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28-Jan-2013

HSP Application note #3

Swelling of Packing Rubber and Hansen Solubility Parameter(HSP)

2010.2.13

HSPiP Team Senior Developer, Dr. Hiroshi Yamamoto

 

A lot of packing are used in chemical engineering area, and manufacturer provide swelling data of their packing for many kind of solvents. But almost all case, that is pure solvent’s data and there are so few data available for mixture solvents. With this article, I show you haw to evaluate mixture of solvents for packing swelling.
For this study, I choose fluoropolymer packing. And Analyze with HSP.

Hansen Solubility Parameters (HSP)

Hansen Solubility Parameters(HSP) were developed by Charles M. Hansen as a way of predicting if one material will dissolve in another and form a solution. They are based on the idea that "like dissolves like" where one molecule is defined as being 'like' another if it bonds to itself in a similar way.
Specifically, each molecule is given three Hansen parameters, each generally measured in MPa0.5:
dD:The energy from dispersion bonds between molecules
dP:The energy from dipolar intermolecular force between molecules
dH:The energy from hydrogen bonds between molecules.
These three parameters can be treated as Vector for a point in three dimensions also known as the Hansen space. The nearer two molecules HSP Vector are in this three dimensional space, the more likely they are to dissolve into each other.

What can perhaps be surprising is that one can assign HSP to so many different things. Gases like carbon dioxide, solids like carbon-60, sugar, and biological materials like human skin, depot fat, DNA, and even some proteins all have HSP. The list can be continued with drugs, polymers, plasticizers, and in fact any organic material and even many inorganic materials like salts. The only requirement for an experimental confirmation is that the material must behave differently in a sufficient number of test solvents upon contact.

Pirika JAVA Demo Applet calculate HSP. HSPLight is available here.
Please refer to e-Book of HSPiP if you want know more about HSP.
About the Power Tools that handle HSP more effectively.

Viton is DuPont’s trade mark, and there are so many swelling data exist on the net. I got several technical catalogs.
DuPont Dow Elastomers, Technical Information Kalrez
VitonGeneralInfo_05-Jul.PDF、Viton05.pdf

2011.4.16 Let's beccome Packing Designer! Please input composition of monomers and push Calc. button. You will get image of polymer.

VdF(A) mol%
HFP(B) mol%
TFE(C) mol%
Ety(D) mol%
Pro(E) mol%



If you want to know much about Radical polymerization, please refer to Pirika polymer

It is not specify, but maybe this solubility data is for Viton A.
Viton A is vinylidene fluoride and Hexafluoro propylene copolymer. (Please refer to PVdF solubility article)
More than 50% swelling solvents, I set score 1.

Hcode Name dD dP dH Score temp Vol
195 trans-decahydronaphthalene 18 0 0 0 159.3
46 aniline 20.1 5.8 11.2 0 91.6
122 carbon tetrachloride 17.8 0 0.6 0 97.1
181 cyclohexane 16.8 0 0.2 0 108.9
366 1,2-dibromoethane 19.2 3.5 8.6 0 86.6
182 cyclohexanol 17.4 4.1 13.5 0 105.7
670 2,2,4-trimethylpentane 14.1 0 0 0 165.5
396 formaldehyde 12.8 14.4 15.4 0 36.9
398 formic acid 14.6 10 14 0 37.9
456 methyl alcohol 14.7 12.3 22.3 0 40.6
325 ethyl alcohol 15.8 8.8 19.4 0 58.6
52 benzene 18.4 0 2 0 89.5
333 ethylbenzene 17.8 0.6 1.4 0 122.8
637 toluene 18 1.4 2 0 106.6
698 o-xylene 17.8 1 3.1 0 121.1
417 hexane 14.9 0 0 0 131.4
531 nitrobenzene 20 10.6 3.1 0 102.7
649 trichloroethylene 18 3.1 5.3 0 90.1
814 p-chlorotoluene 19.1 6.2 2.6 0 119.1
156 chloroform 17.8 3.1 5.7 0 80.5
270 2-(2-methoxyethoxy)ethanol 16.2 7.8 12.6 0 118.2
404 furfural 18.6 14.9 5.1 0 83.2
1145 dimethyl maleate 16.3 8.3 9.8 0 125.5
306 1,4-dioxane 17.5 1.8 9 0 85.7
598 pyridine 19 8.8 5.9 0 80.9
115 gamma-butyrolactone 18 16.6 7.4 0 76.5
11 acetophenone 18.8 10 4 0 117.4
209 diacetone alcohol 15.8 8.2 10.8 0 124.3
1016 ethylacetoacetate 16.5 7.3 8.3 0 127.3
1037 methyl acetoacetate 16.4 8.6 8.9 0 108.3
6 acetic anhydride 16 11.7 10.2 0 95
25 acrylonitrile 16 12.8 6.8 0 66.2
297 N,N'-dimethylformamide 17.4 13.7 11.3 1 77.4
429 isopentyl acetate 15.3 3.1 7 1 150.2
997 2-methyltetrahydrofuran 16.9 5 4.3 1 100.2
617 tetrahydrofuran 16.8 5.7 8 1 81.9
328 ethyl acetate 15.8 5.3 7.2 1 98.6
285 N,N'-dimethylacetamide 16.8 11.5 10.2 1 93
467 methyl acrylate 15.3 6.7 9.4 1 90.7
1143 diethyl oxalate 16.2 8 8.8 1 136.2
659 triethyl phosphate 16.7 11.4 9.2 1 170.8
438 isophorone 17 8 5 1 150.3
491 4-methyl-2-pentanone 15.3 6.1 4.1 1 125.8
464 methyl acetate 15.5 7.2 7.6 1 79.8
254 diethyl carbonate 15.1 6.3 3.5 1 121.7
481 methyl ethyl ketone 16 9 5.1 1 90.2
17 acetylacetone 16.1 10 6.2 1 103.1
7 acetone 15.5 10.4 7 1   73.8

