Crc Handbook Of Solubility Parameters And Other Cohesion Parameters Pdf
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Physical Properties of Polymers Handbook pp Cite as.
- Prediction of Hansen Solubility Parameters with a New Group-Contribution Method
- CRC Handbook of Solubility Parameters and Other Cohesion Parameters Second Edition Free Books
- 1 Solubility Parameters — An Introduction
- CRC Handbook of Solubility Parameters and Other Cohesion Parameters - Ebook
I only wish you were here more often to enjoy it with us. The CRC Handbook of Solubility Parameters and Other Cohesion Parameters, Second Edition, which includes 17 new sections and 40 new data tables, incorporates information from a vast amount of material published over the last ten years. The volume is based on a bibliography of 2, reports, including 1, new citations. Life in the Senate will be that much harder.
Prediction of Hansen Solubility Parameters with a New Group-Contribution Method
The major results of this work were the realization that polymer film formation by solvent evaporation took place in two distinct phases and the development of what has come to be called Hansen solubility or cohesion parameters, abbreviated in the following by HSP. The first phase of film formation by solvent evaporation is controlled by surface phenomena such as solvent vapor pressure, wind velocity, heat transfer, etc. It is not controlled by the binding of solvent molecules to polymer molecules by hydrogen bonding as was previously thought.
My solubility parameter work was actually started to define affinities between solvent and polymer to help predict the degree of this binding which was thought to control solvent retention. This was clearly a futile endeavor as there was absolutely no correlation.
The solvents with smaller and more linear molecular structure diffused out of the films more quickly than those with larger and more branched molecular structure.
HSP were developed in the process, however. HSP have been used widely since to accomplish correlations and to make systematic comparisons which one would not have thought possible earlier. The effects of hydrogen bonding, for example, are accounted for quantitatively. Many of these correlations are discussed later, including polymer solubility, swelling, and permeation; surface wetting and dewetting; solubility of inorganic salts; and biological applications including wood, cholesterol, etc.
The experimental limits on this seemingly universal ability to predict molecular affinities are apparently governed by the limits represented by energies of the liquid test solvents themselves. I decided to try to collect my experience for the purpose of a reference book, both for myself and for others. At the same time, a search of the major theories of polymer solution thermodynamics was undertaken to explore how the approaches compared.
A key element in this was to explain why the correlations all seemed to fit with an apparently "universal" 4 or 0. This is described in more detail in Chapter 2 Equation 2. My present view is that the "4" is the result of the validity of the geometric mean rule to describe not only dispersion interactions but also permanent dipole-permanent dipole and hydrogen bonding electron interchange interactions in mixtures of unlike molecules.
The Hildebrand approach uses this and was the basis of my earliest approach. The Prigogine corresponding states theory yields the "4" in the appropriate manner when the geometric mean rule is adopted Chapter 2, Equation 2. Any other kind of averaging gives the wrong result. Considering these facts and the massive amount of data that has been correlated using the "4" in the following, it appears proven beyond a reasonable doubt that the geometric mean assumption is valid not only for dispersion-type interactions or perhaps more correctly in the present context those interactions typical of aliphatic hydrocarbons but also for permanent dipole-permanent dipole and hydrogen bonding as well.
For those who wish to try to understand the Prigogine theory, I recommend starting with an article by Donald Patterson. Patterson 2 has also reviewed in understandable language the progression of developments in polymer solution thermodynamics from the Flory-Huggins theory, through that of Prigogine and coworkers, to the so-called "New Flory Theory.
All of the previous theories and their extensions also can be found in a more recent book. The striking aspect about all of this previous work is that no one has dared to enter into the topic of hydrogen bonding. The present quantitative treatment of permanent dipole-permanent dipole interactions and hydrogen bonding is central to the results reported in every chapter in this book. An attempt to relate this back to the previous theories is given briefly here and more extensively in Chapter 2.
This attempt has been directed through Patterson, 1 which may be called the Prigogine-Patterson approach, rather than through the Flory theory, as the relations with the former are more obvious.
I strongly recommend that studies be undertaken to confirm the usefulness of the "structural parameters" in the Prigogine theory or the Flory theory.
