Barton Handbook Of Solubility Parameters
2021年12月17日Download here: http://gg.gg/xa5vo
*Barton Handbook Of Solubility Parameters Worksheet
*Barton Handbook Of Solubility Parameters
*Barton Handbook Of Solubility Parameters PdfChapter 35, A Short History of the Hansen Solubility Parameters
HANDBOOK of SOLUBILITY PARAMETERS and OTHER COHESION PARAMETERS Second Edition Allan E M. Associate Professor of Chemistry Murdoch University Perth, Western Australia CRC Press Boca Raton London New York Washington, D.C. In a world of aqueous and nonaqueous electrolytes. Barton’s recent work, ’Handbook of Solubility Parameters and Other Cohesion Parameters”2 is a good starting point for a serious study. Kamlet et a13 offer some newer thoughts on solubility including more recent references. Jensen4 in a recent chapter correctly notes that most of the solubility.
Handbook of Poylmer-Liquid Interaction Parameters and Solubility Parameters (Hardback) Allan F.M. Published by Taylor & Francis Inc, United States (1990) ISBN 10: ISBN 13: 440. Solubility Parameter Furfuryl Alcohol Cohesive Energy Density Diethyl Ketone Dibenzyl Ether These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves. Barton CRC Press, Oct 29, 1991 - Science - 768 pages 1 Review The CRC Handbook of Solubility Parameters and Other Cohesion Parameters, Second.
Figure 1‑1Where it all began: the initial HSP values for the 88 solvents were determined the hard way on this equipment in Hansen’s lab. δD is in the direction of the rods which had rings at regular intervals. δD = 14.9 and δP= δH=0 is at the lower foremost corner where there is a white label for n-hexane [14.9, 0, 0]. Magnets with wires glued to them were used to plot data for the provisional values for the three parameters using colored beads.
The Main Track
I was bornin Louisville, Kentucky. I graduated from the University of Louisville, SpeedScientific School with a B.Ch.E in 1961. Wanting to continue for a doctorate, Iwas in the process of working for a Ph.D. at the University of Wisconsin,Madison, having gotten a Masters degree, but wanting to take a year in Denmarkbefore having to “settle down” with the advanced degree. My father came fromDenmark, arriving in the US in 1929, and my mother’s family came to the US inthe late 1800’s. Not really knowing what had been done to accommodate a usefulstudy, I arrived in Denmark to find that I was able to stay not one year, buttwo years, provided I wrote a thesis to obtain a degree then called “teknisklicentiat”. I accepted and delivered the thesis in exactly 24 months asplanned. I knew from earlier correspondence that I could either work on anautomatic process control project or on a question in the coatings industryrelated to why solvent is retained in polymer films for years. I chose thelatter.
When I wasfinishing the work for the technical licentiate degree in 1964 [1] there were acouple of Master’s candidates working as a team on the use of solubilityparameters in the coatings industry at the Central Research Laboratory of theDanish Paint and Varnish Industry. I advised them occasionally and this leadindirectly to the development of what are now called Hansen solubilityparameters. I was formally associated with the Technical University of Denmark(at that time called Den polytekniske Læreanstalt) where Prof. AndersBjörkman arranged for my stay. The actual work was done at the abovelaboratory led by Mr. Hans Kristian Raaschou Nielsen, in a rather small roomwith a slanting ceiling on the uppermost floor at Odensegade 14, Copenhagen Ø.
As statedabove, my licentiate thesis was to explain how solvent could be retained incoatings for many years. It was thought that this was caused by hydrogenbonding. I showed solvent was retained because of very low diffusioncoefficients. It is especially difficult to get through the surface of acoating where there is essentially no solvent and diffusion coefficients arevery low. The diffusion controlled phase followed a phase where most of thesolvent initially present freely evaporated. In the meantime it was necessaryto account for the hydrogen bonding capability of the test solvents, because ofwhat was believed at the time. The work of Harry Burrell [2] provided the basisfor selecting test solvents. He qualitatively ranked a number of solvents accordingto weak, moderate, or strong hydrogen bonding. The licentiate thesis did nottreat solubility parameters as such, dealing only with diffusion and filmdrying, since it was not hydrogen bonding or the solubility parameter that hadanything to do with the problem, other than allowing solution in the firstplace. There was, however, established a battery of solvents and knowledgeabout solubility parameters at the laboratory, and the Master’s candidates wereto further the development of this area.
