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Polydispersity
In chemistry, the dispersity is a measure of the heterogeneity of sizes of molecules or particles in a mixture. A collection of objects is called uniform if the objects have the same size, shape, or mass. A sample of objects that have an inconsistent size, shape and mass distribution is called non-uniform. The objects can be in any form of chemical dispersion, such as particles in a colloid, droplets in a cloud, crystals in a rock, or polymer macromolecules in a solution or a solid polymer mass. Polymers can be described by molecular mass distribution; a population of particles can be described by size, surface area, and/or mass distribution; and thin films can be described by film thickness distribution. IUPAC has deprecated the use of the term ''polydispersity index'', having replaced it with the term ''dispersity'', represented by the symbol Đ (pronounced D-strokeStepto, R. F. T.; Gilbert, R. G.; Hess, M.; Jenkins, A. D.; Jones, R. G.; Kratochvíl P. (2009).Dispersity in ...
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Dynamic Light Scattering
Dynamic light scattering (DLS) is a technique in physics that can be used to determine the size distribution profile of small particles in suspension or polymers in solution. In the scope of DLS, temporal fluctuations are usually analyzed using the intensity or photon auto-correlation function (also known as photon correlation spectroscopy or quasi-elastic light scattering). In the time domain analysis, the autocorrelation function (ACF) usually decays starting from zero delay time, and faster dynamics due to smaller particles lead to faster decorrelation of scattered intensity trace. It has been shown that the intensity ACF is the Fourier transform of the power spectrum, and therefore the DLS measurements can be equally well performed in the spectral domain. DLS can also be used to probe the behavior of complex fluids such as concentrated polymer solutions. Setup A monochromatic light source, usually a laser, is shot through a polarizer and into a sample. The scattered light then ...
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Living Polymerization
In polymer chemistry, living polymerization is a form of chain growth polymerization where the ability of a growing polymer chain to terminate has been removed. This can be accomplished in a variety of ways. Chain termination and chain transfer reactions are absent and the rate of chain initiation is also much larger than the rate of chain propagation. The result is that the polymer chains grow at a more constant rate than seen in traditional chain polymerization and their lengths remain very similar (i.e. they have a very low polydispersity index). Living polymerization is a popular method for synthesizing block copolymers since the polymer can be synthesized in stages, each stage containing a different monomer. Additional advantages are predetermined molar mass and control over end-groups. Living polymerization is desirable because it offers precision and control in macromolecular synthesis. This is important since many of the novel/useful properties of polymers result from t ...
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Living Polymerization
In polymer chemistry, living polymerization is a form of chain growth polymerization where the ability of a growing polymer chain to terminate has been removed. This can be accomplished in a variety of ways. Chain termination and chain transfer reactions are absent and the rate of chain initiation is also much larger than the rate of chain propagation. The result is that the polymer chains grow at a more constant rate than seen in traditional chain polymerization and their lengths remain very similar (i.e. they have a very low polydispersity index). Living polymerization is a popular method for synthesizing block copolymers since the polymer can be synthesized in stages, each stage containing a different monomer. Additional advantages are predetermined molar mass and control over end-groups. Living polymerization is desirable because it offers precision and control in macromolecular synthesis. This is important since many of the novel/useful properties of polymers result from t ...
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Number Average Molecular Weight
The molar mass distribution (or molecular weight distribution) describes the relationship between the number of moles of each polymer species (Ni) and the molar mass (Mi) of that species. In linear polymers, the individual polymer chains rarely have exactly the same degree of polymerization and molar mass, and there is always a distribution around an average value. The molar mass distribution of a polymer may be modified by polymer fractionation. Definitions of molar mass average Different average values can be defined, depending on the statistical method applied. In practice, four averages are used, representing the weighted mean taken with the mole fraction, the weight fraction, and two other functions which can be related to measured quantities: *''Number average molar mass'' (Mn), also loosely referred to as ''number average molecular weight'' (NAMW). *''Mass average molar mass'' (Mw), where ''w'' stands for weight; also commonly referred to as ''weight average'' or ''weight ...
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Weight Average Molecular Weight
The molar mass distribution (or molecular weight distribution) describes the relationship between the number of moles of each polymer species (Ni) and the molar mass (Mi) of that species. In linear polymers, the individual polymer chains rarely have exactly the same degree of polymerization and molar mass, and there is always a distribution around an average value. The molar mass distribution of a polymer may be modified by polymer fractionation. Definitions of molar mass average Different average values can be defined, depending on the statistical method applied. In practice, four averages are used, representing the weighted mean taken with the mole fraction, the weight fraction, and two other functions which can be related to measured quantities: *''Number average molar mass'' (Mn), also loosely referred to as ''number average molecular weight'' (NAMW). *''Mass average molar mass'' (Mw), where ''w'' stands for weight; also commonly referred to as ''weight average'' or ''weight ...
