How to use Sphere Main Program
Although HSPiP does many things, it’s probably best to start with the Sphere that is at the heart of so much of HSP.
As with everything to do with HSPiP you can find out much more about the background to the topic by reading the eBook which is opened by clicking on the Book icon , or by going to your HSPiP Data folder and opening Hansen Solubility Parameters in Practice.pdf in Acrobat Reader.
Remember what we’re trying to do. We need to define a sphere which says “All (or most) of the solvents inside this sphere dissolve the polymer (or dissolve the ink or disperse the pigment or …) and none (or few) of the solvents outside this sphere dissolve the polymer. The problem is to find the centre of the sphere (the HSPs of the polymer/ink/pigment…) and the radius.
Your task is to select a group of relevant solvents and perform the tests. We can’t tell you which solvents to use, but the examples with the program give you some good ideas. The rule is “as broad a range of D, P, H parameters as possible whilst giving you the least amount of work”. If you try to use too many solvents then you will find it too much work and won’t want to use the technique regularly. If you use too few solvents (or too narrow a range) then the calculated fit might be inaccurate or misleading.
You now label each relevant solvent as "Inside" with a "1" and "Outside" with a "0".
We use “Inside” and “Outside” instead of the conventional “Good” and “Bad” because this generalises the concept. For example, it doesn’t make sense to call something which is inside the sphere “Good” when we mean that it shows high toxicity and we want the Sphere to identify the radius of toxic behaviour. If you enter a space or a “-“ that solvent is ignored. You can, if you wish, score the solvents from 1 (should be very close to the centre of the Sphere) to 6 (should be very far outside the Sphere radius) as discussed below.
You then click the Calculate button and the program finds the best fit of the data, defined as the smallest radius which gives the closest fit to a "1.000" which is perfect.
Perfection is defined as all Inside solvents (Blue solid circles) being within the radius and all Outside solvents (Red solid squares) outside the radius. Any Inside solvents outside the radius (or Outside ones within) reduce the Fitness parameter depending on how far outside (inside) they are. Such "wrong" solvents are marked with a "*" in the listing and as Blue open circles (for Inside ones outside) and Red open squares (for Outside ones inside) in the plots.
If you prefer your Sphere to be a wire frame rather than solid, select the WF option.
Obviously it makes no sense to try to calculate a Sphere if all your solvents are “Inside” as the program has no way of knowing the outer limit of your Sphere. Similarly it makes no sense if all your solvents are “Outside”. The program checks for each of these cases and gives you a warning.
The analysis of the fit tells you the number of Inside and Outside solvents (and the total number) the D,P,H and R, plus the goodness of the fit then a list of the Wrong In and Wrong Out solvents so you can quickly identify whether their absence of fit is experimental error or a genuine puzzle.
The data list adds a value for the RED (Relative Energy Difference) number defined by Dr Hansen as HSP distance between the given solvent and the reference value, divided by the radius that defines goodness. An Inside solvent has a RED number <=1. A “Wrong Out” solvent is a solvent that should be Inside but has a RED number >1. An Outside solvent has a RED number >1. A “Wrong In” solvent is a solvent that should be Outside but has a RED number <=1.
Some users prefer to grade the Inside and Outside from 1 to 6 with 1 being Very Much Inside and 6 being Very Much Outside. If you choose this system then your fit depends on whether you include the 2’s or the 3’s (or 4’s or 5’s) as “Inside”. You can play with this by choosing a value from the “Inside” combo-box.
You can also choose a Graded option from the “Inside” choice. If you do this then solvents with a score greater than 1 are penalised if they are inside the calculated sphere, but those with a value of 2 are penalised much less for being inside, the 3 are penalised less, the 4’s are penalised normally and the 5 and 6 values are penalised with increasing severity. If you have Graded selected when you simply have 0’s for the “outside” solvents the behaviour is the same as if you had the standard “1” selected.