An articleby Blanks and Prausnitz appeared [3] and I advised the students to make use ofthe new method of dividing the Hildebrand parameter into two parts, one fordispersion interactions and one for what was called “polar” interactions. Theydid not do so, having already gotten into their study and they needed to finishas planned, being short on time. After I turned in my licentiate thesis forevaluation, I looked at their experimental data using two dimensional plots ofthe dispersion parameter versus the new “polar parameter” as described byBlanks and Prausnitz. I could see there were well-defined regions of solubilityon the plots. For some polymers there were bad solvents within the good regionof the 2D plots. For other polymers these were the good solvents. The otherones had now become bad. The one group was largely alcohols, glycols, and etheralcohols, with the other being ketones, acetates, etc. It seemed logical to usea third dimension, pushing the bad solvents into another dimension, and thiswas the basis for the original terminology “The Three Dimensional SolubilityParameter” that was used in the original publications in 1967 [4-7]. I followedthe rule that the sum of energies in the (now) three partial parameters had toequal the total reflected by the Hildebrand parameter, recognizing that Blanksand Prausnitz were correct as far as they had gone. No one up to that point hadrecognized that the hydrogen bonding effects were included along with the polarand dispersion effects within the Hildebrand parameter itself. The Hildebrand parameter is basedsolely on the total cohesive energy (density) as measured quantitatively by thelatent heat of vaporization (minus RT). Hydrogen bonding was considered toospecial to allow such a simple approach as the HSP division of the totalcohesion energy into dispersion, polar, and hydrogen bonding contributions.Efforts prior to Blanks and Prausnitz had used the Hildebrand parametertogether with some more or less empirical hydrogen bonding parameter, forexample, in efforts to make useful solubility plots. Barton’s handbooks reviewthese earlier attempts in an exemplary manner, and as usual I refer to hishandbooks for these developments rather than repeating their content [8,9].
Prior tothe public defense of the licentiate thesis, I visited the US, returning toDenmark for the big day. While in the US I visited the Univ. of Wisconsin totry to establish a continuation of the earlier studies based on the promisingwork on solubility parameters that had become obvious to me, at least.Professors Ferry (of WLF equation fame), DiBenedetto, and Crosby, all wouldaccept me, but only working on projects for which they already had funding.After return to Denmark for the public defense, Prof. Björkman urged me tostay on to complete a Danish dr. techn. (similar to D.Sc.). I accepted, andfound a room with a relative, rather than in the student dormitory where I alsogot indoctrinated into the student life of the time in Denmark. 1967 was a bigyear. My father had to come to Denmark twice, once for a wedding and once forthe public defense of the dr. techn. thesis, an event he could not quitebelieve would happen. He himself was a chemical engineering graduate from thesame school, and knew that not that many got so far. It is my belief thatbecause of the privileges provided by Prof. Björkman (just do it at yourown speed), that I am the youngest (29) to ever have been awarded this degree.The requirements of the technical doctorate are that one presents and defendshis or her own ideas in a written publication. This must then be defended in avery formal (coat and tails) public event with official opponents that must notlast longer than 6 hours. There was newspaper coverage with an audience of 125,filling every seat in the auditorium. My official opponents were Prof. AndersBjörkman (polymers), Prof. Bengt Rånby (polymers), and Prof.Jørgen Koefoed (physical chemistry). The event lasted about 4 hours. Asan indication of the iconoclastic nature of this thesis, Prof. Koefoedchallenged in advance that I could not assign the three parameters toformamide, and that the mixture of equal molar amounts of chloroform andacetone must give deviations. I then proceeded to assign the three parametersto formamide by calculation and experiment, and tried to experimentally testall of my test solutes in the acetone/chloroform mixture. There were no errorsin the predictions. The thesis was accepted.
