CO-SOLVE-IT! USING HANSEN PARAMETERS TO PREDICT RESIN SOLUBILITY. A COMPUTER APPLICATION. By: Michael Law Technical information and/or assistance contained herein or provided in conjunction with this correspondence, are furnished without charge or obligation, and are given and accepted at recipient's sole risk. Donations and suggestions to encourage future development are gladly accepted. Reasonable efforts were made to verify this information. However, as conditions of user are beyond my control, I make no representation about and I am not responsible or liable for the accuracy or reliability of such data, the results obtained therefrom or the toxicological effects of the material(s) described in this correspondence and computer program. NO WARRANTIES, EXPRESSED OR IMPLIED, INCLUDING BUT NOT LIMITED TO THE WARRANTIES OF MERCHANTABILITY OR FITNESS FOR PARTICULAR PURPOSE, ARE MADE HEREIN OR BY THE PRODUCT PROVIDED. Copyright (c) 1993 Michael P. Law - PRESS ANY KEY TO GO ON CONTENTS PAGE NUMBER COVER SHEET DISCLAIMER INTRODUCTION TO CO-SOLVE-IT!, CO-RESIN, CO-RADII 1-2 AND CO-EVAP. GENERAL REQUIREMENTS FOR SOLVENCY & DISCUSSION OF 3-10 HANSEN SOLUBILITY THEORY RADIUS OF INTERACTION 11-12 AN EXAMPLE - MELAMINE RESIN 13-15 METHOD USED IN CO-RADII 16-23 METHOD USED IN CO-RESIN 24-26 GETTING STARTED & RUNNING THE PROGRAM 27-34 GRAPH INTERPRETATION IN CO-SOLVE-IT! 35-36 AN EXAMPLE - REMOVING A HYDROCARBON SOIL 36-37 AN EXAMPLE - URETHANE CLEANER 38-39 AN EXAMPLE - SOLVENT SYNERGY 40-48 AN EXAMPLE - HYPOTHETICAL LACQUER 49-63 CO-RESIN'S MAIN MENU & HELP FILE 64-75 CO-RADII'S MAIN MENU & HELP FILE 76-81 ALPHABETICAL LISTS OF SOLVENTS, RESINS, PIGMENTS & SURFACTANT 81-115 REFERENCES 116 ACKNOWLEDGEMENTS 117 USING HANSEN SOLUBILITY PARAMETERS TO SELECT SOLVENT AND SOLVENT REPLACEMENT BLENDS FOR COATINGS AND INKS CO-SOLVE-IT! is one of three computer applications, which when completed, should provide useful information for formulators. The first program is called CO-SOLVE-IT!. CO-SOLVE-IT! uses Hansen solubility theory to determine whether or not a resin (whose Hansen parameters are known) will dissolve in a given solvent or solvent blend. A second program is comprised of two subprograms: (CO-RESIN & CO-RADII). These programs are used to approximate the Hansen parameters and the radius of interaction for a resin whose properties are unknown. CO-RESIN and CO-RADII both require some experimental information. In these programs the solubility of a resin, under the influence of a carefully chosen set of potential solvents, is either measured or observed. Once chosen, these programs calculate the Hansen parameters of the resin and approximate the radius of interaction. Once the required information is entered by the user, CO-RESIN & CO-RADII perform a variety of mathematical and statistical calculations to determine the Hansen parameters and the radius of interaction for a resin. The program (CO-RESIN) determines the swell of a resin under the influence of a number of solvents. This method approximates the intrinsic viscosity of a resin and a solvent in a dilute solution. Solution viscosity is measured at a given temperature for each resin solvent mix. The user must enter the solvent's viscosity at 25 degrees Celsius and also the mixing temperature. (the solvent initial viscosity is approximated at the mixing temperature). Both of these methods quantify a resin's properties for later use in CO-SOLVE-IT. Once a resin's Hansen parameters are known, the resin can be added to the CO-SOLVE-IT! database and then be used in solvent replacement calculations. The third program (CO-EVAP) will, when finished, match solvent or solvent blend evaporation rates. This program is intended to estimate phase equilibria for systems for which no data exists. It will, in its first release, be used for the following systems: non-ionic, solvent, and aqueous-solvent systems. This is a difficult undertaking and the precise methods to be adopted will be a function of my improving computer programming skills rather than one of physical understanding. For the time being, I am going to experiment with a variety of methods and pick the method that will yield reasonable results and is manageable in terms of programming difficulty. All three modules, when used together, should suggest possible solvent replacements and starting point formulations. The ability to survey a number of formulations and solvent systems, before doing any experimental work, should be of value to the formulator. As with all computer simulations, or even bench top experiments, certain simplifications and assumptions must be made. Hansen theory is at least 85% correct in predicting whether or not a resin will be soluble in a given solvent. The other programs are more complex. To what extent theory will agree with experiment is unknown, and interpretation is left up to the user. THE PROGRAM "CO-SOLVE-IT" This computer simulation is based on the work of Burrell and Hansen and attempts to predict resin-solvent solubilities. For the benefit of the curious, a brief outline of solubility theory is included. If you find this discussion tiresome, that's OK! "Co-Solve-it" is very easy to use, and the results are fairly easy to interpret. The program is menu driven and a brief 'HELP" file is included. It is important that the files, solvents and resin names be entered and spelled correctly.