I load this data with HSPiP and calculated Sphere.

 

HSPiP(Hansen Solubility Parameters in Practice)

The first edition of HSPiP that appeared in November, 2008, greatly enhanced the usefulness of the Hansen solubility parameters (HSP).

The HSP values of over 1200++ chemicals and 500 polymers are provided in convenient electronic format and have been revised and updated using the latest data sources in the second edition (March, 2009).

A third edition of the HSPiP appeared in March, 2010. There are now 10,000 compounds in the HSP file which also includes data on density, melting point, boiling point, critical parameters, Antoine constants and much more. The user is able to carry out many different sorts of optimisations of solubility, evaporation, diffusion, adhesion, create their own datasets (automatically if required) and explore the huge range of applications for HSP in coatings, paints, nanoparticles, cosmetics, pharma, organic photovoltaics and much more.

The 3rd Edition v3.1 was released on 12 December 2010. Current users can upgrade free (now v3.1.09) by downloading the latest .msi installer from http://hansen-solubility.com

The 4th Edition v4.0.x was released on 2 Jan. 2013. The Current users can upgrade with free charge.

2013.1.28 The Visual How to manual of HSPiP. You can understand what HSPiP can do.
Please check the Functional Group List whether your targets are available with HSPiP.
How to purchase HSPiP
2013..1.2 The HSPiP ver. 4 include Power Tools for HSPiP power user.

Hansen Sphere

To determine if the parameters of two molecules (usually a solvent and a polymer) are within range a value called interaction radius (R0) is given to the substance being dissolved. This value determines the radius of the sphere in Hansen space and its center is the three Hansen parameters.

From version 3.1.X, Double Spheres function is available.

Pirika provide JAVA 3D Demo Applet to browse the Sphere(s).
The HTML5 Sphere Viewer examples are available here.
Now we have Power Tool "Sphere Viewer", GUI HTML5 software on HSPiP ver. 4.

 

And get HSP value of Viton A.
HSP become [14.63, 9.98, 1.59] and Interaction radius become 8.8.

2011.4.14

Drag=Rotate, Drag+Shift=Larger/Smaller, Drag+Alt or Command(Window key)=Translate.

If you are using HTML5 enable browser such as Chrome, Safari or FireFox (IE9 is out of support), you will see the Canvas. If you pick solvent, solvent name will appear.

Once I have HSP of packing polymer, then I can evaluate solvent mixture very easily.
[dDm, dPm, dHm]=[(a*dD1+b*dD2), (a*dP1+b*dP2), (a*dH1+b*dH2)]/(a+b)
If the distance from polymer to [dDm, dPm, dHm] are near(smaller than 8.8), that solvents mixture will dissolve that polymer.

HSP of Solvents Mixture

[dDm, dPm, dHm]=[(a*dD1+b*dD2), (a*dP1+b*dP2),(a*dH1+b*dH2)]/(a+b)

Volume base ratio.

Pirika Java demo applet design solvents mixture. GSD is available here.

 

For Viton A, ethanol[15.8, 8.8, 19.4](5-20% swelling B rank) and isooctane [14.1, 0, 0](less than 5% swelling, A rank) both are poor solvent.
But it is known that mixture of ethanol to gasoline swell Viton A very strongly.

2011.4.14

Drag=Rotate, Drag+Shift=Larger/Smaller, Drag+Alt or Command(Window key)=Translate.

If you are using HTML5 enable browser such as Chrome, Safari or FireFox (IE9 is out of support), you will see the Canvas. If you pick solvent, solvent name will appear.

 

The ratio of Ethanol increase, then distance Viton A to mixture of solvents become smaller than 8.8(interaction radius). And the swelling ration increase according to decrease distance.
Actually, this swelling data is not Viton A. This data is for improved polymer with using 3rd co-monomer. Even though, we can easily understand “Gahole “ swelling effect.

If you want to design new recipe of packing polymer, HSPiP will help you so much!

This packing polymer have double natures.
Please refer to Double Spheres analysis article about this polymer.

If you want to know about radical initiate co-polymer, please visit Pirika site.
Radical polymerization simulator.
Transition state DB.
polymer properties estimation.