I initiallyhad a three dimensional model as shown in the opening figure made with metalrods at equal spacing supported by clear poly(methyl methacrylate) sides. Therewere rings on the rods at uniform intervals. The D parameter was in thedirection of the rods, varying from 7 to 10 in the old units (cal/cc)½.Each of what ultimately became about 90 solvents was represented by a givenmagnet to which a wire was glued so that given points in the space could belabeled. A small green bead was place on the tip of the wire for a good solventand a small red one was used for a bad solvent. One could thus make a 3Dsolubility plot for each of the 33 solutes. These were mainly polymers chosento potentially have such widely different solubility properties as possible. Ifa given solvent seemed to be giving consistent errors, its P and H parameters wereadjusted, keeping the D parameter constant, and the magnet with wire tip wasmoved. This trial and error procedure clearly showed the value of the threedimensional methodology. Tests were made with mixtures of non-solvents. If sucha mixture dissolved a given solute, the solvents had to be on opposite sides ofthe region of solubility. It they did not they were on the same side. Thismethod was used to confirm the parameters for as many of the solvents as wasreasonable. I then took a solvent and willfully placed it on the wrong side ofthe system and started all over. It became obvious that the system wasinverting, so it was concluded that these numbers were reasonably good, butwould probably need revision at some time. Publications were prepared.
The firstrevision came rather quickly in 1967 from the insight of a colleague at theDanish laboratory, Klemen Skaarup. He found the Böttcher equation for thepolar parameter, did a lot of calculations, and plotting, and the initialvalues were revised accordingly. The changes involved in these revisions werenot that great as can be seen from the earlier publications. Mr. Skaarup wasalso responsible for the first use of the “4” in the key equation of themethodology, finding this would give spheres rather than spheroids for thesolubility regions. The “4” was generally considered as empirical for manyyears thereafter.
These“three dimensional” concepts were reported in three articles in the Journal ofPaint Technology and in the dr. techn. thesis, which also included an expandedsection on diffusion in polymers and film formation, in 1967 [4-7]. I havereviewed the dr. techn. thesis many times, and have found nothing wrong with ityet. It can be found as a PDF file on my website www.hansen-solubility.com.
Just priorto the public defense of the dr. techn. thesis I corresponded with Prof.Prausnitz to see whether the studies could be continued with him. The responsewas that there was no funding.Ithen took a job at the PPG Industries Research and Development Center in thePittsburgh area. These eight years were very rewarding with a remarkablyinspiring leadership “Making Science Useful” (Dr. Howard Gerhard and Dr. MarcoWismer). There were many confirmations that the methodology could be used togreat advantage in practical situations. I was popular in the purchasingdepartment during the solvent crisis (oil crisis) where one had to buy whateverwas available on the spot. I could immediately on the phone confirm whether ornot a given solvent could be used and the usual testing was not done. Shiploadsof solvent were bought on this basis only.
Dr. AlanBeerbower at Esso (now Exxon) was just waiting for me, as he said it himself,and took up the developments in the 1967 publications in many areas as can beseen in our article in the Encyclopedia of Chemical Technology [10] and in hismany publications on a variety of topics, often related to surfaces,lubrication, and surfactant behavior, for example in [11,12]. He developedgroup contributions, adding to what was known at that time (citing Fedors),that I used and reported in the handbooks [13,14]. It was Dr. Beerbower whofirst used the term Hansen plot as far as I know. Dr. Beerbower authored abrochure for Esso that appeared in 1970 entitled “Parameters of Solubility”. Hereis the cover of that handbook and inside, Beerbower’s reference to the Hansenprinciple:Barton Handbook Of Solubility Parameters Worksheet
Figure 1‑2Perhaps thefirst reference to Hansen (component) parameters in the literature fromBeerbower’s 1970 handbook and a gratifying confirmation of 97% accuracy forprediction of solubility.