(CASE INDEPENDENCE is one small convenience provided to the user). The program in its present form, is not very forgiving of spelling and type errors. "CO-SOLVE-IT" does not offer pull down menus and sophisticated input screens. It also does not have powerful search capabilities and file indexing, that would be very useful for this type of program, considering the amount of information processed. Despite these obvious inconveniences, this program can produce useful information with fairly good predictions in such areas as: coatings formulations, coatings stripper formulations, de- greasing solvents, and general coatings and cleaners work. A number of large corporations use programs of this type to assist them with solvent selections and replacement blends. This is shareware program, and in the spirit of shareware, may be copied and distributed in its original form. I hope that you will find this program of some value, and use it as a tool to stimulate the creative process. I will try to update and improve this product to provide you with a more civilized and accurate tool. I also welcome suggestions or criticism, especially with regard to accuracy and function. GENERAL REQUIREMENTS FOR SOLVENCY Polymer - Solvent interaction: Whether or not a solvent is a "true solvent" or diluent depends on the polymer or resin and is not an independent property of the solvent. When a solid polymer or resin is mixed with a liquid, three results are possible: If the attraction between the liquid and the solid's molecules is less than the attraction of the solid's molecules for each other, then the liquid will only serve to separate, as in the case of a diluent. If this mixture is agitated, a suspension of the solid material will occur. In all probability, over time, this mixture will settle out. The second possibility is when the liquid's attractive forces are greater than the solid's inter-molecular forces, the solvent will then enter the solid and break away the solid's molecules. The solid will then go into solution. The third possibility is that the solvent will react with the solid. If this happens, the reaction products will behave according to the first or second case.(14) HANSEN SOLUBILITY THEORY In general, theories of solubility present complex relationships involving molecular energy, thermal energy and potential energy. (Gibbs free energy, enthalpy, chemical potential, and entropy.)(2) Substances with like solubility parameters will co-mingle. The basic assumption is that there is a relation between cohesive energy or potential energy per unit volume and solubility. Solids and liquids have strong attractive forces relative to their vapor phase (large negative potential energy). This potential energy is called the molar cohesive energy. The molar cohesive energy is measured relative to the same material, at the same temperature, in its vapor phase. For a substance to dissolve, the Gibbs energy of mixing at constant pressure must be negative. This can occur if the enthalpy is negative or is less positive than the entropy. The three parameter model (HANSEN) makes the simplifying assumption that the total solubility parameter is constant, with regard to temperature and pressure. Also, the relative strength of the three types of forces, assumed to be additive (as represented by the three parameters) will determine whether or not a resin will dissolve in a given solvent or solvent blend. THE 3-D HANSEN SOLUBILITY MODEL The 3-D solubility model is a semi-empirical description of solvent-solvent or solvent-polymer solubility. This model allows for quantitative comparisons to be made between solvents or solvent blends in order to determine whether or not a polymer will dissolve. For any solvent, or polymer, it is assumed that physical properties can be reduced to three parameters, (each describing a specific interaction), and in one case, combined interactions. This model allows for interesting descriptions both numerical and in graphics, to be made with predictive value.(2) The solubility parameter can be considered as a vector comprised of hydrogen bonding, polar and dispersion components. Solvents and plasticizer can be located as points in a 3-D system.(1) Each of the components will be described in the discussion below and an effort will be made to provide theoretical justification for each of the three-components. When molecules are interacting, three primary forces are involved: dispersion or London forces that come about because of the wobble between the nucleus of an atom and its electron cloud. All molecules have dispersion interaction. The second forces are polar interactions, either Debye (induced dipole) or Keesom (dipole-dipole), which both result from charge asymmetry. The third force is hydrogen bonding that comes from specific chemical interactions (alcohols, ethers, ketones).(2) Let us now take each of these interactions in order and see how they contribute to the total cohesive energy that binds molecules together and makes different states of matter possible. When thinking about solubility parameters, it is also important to keep in mind that this is a concept that attempts to relate the macroscopic world of our everyday experiences to the microscopic world of atoms, molecules and forces. In much the same way, and with the same theoretical justification, as does the ideal gas law attempt to connect molecular events to gross measurements of pressure, volume, and temperature. In fact, even the evolution of the solubility parameter is similar to the way the ideal gas law is parameterized and modified to account for the behavior of real gases. (van der Waals' equation of state) The conceptual process is the same; what is different is the state of matter described. The solubility parameter is primarily concerned with liquid interactions. One reason this parameterized semi-empirical description of matter lends itself so well to the computer is that, unlike strict thermodynamic considerations, this concept is easy to implement, because