How good is the fit? If the data are good then there is mathematically only one good solution and however often you click the Calculate button, you will get (nearly) the same answer. If the data are bad (or if there are too few data points to define a good Sphere) then there isn’t a unique good fit. The program deliberately starts its search from a different point in HSP space and if the space is bad, the optimum will be different each time. So it is always a good idea to click Calculate a few times. If the calculated values change a lot then you have a broad optimum which is hard to find. This means either that the sample you are testing is very inhomogeneous (impurities, co-polymers…), that you have some errors in your data or that you’ve used too few solvents to define the Sphere unambiguously.
Another way to evaluate the fit is to look at the Core values shown in the outputs.
Around the best fit is an area where the fit is almost as good. The question is, how wide is that area. If it is small then the fit is very precise. If it is large (maybe just in one dimension) then the data are not good enough to provide a high-quality fit. The Core values represent the ± values for the three parameters around the best fit which are considered “close” to the best fit. The definition of “close” has been chosen on the basis of tests on a variety of good and bad fits and seems to be a reasonable indicator that can show good fits (e.g. ±0.25 in all three parameters) and bad fits (±0.75 in at least on parameter). If the fit is bad in one parameter that probably means that the suite of test solvents did not cover a wide-enough range in that parameter.
When you are exploring data you sometimes get a very large radius which seems improbable to you. You can force the fit to not exceed the value you include in the Double-click radius (see below for an explanation of this value) by checking the Limit box below the double-click radius input.
If you accidentally leave this on you might get some funny results later on, so use this trick with some caution.
Further Genetic Algorithm (GA) fitting options are described below
What list of solvents do you use? You can start with ~1200 solvents provided as the default (you can load this at any time with Open Master Data Set) or the 88 original Hansen solvents (provided as a reference and also as part of the exhaustive 33/88 file set of all 33 polymers tested with the 88 solvents as in Appendix 3 of the second edition of the Hansen handbook), or a modest Hansen set or you can create one of your own.
Open Master Data Set
Files are saved as simple text files labelled as .HSD (HSPiP Solvent Data). If you want to create a standard set from a larger set then place a 0 or 1 in the relevant solvents (to show that they are being Used) and click File Save Used Only and only those solvents will be included in the .HSD file saved.
To see just the Used solvents, click the Hide Unused option.
If you over-write an existing file, a backup is automatically made.
If you’ve loaded a file and want to get rid of the scores in the column, the Clear button sets them all to a neutral “-“, preceded by a warning.
If you often want to do this and don’t like the warning, then Shift-Clear just clears it. If you want them all to be cleared to “0” then press Ctrl-Clear (with a warning) or Ctrl-Shift-Clear (no warning).
There are 4 options for opening files:
Open simply opens a file.
Open with Merge merges your chosen file with the current file. It checks if the number or name is the same as a current entry and if it is it then checks the HSP and MVol values. If they are all identical then this entry in the dataset is ignored because it’s already in the dataset. If there is difference in one or more of the values then the data are added as a row with a light blue color. At the end of the merge the table is automatically sorted by name and you can then look for all light blue entries which should be next to their equivalents. You then have to decide which is the correct value – knowing that the non-coloured row was the original in the table. Once you’ve decided on the correct row, simply highlight the bad row and press Delete to remove it. Remember to save the merged file when you’ve done all the corrections.
Open with AutoCheck checks each entry and if it matches the name and number of the entry in the Master Data Set its HSP are automatically updated to that in the dataset. You should do this for critical datasets each time there’s a major revision of the HSPiP program with, therefore, some changes in some of the values. The number of changes is usually very small and the chances that you have older values is even smaller, but it’s worth doing if you want to be absolutely sure. The checking can be a bit slow, so be patient. At the end of the checking a message appears to tell you what values (if any) were changed. Remember to save the revised version if you are happy with the changes.
Open Master Data Set, as mentioned above, opens the whole official set if that’s useful for you.
You can sort the list of solvents simply by clicking on the relevant column. One click will sort that column Descending, the next click will sort it Ascending. The sorting of the Name column makes an attempt to conform to intelligent chemical sorting criteria, but you’ll have to forgive occasional lapses.
To Delete an entry, click on the row selector at the edge (just as in Excel) and the whole line is selected. Then press the Del key. You can highlight multiple rows using combinations of Ctrl-Click and Shift-Click so that you can delete multiple rows with one action.