I have put one of his figures in theHandbooks [13,14]. In the Second Edition this is on page 338. This figure alsoappeared in Beerbower’s publications but I got it only as a personalcommunication. Sometime after the appearance of the article in the Encyclopediaof Chemical Technology [10] in 1971, where the terminology was not changed, probablybecause I did not use it, Hansen (solubility/cohesion) parameters replaced the“three dimensional” terminology on a more general basis. Van Krevelen did notlike three dimensional systems, but did the group contributions for the“solubility parameters” anyway in his “Properties of Polymers” from 1975, sothe change in terminology was not complete at this point in time.Barton’ handbook in 1983 used the Hansenparameter terminology as cited below. I have never had contact with VanKrevelen. A US Coast Guard project in 1988-9 studying chemical protectiveclothing brought me back on track in terms of adding a significant number ofsolvents to the database. I was to find solvents for testing that couldpermeate a PTFE body suit after having established a correlation for thosesolvents that had been tested. As it turned out there were indeed quite a fewsolvents that permeated the PTFE suitthat were characterized by molar volumes less than about 60 cc/mole andmonomers with terminal double bonds that could be somewhat larger [13,14] (seethe figure on page 247 of the second edition of the handbook). I actuallyinitially had a technician looking at the published Van Krevelen groupcontribution approach early in this project, before realizing that I had to doit myself with the Beerbower group contributions that I had gotten as a privatecommunication. The Van Krevelen and Hoy approaches are now outdated, beingsurpassed by the work of Stefanis and Panayiotou (See for example Chapter 3 inthe Second edition of the handbook or their other publications. HSP estimates by the S-P statisticalthermodynamics methodology are also included in HSPiP). Even this has beenoutdated very recently by the work of Dr. Hiroshi Yamamoto in the HSPiP whereit is called the Y-MB method for Yamamoto Molecular Breaking. Both Hiroshi andI independently found that one did much better when using larger “groups” forthe still larger molecules, even to the extent of directly using the existingHSP of multifunctional molecules as a whole as a single group.
Thesuperiority of modern computers that are capable of working with huge databasesto generate correlations with rapidity and flexibility stands in contrast towhat was done earlier. The first calculations for dividing the latent heatsinto partial solubility parameters were done using a slide rule. Indeed therewere computers that could have helped with this at the time, but this costmoney, and the data were very scattered in the literature. The first computerprogram to calculate the HSP spheres from experimental data was probably thatat PPG Industries around 1968. My lab there was set up to routinely determinethe experimental data that helped to optimize solvents and to predictcompatibility. Safety and the environment were emphasized. A similar programwas available at the single, central computer of the Scandinavian Paint andPrinting Ink Research Institute, and later on my son, Kristian, wrote the sametype of program for use at our home on a Commodore 64. This typically tookabout 20-30 minutes to calculate the HSP sphere from data on approximately 40solvents. Much of the data in the handbooks was done on this computer.
I left PPGin 1976 to become director of the Scandinavian Paint and Printing Ink ResearchInstitute, being invited to do so largely at the suggestion of the Swedishparticipants (Prof. Bengt Rånby, Prof. Sven Brohult). This was aDanish-Swedish organization at the time, but when I left 10 years later,Finland and Norway were also part of the Nordic cooperation. These 10 yearsalso led to further progress and development of knowledge in the area, mostlyin the further characterization of materials and from applications in industry.Research as such was not permitted at my final place of employment, FORCETechnology, so the developments were not as extensive as what might have beenexpected. I did manage to write the first edition of the handbook (at home)[13], and to search for and find what I believe to be theoretical justificationfor the “4” in the key HSP equation. The Prigogine corresponding states theoryof polymer solutions has the “4” in the first term of the free energy equation,but only when the geometric mean is used to predict interactions between unlikemolecules. Other averages give quite different results. The HSP approach also uses thecorresponding states approach wisely chosen by Blanks and Prausnitz, comparingdata for a given solvent with corresponding states data for its look-alikehydrocarbon solvent (homomorph). Blanks and Prausnitz inherently also assumedthe geometric mean for the molecular dipole-dipole interactions. To this daythere are those who protest inclusion of the hydrogen bonding as is done in theHansen methodology. These interactions are considered non-symmetrical with onlysymmetrical interactions being describable by the solubility parameter theory.It seems that if dipolar molecular interactions and the orientation inv
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*Barton Handbook Of Solubility Parameters Worksheet
*Barton Handbook Of Solubility Parameters
*Barton Handbook Of Solubility Parameters PdfChapter 35, A Short History of the Hansen Solubility Parameters
HANDBOOK of SOLUBILITY PARAMETERS and OTHER COHESION PARAMETERS Second Edition Allan E M. Associate Professor of Chemistry Murdoch University Perth, Western Australia CRC Press Boca Raton London New York Washington, D.C. In a world of aqueous and nonaqueous electrolytes. Barton’s recent work, ’Handbook of Solubility Parameters and Other Cohesion Parameters”2 is a good starting point for a serious study. Kamlet et a13 offer some newer thoughts on solubility including more recent references. Jensen4 in a recent chapter correctly notes that most of the solubility.