numbers are counted and because numbers are compared. Also, parameterized functions that would be very difficult to solve by analytic methods can be approximated using numerical methods. The basic idea is to link these solubility parameters to some physical reality and then try to find if they have some predictive value. Well, back to the discussion and summary of the interactive forces involved. The first interaction, (dispersion or London) is common to all molecules and is the only interaction possible for saturated hydrocarbons. This force is induced-dipole/induced- dipole. Pairs of molecules approach each other and interact, distorting their electron cloud and causing an asymmetric arrangement, which results in intermolecular attraction. The rotation of these molecules continue and they tend to follow one another as instantaneous forces pull them along. These are non- polar interactions. However, nonpolar molecules can in the presence of an electric field, acquire a temporary dipole. In fact, the constant relating the electric field strength to the dipole moment is the polarizability constant. This constant is also related to the refractive index, by the Lorentz-Lorenz equation. The dispersion energy depends on both the polarizability and the first ionization potential of each molecule. Approximations can be calculated as:(2) <> With dipole-dipole or Keesom forces, molecules tend to align themselves in energy favorable ways. These molecules have permanent dipole moments and this alignment process is randomized by thermal agitation that degrades the orientation process.(2) Dipole-Induced Dipole or Debye interactions are caused by the polarization of either polar or non-polar molecules in the proximity of a polar molecule. Thermal motion is not very important as the induced dipoles persist. (2) In CO-RESIN and CO-RADII, the object is to find the Hansen parameters for a resin for which these parameters are unknown. This is done by finding the coordinates and radius of interaction and by fitting a set of solvents known to solubilize the resin of interest. This solubility sphere is described by a "cloud" of solvent points that maps out this "solubility sphere". Once the coordinate points are determined and a radius has been calculated, this data can be put back in CO-SOLVE-IT!, for possible reformulation work with other solvents. Most of the resins in the resins database (RESINS.IN) are from published sources (listed in the references at the end of this documentation). Both CO-RESIN and CO-RADII use powerful techniques to link observations to solvent properties (modified moments routine and nonlinear regression analysis). The method used for performing swell calculations in CO-RESIN requires the use of another shareware program called NONLIN (tm). CO-RADII uses a simpler routine to accomplish the same goal, but with less feedback provided to the user. NONLIN (tm) has many other uses, other than the use I have given it. On Phillip Sherrod's (author of NONLIN (tm)) distribution disk, there are many examples of other potential uses. Please obtain a registered copy from Phillip Sherrod. His program is very elegant and powerful and I do not have the skills to improve upon his work; he also has a graphing program that is very high quality. Phillip's products exceed many commercial programs of this type in capability. Again, if you want to use CO-RESIN for swell calculations, you need NONLIN (tm). This program can be downloaded from bulletin boards or obtained from Phillip Sherrod, whose address is provided with this doc's references. Perhaps the best way to show how CO-SOLVE-IT! performs a calculation is by example. The table and graph on the next two pages are simulated runs for a melamine type resin with a single solvent system. Blends could also have been run to optimize the results below. Note that all values are calculated and based on published sources. This is a simulation and actual experiments were not done. The solvents chosen are (with abbreviations): All this arithmetic does not, in and of itself, prove that these relationships have any real physical meaning. What makes this type of calculation process meaningful is that observations, (albeit) somewhat subjective, are linked to the factor W. Hansen used a visual scale with a range of 6, to describe resin solubility. Hansen's Scale for 0.5 g solute is mixed in 5 ml solvent. Solutions were evaluated repeatedly until an agreed value was found:(1) 1-Soluble 2-Almost soluble 3-Strongly swollen, slight solubility 4-Swollen 5-Little swelling 6-No visible effect In the case of highly viscous samples, heat was applied but judgment was made at room temperature. In CO-Radii, a 10 point scale is used, for reasons of scaling, also, the opposite end of the scale is used for maximum solvent power. Solution make-up is done using the same method Hansen used. In CO-Radii: 10-Extremely Soluble, quickly goes in solution, like sugar in water. 9-Very soluble, not much agitation required. No observed particles in suspension, clear miscible solution. 8-Soluble but slow to go into solution. Overnight on a rotary mixer: ASTM D3132-84 (reapproved 1990) 7-Most of the material goes into solution. Solution may have a slight haze. 6-Strongly swollen, slight solubility. 