To see a plot of all your current solvents without performing a calculation, click the S Show button.
If you are trying to create your own solvent set, this Show function is useful as you can see how much of HSP space your solvents cover and whether you have too many in one area and too few in another. There is a mixture of art and science in getting a good test set for your own application. You have to balance precision (the more solvents, well distributed, the more accurate the values) with speed (the fewer the faster) and safety/convenience (some solvents in “interesting” locations can be hazardous). If you know your polymers are rather aromatic, there’s little point in testing with lots of solvents with high H/P values, and hydrophilic polymers will gain little insight from a lot of tests with low H/P values.
Note that many users are so used to the P vs H plot that the D values tend to get neglected. This can be a major error. Focus as much on the H vs D and P vs D plots as on the P vs H plot.
Improving your fit
One way to improve the fit is to use the MVC Molar Volume Correction.
This modifies the fitting algorithm so that bigger good molecules and smaller bad molecules are accepted as “out” and “in” respectively on the basis that their molar volumes decrease and increase their solubility respectively. The Sphere that results can show good molecules outside, but that’s OK if they are small. The relative molar volumes are shown (exaggerated) as different sized spheres are cubes.
Another way to look at the quality of the fit is via the “Core” values shown in the output.
This attempts to show how much the centre of the Sphere can move in the different directions without incurring too high a penalty. Clearly the larger the Core values, the less tightly the Sphere is defined, so some extra solvents might be necessary to refine it. This links in to the SRC option, described next.
How do you know if you’ve used enough test solvents to really define the Sphere and its Radius? Following a user’s suggestion we’ve added an interesting technique. By clicking the SRC option before pressing the Calculate button the program carries out a Sphere Radius Check. It goes through a list of 80+ solvents (based on the classic 88 solvent list from Charles) and finds any that are near the boundary of the Sphere (i.e. they have an RED of 0.9 to 1.1). It then checks each of those solvents for closeness to solvents in your test list. If they are close then you already have sufficient data in that area. But if none of your solvents is close then it’s likely that this test solvent would provide useful new information to help improve the quality of the fit.
Each of these solvents is added to your current list and a message appears summarising what has happened. These solvents also appear in orange on the 3 2D and 1 3D plot so you can see which holes in solvent space they are filling.
What do you now do? You are smarter than the computer. So you use your own judgement. Are any of these solvents really providing useful extra information? If so are these solvents available/safe/convenient? Is it worth doing an extra few solvent checks?
You even have a different judgement to make. If you think that that part of solvent space would really be useful to fill, but you don’t like the suggested solvent (or it’s not in the lab) you can go to Solvent Optimizer to find a solvent blend that would give you something close.
Finally, you may want to use a different set of solvents for the SRC. Feel free to open SphereCheckMaster.hsd file and add/remove solvents via the usual manner.
In other words, don’t click the SRC option unless you want to get involved in more work and more decisions. If “good enough” is good enough for your fitting data, then maybe it’s not worth trying the SRC option. But it might just suggest a relatively easy 1 or 2 extra tests that would help pin down the Sphere values, so it’s a good idea to at least have one go with the SRC option.
Genetic Algorithm Advanced fitting options
If the GA option is selected then a new window appears offering you a choice of 3 methods:
• Classic GA. This sets different criteria for optimal fit and, of course, reaches its optimum via a different method from the classic Hansen Sphere algorithm. The “Fit” quality is calculated differently from the classic algorithm and is only intended for comparison with other GA fits – not for comparison with the classic Hansen fit.
• Double Sphere. This assumes that your material (e.g. a di-block co-polymer) is best described with two spheres.
• Data points. This assumes that your values are real data such as solubility, where more is better (unless you select the “Good is small” option).
This fit makes the maximum use of your hard-won data and will generally be more accurate than any “good/bad” split. The downside is that “Radius” becomes meaningless so you have to provide your own value for the plot and RED calculations.