Handbook of Poylmer-Liquid Interaction Parameters and Solubility Parameters (Hardback) Allan F.M. Published by Taylor & Francis Inc, United States (1990) ISBN 10: ISBN 13: 440. Solubility Parameter Furfuryl Alcohol Cohesive Energy Density Diethyl Ketone Dibenzyl Ether These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves. Barton CRC Press, Oct 29, 1991 - Science - 768 pages 1 Review The CRC Handbook of Solubility Parameters and Other Cohesion Parameters, Second.
Figure 1‑1Where it all began: the initial HSP values for the 88 solvents were determined the hard way on this equipment in Hansen’s lab. δD is in the direction of the rods which had rings at regular intervals. δD = 14.9 and δP= δH=0 is at the lower foremost corner where there is a white label for n-hexane [14.9, 0, 0]. Magnets with wires glued to them were used to plot data for the provisional values for the three parameters using colored beads.
The Main Track
I was bornin Louisville, Kentucky. I graduated from the University of Louisville, SpeedScientific School with a B.Ch.E in 1961. Wanting to continue for a doctorate, Iwas in the process of working for a Ph.D. at the University of Wisconsin,Madison, having gotten a Masters degree, but wanting to take a year in Denmarkbefore having to “settle down” with the advanced degree. My father came fromDenmark, arriving in the US in 1929, and my mother’s family came to the US inthe late 1800’s. Not really knowing what had been done to accommodate a usefulstudy, I arrived in Denmark to find that I was able to stay not one year, buttwo years, provided I wrote a thesis to obtain a degree then called “teknisklicentiat”. I accepted and delivered the thesis in exactly 24 months asplanned. I knew from earlier correspondence that I could either work on anautomatic process control project or on a question in the coatings industryrelated to why solvent is retained in polymer films for years. I chose thelatter.
When I wasfinishing the work for the technical licentiate degree in 1964 [1] there were acouple of Master’s candidates working as a team on the use of solubilityparameters in the coatings industry at the Central Research Laboratory of theDanish Paint and Varnish Industry. I advised them occasionally and this leadindirectly to the development of what are now called Hansen solubilityparameters. I was formally associated with the Technical University of Denmark(at that time called Den polytekniske Læreanstalt) where Prof. AndersBjörkman arranged for my stay. The actual work was done at the abovelaboratory led by Mr. Hans Kristian Raaschou Nielsen, in a rather small roomwith a slanting ceiling on the uppermost floor at Odensegade 14, Copenhagen Ø.
As statedabove, my licentiate thesis was to explain how solvent could be retained incoatings for many years. It was thought that this was caused by hydrogenbonding. I showed solvent was retained because of very low diffusioncoefficients. It is especially difficult to get through the surface of acoating where there is essentially no solvent and diffusion coefficients arevery low. The diffusion controlled phase followed a phase where most of thesolvent initially present freely evaporated. In the meantime it was necessaryto account for the hydrogen bonding capability of the test solvents, because ofwhat was believed at the time. The work of Harry Burrell [2] provided the basisfor selecting test solvents. He qualitatively ranked a number of solvents accordingto weak, moderate, or strong hydrogen bonding. The licentiate thesis did nottreat solubility parameters as such, dealing only with diffusion and filmdrying, since it was not hydrogen bonding or the solubility parameter that hadanything to do with the problem, other than allowing solution in the firstplace. There was, however, established a battery of solvents and knowledgeabout solubility parameters at the laboratory, and the Master’s candidates wereto further the development of this area.
