyclic monomers such as norbornene or cyclooctadiene can be polymerized to high molecular weight polymers by using metal catalysts. ROP is a versatile method for the synthesis of biopolymers.
In polymer chemistry, emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomers, and surfactants. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer are emulsified in a continuous phase of water. Water-soluble polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses, can also be used to act as emulsifiers/stabilizers. The name "emulsion polymerization" is a misnomer that arises from a historical misconception. Rather than occurring in emulsion droplets, polymerization takes place in the latex/colloid particles that form spontaneously in the first few minutes of the process. These latex particles are typically 100 nm in size, and are made of many individual polymer chains. The particles are prevented from coagulating with each other because each particle is surrounded by the surfactant ('soap'); the charge on the surfactant repels other particles electrostatically. When water-soluble polymers are used as stabilizers instead of soap, the repulsion between particles arises because these water-soluble polymers form a 'hairy layer' around a particle that repels other particles, because pushing particles together would involve compressing these chains.
Polymer chemistry is a sub-discipline of chemistry that focuses on the structures of chemicals, chemical synthesis, and chemical and physical properties of polymers and macromolecules. The principles and methods used within polymer chemistry are also applicable through a wide range of other chemistry sub-disciplines like organic chemistry, analytical chemistry, and physical chemistry. Many materials have polymeric structures, from fully inorganic metals and ceramics to DNA and other biological molecules. However, polymer chemistry is typically related to synthetic and organic compositions. Synthetic polymers are ubiquitous in commercial materials and products in everyday use, such as plastics, and rubbers, and are major components of composite materials. Polymer chemistry can also be included in the broader fields of polymer science or even nanotechnology, both of which can be described as encompassing polymer physics and polymer engineering.
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.
The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency towards further change. For a given set of reaction conditions, the equilibrium constant is independent of the initial analytical concentrations of the reactant and product species in the mixture. Thus, given the initial composition of a system, known equilibrium constant values can be used to determine the composition of the system at equilibrium. However, reaction parameters like temperature, solvent, and ionic strength may all influence the value of the equilibrium constant.
In materials science, the sol–gel process is a method for producing solid materials from small molecules. The method is used for the fabrication of metal oxides, especially the oxides of silicon (Si) and titanium (Ti). The process involves conversion of monomers into a colloidal solution (sol) that acts as the precursor for an integrated network of either discrete particles or network polymers. Typical precursors are metal alkoxides. Sol–gel process is used to produce ceramic nanoparticles.
In polymer chemistry, step-growth polymerization refers to a type of polymerization mechanism in which bi-functional or multifunctional monomers react to form first dimers, then trimers, longer oligomers and eventually long chain polymers. Many naturally-occurring and some synthetic polymers are produced by step-growth polymerization, e.g. polyesters, polyamides, polyurethanes, etc. Due to the nature of the polymerization mechanism, a high extent of reaction is required to achieve high molecular weight. The easiest way to visualize the mechanism of a step-growth polymerization is a group of people reaching out to hold their hands to form a human chain—each person has two hands. There also is the possibility to have more than two reactive sites on a monomer: In this case branched polymers production take place.
In polymer chemistry, free-radical polymerization (FRP) is a method of polymerization by which a polymer forms by the successive addition of free-radical building blocks. Free radicals can be formed by a number of different mechanisms, usually involving separate initiator molecules. Following its generation, the initiating free radical adds (nonradical) monomer units, thereby growing the polymer chain.
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 step-growth polymerization, the Carothers equation gives the degree of polymerization, Xn, for a given fractional monomer conversion, p.
Curing is a chemical process employed in polymer chemistry and process engineering that produces the toughening or hardening of a polymer material by cross-linking of polymer chains. Even if it is strongly associated with the production of thermosetting polymers, the term "curing" can be used for all the processes where a solid product is obtained from a liquid solution, such as with PVC plastisols.
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.
In polymer chemistry, gelation is the formation of a gel from a system with polymers. Branched polymers can form links between the chains, which lead to progressively larger polymers. As the linking continues, larger branched polymers are obtained and at a certain extent of the reaction, links between the polymer result in the formation of a single macroscopic molecule. At that point in the reaction, which is defined as gel point, the system loses fluidity and viscosity becomes very large. The onset of gelation, or gel point, is accompanied by a sudden increase in viscosity. This "infinite" sized polymer is called the gel or network, which does not dissolve in the solvent, but can swell in it.
In polymer chemistry, an organogel is a class of gel composed of an organic liquid phase within a three-dimensional, cross-linked network. Organogel networks can form in two ways. The first is classic gel network formation via polymerization. This mechanism converts a precursor solution of monomers with various reactive sites into polymeric chains that grow into a single covalently-linked network. At a critical concentration, the polymeric network becomes large enough so that on the macroscopic scale, the solution starts to exhibit gel-like physical properties: an extensive continuous solid network, no steady-state flow, and solid-like rheological properties. However, organogels that are “low molecular weight gelators” can also be designed to form gels via self-assembly. Secondary forces, such as van der Waals or hydrogen bonding, cause monomers to cluster into a non-covalently bonded network that retains organic solvent, and as the network grows, it exhibits gel-like physical properties. Both gelation mechanisms lead to gels characterized as organogels.
Flory–Stockmayer theory is a theory governing the cross-linking and gelation of step-growth polymers. The Flory–Stockmayer theory represents an advancement from the Carothers equation, allowing for the identification of the gel point for polymer synthesis not at stoichiometric balance. The theory was initially conceptualized by Paul Flory in 1941 and then was further developed by Walter Stockmayer in 1944 to include cross-linking with an arbitrary initial size distribution. The Flory–Stockmayer theory was the first theory investigating percolation processes. Flory–Stockmayer theory is a special case of random graph theory of gelation.
In chemistry, a silicic acid is any chemical compound containing the element silicon attached to oxide and hydroxyl groups, with the general formula [H2xSiOx+2]n or, equivalently, [SiOx(OH)4−2x]n. Orthosilicic acid is a representative example. Silicic acids are rarely observed in isolation, but are thought to exist in aqueous solutions, including seawater, and play a role in biomineralization. They are typically colorless weak acids that are sparingly soluble in water. Like the silicate anions, which are their better known conjugate bases, silicic acids are proposed to be oligomeric or polymeric. No simple silicic acid has ever been identified, since these species are primarily of theoretical interest.
Random graph theory of gelation is a mathematical theory for sol–gel processes. The theory is a collection of results that generalise the Flory–Stockmayer theory, and allow identification of the gel point, gel fraction, size distribution of polymers, molar mass distribution and other characteristics for a set of many polymerising monomers carrying arbitrary numbers and types of reactive functional groups.