As a check, you can select the Split High/Low option and set a value dividing good from bad and then get a Classic GA fit. You can choose a Use Log Fit option which changes the numerics and might give a different answer. An alternative way of fitting to Data points is via Fit to Exponential. This has the advantage of showing the results of the fit, either as a plot of experimental v calculated (Show Fit) or as a plot of solubility against distance (Show Distance). The MVC option should be selected if the solubilities are by weight rather than molarity – but in practice you can try the fits with and without this option to see which is better.
In all cases the algorithms require an initial guess. This can be provided automatically from the data. But if you have reason to believe the true value is in a certain region, you can get the GA algorithm searching in the right area by providing your own initial guess. If the fitting space is very clean then the results are independent of the initial guess – the algorithms always reach the right answer. If the space is very complex then the initial guess might help steer the algorithm into the right area.
The GA algorithms can be slow. You can choose a trade-off between Accuracy (Lower, Medium, Higher) and speed (Faster Slower). Use the Lower setting when you want to explore whether the GA options are relevant and Higher when you want a definitive final value. Medium will be adequate for most purposes if you want a single setting.
Those who require even more options (including “elliptical” or “variable coefficient” fits) can use the Y-Fit Power Tool.
To close the Advanced options de-select the GA option.
Adding solvents to your list
It often happens that you have a list of solvents and want to add another. It would be very inconvenient to have to look up the HSP of the new solvent and to type them into your list. If you click the Master List option then the 3D diagram is replaced by the master list of solvents supplied with HSPiP. (You can see the “official” list or, by checking 10K, the entire database of 10,000 molecules). If you double click (or Alt-click) on a solvent then the HSP (and MVol) parameters are added to the end of your solvent file.
To hide the list either de-select Master List or click any of the calculation buttons. See below for creating your own Master List
As the solvent list is so long, it is helpful to be able to use the Search tool to find the solvent you want. When the master list is visible then Search applies to this list, not to your current solvent list. As soon as the master list is closed then Search applies to your current solvent list.
If your list is the Master Dataset then you can also search by CAS number and formula. The search also checks for alternative names. For example a search for Hydroquinone (which is not a name shown in the Master Dataset) finds 1,4-Dihydroxybenzene (1,4-Benzenediol).
Starting a whole new set of solvents
If you already have a reasonable list of solvents then adding/deleting a few for a different experiment is simple. But if you have a very different set of solvents, it’s often easier to do File New (or Ctrl-N) and start with an empty table. Creating a fresh solvent list using the trick in the previous paragraph (the Master list is automatically opened) is quick and efficient.
The more you use Sphere, the more you find yourself wanting to transfer HSP values from one part of the program to another. Wherever it makes sense, if you click on some HSP (within a table or within a set of 3 HSP values) and click Ctrl-D (for Duplicate) and Ctrl-P (for Paste) you can transfer the HSP values and, where relevant, the Molar Volume as well. It’s far easier than having to type them in from memory! We use Ctrl-D and Ctrl-P because you might want to use the conventional Ctrl-C and Ctrl-V for conventional Copy/Paste activities.
For copying a Full line of data from the Master database, use Ctrl-F.
The classic HSP plot is Hydrogen Bonding along the X-axis and Polarity along the Y-axis. When you look at this plot you often see Outside solvents inside the radius. But of course, HSP space is 3-dimensional. You need to look at the H vs D plot and P vs D plot to get the full picture. Note that the D-scale in these two plots is expanded by a factor of 2 as is standard (relating to the factor of 4 in the “Distance” calculations).
The default setup for the graphics is that D varies from 10 – 22.5, P, H vary from 0 – 25.
This gives you the classical spherical plots and covers a good general range. For specialist applications you can choose to change the D-min down to 0, but always with a fixed range of 12.5. P-Max and H-Max can be varied over a wide range, always with a minimum of 0 to suit your application. The options may seem somewhat odd, but having tested the application with numerous data sets covering a wide range of different applications, this seems the best mix of power and convenience. With different scale values then, of course, you get non-spherical plots. Remember, the plots are only a visual aid so don’t get too worried if they are elliptical instead of spherical. Changing any of these graphical parameters has no effect on the calculations.