An articleby Blanks and Prausnitz appeared [3] and I advised the students to make use ofthe new method of dividing the Hildebrand parameter into two parts, one fordispersion interactions and one for what was called “polar” interactions. Theydid not do so, having already gotten into their study and they needed to finishas planned, being short on time. After I turned in my licentiate thesis forevaluation, I looked at their experimental data using two dimensional plots ofthe dispersion parameter versus the new “polar parameter” as described byBlanks and Prausnitz. I could see there were well-defined regions of solubilityon the plots. For some polymers there were bad solvents within the good regionof the 2D plots. For other polymers these were the good solvents. The otherones had now become bad. The one group was largely alcohols, glycols, and etheralcohols, with the other being ketones, acetates, etc. It seemed logical to usea third dimension, pushing the bad solvents into another dimension, and thiswas the basis for the original terminology “The Three Dimensional SolubilityParameter” that was used in the original publications in 1967 [4-7]. I followedthe rule that the sum of energies in the (now) three partial parameters had toequal the total reflected by the Hildebrand parameter, recognizing that Blanksand Prausnitz were correct as far as they had gone. No one up to that point hadrecognized that the hydrogen bonding effects were included along with the polarand dispersion effects within the Hildebrand parameter itself. The Hildebrand parameter is basedsolely on the total cohesive energy (density) as measured quantitatively by thelatent heat of vaporization (minus RT). Hydrogen bonding was considered toospecial to allow such a simple approach as the HSP division of the totalcohesion energy into dispersion, polar, and hydrogen bonding contributions.Efforts prior to Blanks and Prausnitz had used the Hildebrand parametertogether with some more or less empirical hydrogen bonding parameter, forexample, in efforts to make useful solubility plots. Barton’s handbooks reviewthese earlier attempts in an exemplary manner, and as usual I refer to hishandbooks for these developments rather than repeating their content [8,9].
Prior tothe public defense of the licentiate thesis, I visited the US, returning toDenmark for the big day. While in the US I visited the Univ. of Wisconsin totry to establish a continuation of the earlier studies based on the promisingwork on solubility parameters that had become obvious to me, at least.Professors Ferry (of WLF equation fame), DiBenedetto, and Crosby, all wouldaccept me, but only working on projects for which they already had funding.After return to Denmark for the public defense, Prof. Björkman urged me tostay on to complete a Danish dr. techn. (similar to D.Sc.). I accepted, andfound a room with a relative, rather than in the student dormitory where I alsogot indoctrinated into the student life of the time in Denmark. 1967 was a bigyear. My father had to come to Denmark twice, once for a wedding and once forthe public defense of the dr. techn. thesis, an event he could not quitebelieve would happen. He himself was a chemical engineering graduate from thesame school, and knew that not that many got so far. It is my belief thatbecause of the privileges provided by Prof. Björkman (just do it at yourown speed), that I am the youngest (29) to ever have been awarded this degree.The requirements of the technical doctorate are that one presents and defendshis or her own ideas in a written publication. This must then be defended in avery formal (coat and tails) public event with official opponents that must notlast longer than 6 hours. There was newspaper coverage with an audience of 125,filling every seat in the auditorium. My official opponents were Prof. AndersBjörkman (polymers), Prof. Bengt Rånby (polymers), and Prof.Jørgen Koefoed (physical chemistry). The event lasted about 4 hours. Asan indication of the iconoclastic nature of this thesis, Prof. Koefoedchallenged in advance that I could not assign the three parameters toformamide, and that the mixture of equal molar amounts of chloroform andacetone must give deviations. I then proceeded to assign the three parametersto formamide by calculation and experiment, and tried to experimentally testall of my test solutes in the acetone/chloroform mixture. There were no errorsin the predictions. The thesis was accepted.