It is recognized that the effects of solvent molecular size, segment size, and polymer molecular size and shapes are not fully accounted for at the present time. There is hope that this can be done with structural parameters. The material presented here corresponds to my knowledge and experience at the time of writing, with all due respect to confidentiality agreements, etc. I am greatly indebted to many colleagues and supporters who have understood that at times one can be so preoccupied and lost in deep thought that the present just seems not to exist.
HansenWhen the question about a second edition of this handbook was posed, I was not in doubt that several additional authors were necessary to meet the demands it would require. The writings of the five contributors that were chosen speak for themselves.
Chapter 3 introduces statistical thermodynamics to confirm the division of cohesive energy into three parts enabling separate calculation of each. Chapter 4 describes how the Hansen solubility parameters HSP fit into other theories of polymer solutions. The practical applications and understanding provided in Chapter 9 Per Redelius related to asphalt, bitumen, and crude oil should accelerate new thinking in this area and emphasize that simple explanations of seemingly complex phenomena are usually the right ones.
The thermodynamic treatment of carbon dioxide given in Chapter 10 Laurie L. Williams is a model for similar work with other gases and emphatically confirms the usefulness of Hansen solubility parameters for predicting the solubility behavior of gases in liquids and therefore also in polymers. Chapter 11 John Durkee goes through the process of demonstrating how "designer" solvents can be used in cleaning operations to replace, or partly replace, ozone-depleting solvents, in spite of the problem of their HSP not being sufficiently close to the HSP of the soils that are to be removed.
I have added two chapters because of apparent need. Chapter 14 discusses environmental stress cracking ESC. ESC is a major cause of unexpected and sometimes catastrophic failure of plastics. The recent improved understanding provided by HSP seemed appropriate for inclusion in this context. Chapter 16 discusses absorption and diffusion in polymers. Many of the HSP correlations presented in this handbook cannot stand on HSP alone but must include consideration of absorption and diffusion of chemicals in polymers.
Polymer surface layers are often significantly different from the bulk polymer. This chapter tries to unify the effects of a verifiable surface resistance and verifiable concentration-dependent diffusion coefficients.
Solutions to the diffusion equation simultaneously considering these two effects explain the "anomalies" of absorption and also correctly model desorption phenomena, including the drying of a lacquer film from start to finish. Each of the chapters in the first edition has been reviewed and added to where this was felt appropriate without increasing the number of pages unduly.
There is still a lack of significant activity in the biological area, in controlled release applications, and in other areas discussed in Chapter 18, such as nanotechnology. The relative affinity of molecules or segments of molecules for each other can be predicted and in many cases controlled in self-assembly with the understanding provided by HSP.
Chapter 15 treating biological materials has been expanded more than the others included in the first edition. This was done with the help of Tim Svenstrup Poulsen. A lack of total success has stimulated further research. The skill with which solvents can be optimally selected with respect to cost, solvency, workplace environment, external environment, evaporation rate, flash point, etc. Most commercial suppliers of solvents have computer programs to help with solvent selection.
One can now easily predict how to dissolve a given polymer in a mixture of two solvents, neither of which can dissolve the polymer by itself. Unfortunately, this book cannot include discussion of all the significant efforts leading to our present knowledge of the solubility parameters. An attempt is made to outline developments, provide some background for a basic understanding, and give examples of uses in practice.
The key factor is to determine those affinities that the important components in a system have for each other.
For many products this means evaluating or estimating the relative affinities of solvents, polymers, additives, pigment surfaces, filler surfaces, fiber surfaces, and substrates.
It is noteworthy that the concepts presented here have developed toward not just predicting solubility that requires high affinity between solvent and solute, but for predicting affinities between different polymers, leading to compatibility, and affinities to surfaces to improve dispersion and adhesion.
In these applications the solubility parameter has become a tool, using well-defined liquids as energy probes, to measure the similarity, or lack of the same, of key components. Materials with widely different chemical structures may be very close in affinities. Only those materials that interact differently with different solvents can be characterized in this manner. It can be expected that many inorganic materials, such as fillers, will not interact differently with these energy probes as their energies are very much higher.