If you click the Spherical option the program finds the maximum scale and sets everything to that to ensure you get a spherical plot. This might mean that you reduce the visibility of details in the smaller directions – but you can turn it on or off as you wish.
When you move your mouse over the plots you get the appropriate parameters and, if close to a solvent, the name.
A 3D plot gives you a global overview. The colour/shape scheme in the 3D plot is matched to that of the 2D plots. You can click and drag the mouse to change the orientation of the plot. As elements move behind or in front of other elements their colours change to give a further idea of the 3D dimensionality. It will take some exploration before you are confident of what you are seeing in the 3D view. If you press the Shift key whilst doing this then moving the mouse zooms the 3D view.
If you press the Ctrl key whilst moving the mouse then you can pan the graph left/right and up/down. Just experiment with a plot and you’ll quickly work out how to move around in 3 dimensions.
Anytime you want to bring the 3D view back to normal, click the little X button below the 3D graph.
If the size of the form is changed, the 3D view is kept to its original aspect ratio (width/height) to avoid 3D distortions. This means, for example, that if the form is stretched only in the width direction, although the 3D box expands to fill the width, the 3D view expands rather less so that if you pan the 3D image it gets cut off towards the right hand side.
So, for a larger 3D view make sure you expand both width and height.
Sometimes you want to see just the Inside solvents, sometimes just the Outside. And sometimes it’s useful to have a label on each 3D element to tell you where your solvent is – the label can be either the number (less cluttered) or the name (more cluttered but more direct). You can choose from each of the 9 possible options to get the view that is most helpful to you.
And you can choose a 10th option – the minimum sphere that encloses all the Inside solvents. This is handy when you are checking for a property (such as reactivity) where being inside is necessary but not sufficient. In other words, many chemicals might be inside the sphere but don’t (e.g. for functionality reasons) react with the target. So a classic Sphere calculation tries to minimize the number of these “wrong in” compounds, even though they aren’t strictly “wrong”.
Finally the 11th option, “Data only” shows just the data points without the sphere.
Identifying individual solvents
Moving the mouse over the 3D plot shows the name of the solvent.
Identifying a 3D element from a 2D screen is a somewhat complex task so the response can be somewhat slow if there are a lot of solvents. For the full data set the technique isn’t 100% reliable so some solvents come out as “Unidentified”.
To see a few solvents more clearly, if you select one or more solvents by clicking on the left-hand edge so that the whole line is highlighted, and then click the SSel (Show Selected) option then when you plot the Sphere, the solvent(s) will be shown in orange in the 2D and 3D plots. If you select either the Name or No. option then only the name (or number) of the selected solvent(s) will be shown in the 2D and 3D plots. This trick can sometimes be useful for identifying interesting features in your data.
Finding a solvent in the list
If you have a long solvent list, it can be tricky to find a particular solvent as you might have a different naming convention from that in the list. If you know the standard Hansen number for a solvent (e.g. 325 for Ethanol) simply type the number into the search box and press Enter or click the Find button. If you want to find all solvents containing the fragment “pyrrol” then the table will show only those chemicals. The less you type (“pyr”) the more chemicals will appear in the table.
The searches are case insensitive so PYRROL, Pyrrol and pyrrol will each find the same entries in the list.
Note that chemicals are automatically put into “proper case” when the file is loaded. This avoids the user and/or the author from having to fuss about whether to enter ethyl acetate or Ethyl acetate or Ethyl Acetate. Whatever you enter, next time the file is loaded it will come out as Ethyl Acetate. The exception is small names such as GBL (Gamma Butyrolactone) which remain exactly as entered. Of course the program tries (and usually succeeds) to make sense of entries such as n-butyl acetate which comes out as n-Butyl Acetate and n-methyl-2-pyrrolidone which comes out as N-Methyl-2-Pyrrolidone. Please forgive the occasional glitch.
You can also search by CAS number.
To restore the whole list, click the X button.