I initiallyhad a three dimensional model as shown in the opening figure made with metalrods at equal spacing supported by clear poly(methyl methacrylate) sides. Therewere rings on the rods at uniform intervals. The D parameter was in thedirection of the rods, varying from 7 to 10 in the old units (cal/cc)½.Each of what ultimately became about 90 solvents was represented by a givenmagnet to which a wire was glued so that given points in the space could belabeled. A small green bead was place on the tip of the wire for a good solventand a small red one was used for a bad solvent. One could thus make a 3Dsolubility plot for each of the 33 solutes. These were mainly polymers chosento potentially have such widely different solubility properties as possible. Ifa given solvent seemed to be giving consistent errors, its P and H parameters wereadjusted, keeping the D parameter constant, and the magnet with wire tip wasmoved. This trial and error procedure clearly showed the value of the threedimensional methodology. Tests were made with mixtures of non-solvents. If sucha mixture dissolved a given solute, the solvents had to be on opposite sides ofthe region of solubility. It they did not they were on the same side. Thismethod was used to confirm the parameters for as many of the solvents as wasreasonable. I then took a solvent and willfully placed it on the wrong side ofthe system and started all over. It became obvious that the system wasinverting, so it was concluded that these numbers were reasonably good, butwould probably need revision at some time. Publications were prepared.
The firstrevision came rather quickly in 1967 from the insight of a colleague at theDanish laboratory, Klemen Skaarup. He found the Böttcher equation for thepolar parameter, did a lot of calculations, and plotting, and the initialvalues were revised accordingly. The changes involved in these revisions werenot that great as can be seen from the earlier publications. Mr. Skaarup wasalso responsible for the first use of the “4” in the key equation of themethodology, finding this would give spheres rather than spheroids for thesolubility regions. The “4” was generally considered as empirical for manyyears thereafter.
These“three dimensional” concepts were reported in three articles in the Journal ofPaint Technology and in the dr. techn. thesis, which also included an expandedsection on diffusion in polymers and film formation, in 1967 [4-7]. I havereviewed the dr. techn. thesis many times, and have found nothing wrong with ityet. It can be found as a PDF file on my website www.hansen-solubility.com.
Just priorto the public defense of the dr. techn. thesis I corresponded with Prof.Prausnitz to see whether the studies could be continued with him. The responsewas that there was no funding.Ithen took a job at the PPG Industries Research and Development Center in thePittsburgh area. These eight years were very rewarding with a remarkablyinspiring leadership “Making Science Useful” (Dr. Howard Gerhard and Dr. MarcoWismer). There were many confirmations that the methodology could be used togreat advantage in practical situations. I was popular in the purchasingdepartment during the solvent crisis (oil crisis) where one had to buy whateverwas available on the spot. I could immediately on the phone confirm whether ornot a given solvent could be used and the usual testing was not done. Shiploadsof solvent were bought on this basis only.
Dr. AlanBeerbower at Esso (now Exxon) was just waiting for me, as he said it himself,and took up the developments in the 1967 publications in many areas as can beseen in our article in the Encyclopedia of Chemical Technology [10] and in hismany publications on a variety of topics, often related to surfaces,lubrication, and surfactant behavior, for example in [11,12]. He developedgroup contributions, adding to what was known at that time (citing Fedors),that I used and reported in the handbooks [13,14]. It was Dr. Beerbower whofirst used the term Hansen plot as far as I know. Dr. Beerbower authored abrochure for Esso that appeared in 1970 entitled “Parameters of Solubility”. Hereis the cover of that handbook and inside, Beerbower’s reference to the Hansenprinciple:Barton Handbook Of Solubility Parameters Worksheet
Figure 1‑2Perhaps thefirst reference to Hansen (component) parameters in the literature fromBeerbower’s 1970 handbook and a gratifying confirmation of 97% accuracy forprediction of solubility.