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Polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic and natural polymers play essential and ubiquitous roles in everyday life. Polymers range from familiar synthetic plastics such as polystyrene to natural biopolymers such as DNA and proteins that are fundamental to biological structure and function. Polymers, both natural and synthetic, are created via polymerization of many small molecules, known as monomers. Their consequently large molecular mass, relative to small molecule compounds, produces unique physical properties including toughness, high elasticity, viscoelasticity, and a tendency to form amorphous and semicrystalline structures rather than crystals. The term "polymer" derives from the Greek word πολύς (''polus'', meaning "many, much") and μέρος (''meros'' ...
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Carothers' Equation
In step-growth polymerization, the Carothers equation (or Carothers' equation) gives the degree of polymerization, , for a given fractional monomer conversion, . There are several versions of this equation, proposed by Wallace Carothers, who invented nylon in 1935. Linear polymers: two monomers in equimolar quantities The simplest case refers to the formation of a strictly linear polymer by the reaction (usually by condensation) of two monomers in equimolar quantities. An example is the synthesis of nylon-6,6 whose formula is from one mole of hexamethylenediamine, , and one mole of adipic acid, . For this case :\bar_n=\frac In this equation * is the number-average value of the degree of polymerization, equal to the average number of monomer units in a polymer molecule. For the example of nylon-6,6 \bar_n = 2n ( diamine units and diacid units). *p=\tfrac is the extent of reaction (or conversion to polymer), defined by ** is the number of molecules present initially as monomer ...
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Polyelectrolyte
Polyelectrolytes are polymers whose repeating units bear an electrolyte group. Ion#Anions and cations, Polycations and polyanions are polyelectrolytes. These groups dissociation (chemistry), dissociate in aqueous solutions (water), making the polymers charge (physics), charged. Polyelectrolyte properties are thus similar to both electrolytes (salts) and polymers (high molecular weight compounds) and are sometimes called polysalts. Like salts, their solutions are electrically conductive. Like polymers, their solutions are often viscosity, viscous. Charged molecular chains, commonly present in soft matter systems, play a fundamental role in determining structure, stability and the interactions of various molecular assemblies. Theoretical approaches to describing their statistical properties differ profoundly from those of their electrically neutral counterparts, while technological and industrial fields exploit their unique properties. Many biological molecules are polyelectrolytes. ...
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Damköhler Numbers
The Damköhler numbers (Da) are dimensionless numbers used in chemical engineering to relate the chemical reaction timescale ( reaction rate) to the transport phenomena rate occurring in a system. It is named after German chemist Gerhard Damköhler. The Karlovitz number (Ka) is related to the Damköhler number by Da = 1/Ka. In its most commonly used form, the Damköhler number relates the reaction timescale to the convection time scale, volumetric flow rate, through the reactor for continuous (plug flow or stirred tank) or semibatch chemical processes: : \mathrm = \frac In reacting systems that include interphase mass transport, the second Damköhler number (DaII) is defined as the ratio of the chemical reaction rate to the mass transfer rate : \mathrm_ = \frac It is also defined as the ratio of the characteristic fluidic and chemical time scales: : \mathrm = \frac Since the reaction timescale is determined by the reaction rate, the exact formula for the Damköhler number v ...
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Geometric Distribution
In probability theory and statistics, the geometric distribution is either one of two discrete probability distributions: * The probability distribution of the number ''X'' of Bernoulli trials needed to get one success, supported on the set \; * The probability distribution of the number ''Y'' = ''X'' − 1 of failures before the first success, supported on the set \. Which of these is called the geometric distribution is a matter of convention and convenience. These two different geometric distributions should not be confused with each other. Often, the name ''shifted'' geometric distribution is adopted for the former one (distribution of the number ''X''); however, to avoid ambiguity, it is considered wise to indicate which is intended, by mentioning the support explicitly. The geometric distribution gives the probability that the first occurrence of success requires ''k'' independent trials, each with success probability ''p''. If the probability of succe ...
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Degree Of Polymerization
The degree of polymerization, or DP, is the number of monomeric units in a macromolecule or polymer or oligomer molecule. For a homopolymer, there is only one type of monomeric unit and the ''number-average'' degree of polymerization is given by DP_n\equiv X_n=\frac, where Mn is the number-average molecular weight and M0 is the molecular weight of the monomer unit. For most industrial purposes, degrees of polymerization in the thousands or tens of thousands are desired. This number does not reflect the variation in molecule size of the polymer that typically occurs, it only represents the mean number of monomeric units. Some authors, however, define DP as the number of repeat units, where for copolymers the repeat unit may not be identical to the monomeric unit.Fried J.R. "Polymer Science and Technology" (Pearson Prentice-Hall, 2nd edn 2003), p.27 For example, in nylon-6,6, the repeat unit contains the two monomeric units —NH(CH2)6NH— and —OC(CH2)4CO—, so that a chain ...
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