The Double-Click method
If you know of a solvent that has a good HSP set, you might want to find solvents that are within a close HSP Radius of that solvent (e.g. to find a cheaper or safer alternative to your current solvent). To do this, simply Double-Click (or, if you prefer, Alt-Click) on your solvent, having previously entered a Double-Click Radius. The solvents are then automatically sorted by RED number with your chosen solvent, by definition, having a RED number of 0. Any solvent with a RED number of <=1 (i.e. up to your Double-Click Radius) satisfies your criterion and is shown in solid Blue in the graphs. All others are shown as hollow Blue. If you have too many “Inside” solvents, reduce the Double-Click R and try again.
If you have a target HSP that is not included in the solvent list, go to the bottom of the table and enter a D, P, H set in that empty row. You can add a Number and Name if you wish, but if you don’t they will automatically be assigned “0” and “Target” when you Double-Click.
Diluents in your test samples
Sometimes a polymer or pigment comes with X% of solvent which cannot be removed before doing the Sphere test. If the sample is tested as Y% in the solvent (e.g. a polymer might be tested as soluble/insoluble at 5%) then the HSP of the test solvent is diluted by a certain %. For example, if the polymer’s solvent is 50% then to have 5% of polymer you also have 5% of that solvent in the test vial.
To correct for this, you add an extra line to your .hsd file, with the solvent named as Diluent or Dilutor or Dilution (whichever makes more sense to you – it must start with DILU), in the HSP columns you enter the known value of that solvent, and in the Score column you enter the final % of that solvent. The Sphere fitting automatically adjusts the HSP of the overall test solvent (based on the weighted average of their HSP – just as in Solvent Optimizer). Usually the effects are small, but the feature is added for those who think it might be a problem for their particular case.
Environmental Stress Cracking (ESC) is a complex but important subject involving the interaction of (bad) solvents, stress and the polymer. When the ESC alert option is selected the solvents are colour coded depending on their tendency to cause ESC. This Help file isn’t the appropriate place to discuss what the colour coding means, so please refer to the ESC chapter in the eBook.
Solvent mixtures as “solvents”
Sometimes you need a “solvent” with a specific HSP for testing the Sphere but can’t find a suitable single solvent. You therefore need to make a mixture with the desired values. To make this easy to do, the “S” button in the Solvent Optimizer transfers the HSP value of whatever mix you have created in the Optimizer over to a new line in the Sphere solvent table.
Your own Master List
The master list is encoded within the software and can’t be altered. This is for many reasons, one being certainty that whenever any user refers to the master list they are always referring to the same version.
However, some users want to use their own master list. Here’s how to do it. First create a .hsd file using any relevant technique – including doing a large batch conversion process via the Y-MB DIY. Load it as normal to check that it’s OK. Now save it to the HSPiP Data folder as MyMasterData.hsd. If you now select MyDB that will now be your master data for all relevant activities including FindMols and the Y-MB DIY Analog search. As it’s possible for you to have subtle errors in this set, if the software finds any problems with it, it reverts to the standard master. You’ll have to find the cause of your problem yourself – typically it will be some illegal value in one of the key propertie.
If you want to revert to the standard master, simply un-select the MyDB option. If you want multiple masters, name them something like MyMasterData1, MyMasterData2… then load whichever one you wish to use as the master and save it as MyMasterData.
If you want to find a pair of solvents or a complex mixture of solvents to match a particular HSP then you can use the O Optimize button which brings up the Solvent Optimizer form, with the target solvent automatically set to the solvent you have currently selected.
To transfer solvents from this form to the Solvent Optimizer, select one or more solvents by clicking (or Shift-clicking or Ctrl-clicking, as per any Microsoft-style table) on the “selection” box on the left-hand edge of each solvent, then Ctrl-Click (or Right-Click) on the text of one of the selected lines and, after a message appears for you to confirm that this is what you want to do, the solvents will be added. This isn’t the easiest of things to get right first time, but Ctrl and Shift are used for many things by Microsoft and we’ve done the best we can.
For dealing with polymer issues, click the P Polymer button which opens the Polymer form.
Do It Yourself (DIY)
To generate HSP values from your own chemicals and to investigate a whole range of interesting properties such as activity coefficients, HSE “read across” and solubilities, click on the δ button.