I have put one of his figures in theHandbooks [13,14]. In the Second Edition this is on page 338. This figure alsoappeared in Beerbower’s publications but I got it only as a personalcommunication. Sometime after the appearance of the article in the Encyclopediaof Chemical Technology [10] in 1971, where the terminology was not changed, probablybecause I did not use it, Hansen (solubility/cohesion) parameters replaced the“three dimensional” terminology on a more general basis. Van Krevelen did notlike three dimensional systems, but did the group contributions for the“solubility parameters” anyway in his “Properties of Polymers” from 1975, sothe change in terminology was not complete at this point in time.Barton’ handbook in 1983 used the Hansenparameter terminology as cited below. I have never had contact with VanKrevelen. A US Coast Guard project in 1988-9 studying chemical protectiveclothing brought me back on track in terms of adding a significant number ofsolvents to the database. I was to find solvents for testing that couldpermeate a PTFE body suit after having established a correlation for thosesolvents that had been tested. As it turned out there were indeed quite a fewsolvents that permeated the PTFE suitthat were characterized by molar volumes less than about 60 cc/mole andmonomers with terminal double bonds that could be somewhat larger [13,14] (seethe figure on page 247 of the second edition of the handbook). I actuallyinitially had a technician looking at the published Van Krevelen groupcontribution approach early in this project, before realizing that I had to doit myself with the Beerbower group contributions that I had gotten as a privatecommunication. The Van Krevelen and Hoy approaches are now outdated, beingsurpassed by the work of Stefanis and Panayiotou (See for example Chapter 3 inthe Second edition of the handbook or their other publications. HSP estimates by the S-P statisticalthermodynamics methodology are also included in HSPiP). Even this has beenoutdated very recently by the work of Dr. Hiroshi Yamamoto in the HSPiP whereit is called the Y-MB method for Yamamoto Molecular Breaking. Both Hiroshi andI independently found that one did much better when using larger “groups” forthe still larger molecules, even to the extent of directly using the existingHSP of multifunctional molecules as a whole as a single group.
Thesuperiority of modern computers that are capable of working with huge databasesto generate correlations with rapidity and flexibility stands in contrast towhat was done earlier. The first calculations for dividing the latent heatsinto partial solubility parameters were done using a slide rule. Indeed therewere computers that could have helped with this at the time, but this costmoney, and the data were very scattered in the literature. The first computerprogram to calculate the HSP spheres from experimental data was probably thatat PPG Industries around 1968. My lab there was set up to routinely determinethe experimental data that helped to optimize solvents and to predictcompatibility. Safety and the environment were emphasized. A similar programwas available at the single, central computer of the Scandinavian Paint andPrinting Ink Research Institute, and later on my son, Kristian, wrote the sametype of program for use at our home on a Commodore 64. This typically tookabout 20-30 minutes to calculate the HSP sphere from data on approximately 40solvents. Much of the data in the handbooks was done on this computer.
I left PPGin 1976 to become director of the Scandinavian Paint and Printing Ink ResearchInstitute, being invited to do so largely at the suggestion of the Swedishparticipants (Prof. Bengt Rånby, Prof. Sven Brohult). This was aDanish-Swedish organization at the time, but when I left 10 years later,Finland and Norway were also part of the Nordic cooperation. These 10 yearsalso led to further progress and development of knowledge in the area, mostlyin the further characterization of materials and from applications in industry.Research as such was not permitted at my final place of employment, FORCETechnology, so the developments were not as extensive as what might have beenexpected. I did manage to write the first edition of the handbook (at home)[13], and to search for and find what I believe to be theoretical justificationfor the “4” in the key HSP equation. The Prigogine corresponding states theoryof polymer solutions has the “4” in the first term of the free energy equation,but only when the geometric mean is used to predict interactions between unlikemolecules. Other averages give quite different results. The HSP approach also uses thecorresponding states approach wisely chosen by Blanks and Prausnitz, comparingdata for a given solvent with corresponding states data for its look-alikehydrocarbon solvent (homomorph). Blanks and Prausnitz inherently also assumedthe geometric mean for the molecular dipole-dipole interactions. To this daythere are those who protest inclusion of the hydrogen bonding as is done in theHansen methodology. These interactions are considered non-symmetrical with onlysymmetrical interactions being describable by the solubility parameter theory.It seems that if dipolar molecular interactions and the orientation inv
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