An adsorbed layer of water on the high-energy surface can also play an important role. Regardless of these concerns, it has been possible to characterize pigments, both organic and inorganic, as well as fillers like barium sulfate, zinc oxide, etc. Changing the surface energies by various treatments can lead to a surface that can be characterized more readily and often interacts more strongly with given organic solvents. When the same solvents that dissolve a polymeric binder are those which interact most strongly with a surface, it can be expected that the binder and the surface have high affinity for each other.
Solubility parameters are sometimes called cohesion energy parameters as they are derived from the energy required to convert a liquid to a gas. The energy of vaporization is a direct measure of the total cohesive energy holding the liquid's molecules together.
All types of bonds holding the liquid together are broken by evaporation, and this has led to the concepts described in more detail later. The term cohesion energy parameter is more appropriately used when referring to surface phenomena.
The solubility parameter is an important quantity for predicting solubility relations, as can be seen from the following brief introduction. Thermodynamics requires that the free energy of mixing must be zero or negative for the solution process to occur spontaneously.
Equation 1. This is discussed more in Chapter 2. Therefore, both positive and negative heats of mixing can be expected from theoretical considerations and have been measured accordingly. It has been clearly shown that solubility parameters can be used to predict both positive and negative heats of mixing. Previous objections to the effect that only positive values are allowed in this theory are incorrect. This discussion clearly demonstrates why the solubility parameter should be considered as a free energy parameter.
This is more in agreement with the use of the solubility parameter plots to follow. These use solubility parameters as axes and have experimentally determined boundaries of solubility defined by the fact that the free energy of mixing is zero. The combinatorial entropy enters as a constant factor in the plots of solubility in different solvents, for example, as the concentrations are usually constant for a given study. It is important to note that the solubility parameter, or rather the difference in solubility parameters for the solvent-solute combination, is important in determining the solubility of the system.
It is clear that a match in solubility parameters leads to a zero change in noncombinatorial free energy, and the positive entropy change the combinatorial entropy change , found on simple mixing to result in a disordered mixture compared to the pure components, will ensure that a solution is possible from a thermodynamic point of view.
CRC Handbook of Solubility Parameters and Other Cohesion Parameters Second Edition Free Books
The Hildebrand solubility parameter is the square root of the cohesive energy density :. The cohesive energy density is the amount of energy needed to completely remove unit volume of molecules from their neighbours to infinite separation an ideal gas. This is equal to the heat of vaporization of the compound divided by its molar volume in the condensed phase. In order for a material to dissolve, these same interactions need to be overcome, as the molecules are separated from each other and surrounded by the solvent. In Joel Henry Hildebrand suggested the square root of the cohesive energy density as a numerical value indicating solvency behavior. Materials with similar solubility parameters will be able to interact with each other, resulting in solvation , miscibility or swelling.
A group-contribution method for the estimation of Hansen solubility parameters of pure organic compounds is presented. It uses two kinds of characteristic groups: first-order groups that describe the basic molecular structure of compounds and second-order groups, which are based on the conjugation theory and improve the accuracy of predictions. A large variety of characteristic groups ensure the prediction of Hansen solubility parameters for a broad series of organic compounds, including those having complex multi-ring, heterocyclic, and aromatic structures. The predictions are exclusively based on the molecular structure of compounds, and no experimental data are needed. The predicted values permit a fairly reliable selection of solvents based on the radius of a Hansen solubility parameter sphere or on a Teas parameter ternary plot.
The CRC Handbook of Solubility Parameters and Other Cohesion Parameters, Second Edition, which includes 17 new sections and 40 new.
1 Solubility Parameters — An Introduction
Barton, Allan F. Second Edition in two Dunn. Parameters and otherCohesion Parameters, A. Handbook of SolubilityParameters and Other. Cohesion Parameters, Allan F.
This year is no exception. New tables, extensive updates, and added sections mean the Handbook has once again set a new standard for reliability, utility, and thoroughness. Barton, Oct 29, , Science, pages.
CRC Handbook of Solubility Parameters and Other Cohesion Parameters - Ebook
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CRC. HANDBOOK of. SOLUBILITY. PARAMETERS and. OTHER COHESION. PARAMETERS. Second Edition. Allan E M. Barton, Ph.D. Associate Professor of.
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