5-Swollen 4-Some swelling 3-softening 2-Little visible effect 1-No visible effect Clearly, CO-Radii is used to rough out some numbers. How well it does depends on the selection of solvents. Diverse solvents that have strong predominating effects along one of the 3-Hansen axis is what you look for in the test set. The solvents suggested in the program CO-Radii should do the job for many resins. For now, and until I am comfortable with this selection and this method (if it holds up). The list is provided in the help file. As for the radius, in this case, a family of quadratic surfaces from the center, (resin hansen coordinates) are drawn. The radius of interaction is the radius of the solubility envelope formed by and including all the solvents in this envelope. This envelope is then approximated by a "sphere of solubility". This is done by adjusting the "fit" and calculating the length of the radius vector. After the resin's Hansen parameters and radius of interaction are determined, these values can be entered in "resins.in" (or one of your creation) and CO- SOLVE-IT! for blend calculations or just simple one-to-one replacements. Some limitations of polymer solubility determination: 1. Strictly valid at the original temperature and the original concentration. 2. During solvent evaporation, i.e., from a coating, there is a decrease in film temperature, which may cause the resin to become incompatible and stratify. 3. In addition, as with CO-SOLVE-IT!. The entropy is assumed to be constant and clearly this is not so, and depends on the molar volume of the solvent, and other factors. Also, it is assumed that hydrogen-bond sites act at same time as proton donors and acceptors, some molecules can only act as one or the other. CO-RESIN Co-RESIN is a little more elaborate. This program also attempts to rough it out, but it also relates solvent properties to intrinsic viscosity of resins in dilute solutions. With a judicious selection of solvents, (the W factor in this case is the observed solution viscosity), a parameterized function can be 2found to predict solution viscosities for other solvents and solvent blends. In CO-RESIN the basic idea is to take a small number (but statistically significant) group of solvents, whose Hansen parameters are known, and use this information to predict resin swell for solvents and solvent blends for which test information is not on hand. After all the required information is entered, CO-RESIN approximates the resin's hansen parameters and the radius of interaction, using a method similar to that of CO- RADII. If a fit cannot be found, CO-RESIN suggests adding or deleting a solvent. At the same time CO-RESIN writes several ascii files to disk called: "RADCALC.NLR & RAD.DAT". NOTE: BEFORE MAKING A RUN, FIRST PICK (OPTION X) WHICH CLEARS THE OLD FILES AND MAKES THESE FILES READY FOR NEW DATA. The file that CO-RESIN writes to disk is in the form: Dependent Variable = (parameterized) Independent Variables. OPTION Y executes NONLIN (tm): this program has its own report generation and graphics capabilities. Check nonlin (tm) documentation for an explanation of the report generated. After running NONLIN (tm) and if the parameterized function converges, reports are generated. The user must decide if this report has satisfactory validity. The object is to determine a number of 'k' values for substitution back into CO-RESIN for the purposes of investigating other solvent systems. It is possible that this fit will not converge or will produce low correlations between dependent and independent variables. If this happens try some other combination of solvent(s). The hope is that "relative swell" parameters will provide a way to survey a large number of solvents and solvent blends without having to run every sample in the laboratory. Once some likely candidates are found by simulation, some experimentation can be done to adjust and optimize these solvent(s). The use of swell is only one type of observable that could have been chosen. Any observable for which solvent interactions play an important role could have been chosen. Weight loss from test panels (under controlled conditions) immersed in a solvent where the solvent plays a predominant role is another possible observable. Swell measurements for elastomers is another example. Even hardness measurements for a coating can be the observable in question. How is this observable related to the Hansen "sphere of solubility"? The equation of a sphere is:(11) If the sphere is centered at the origin, (R is a constant). If the center is not at the origin then: where k is a constant. If the sphere is in Hansen space then: then, ka, kb, kc are located at the center of the sphere. These are the models parameters. The constant (k or r) becomes the dependent variable "s" and a system of equations is related to the parameterized independent variables. In a physical system, "s" is an observable that can be measured. (as mentioned previously). This system is a constrained system, in which you want the data to fit the model, by adjusting the model to find the best possible fit for the data. The underlying assumption is that the observable must be a function of solvent effect, If the observable is only partially a function of solvent effect, then the model is weakened and may give erroneous results. Remember that Hansen solubility theory already makes some simplifications, especially with regard to the question of the entropy of mixing. Careful choice for your observable is crucial if useful information is to be gained from computer simulations of this type. Functions of this class are known as: "merit functions". If the model is not appropriate, as determined by comparing "goodness of fit statistics", against some statistical standard, then you may need to adjust the model or your choice of the observable. Also, you need a way to test whether or not the merit function is unimodal. Can there be a better fit in the neighborhood of the fit found? In addition to "Hansen space", we need to concern our search with "parameter space" too! Remember, think about your results and ask yourself: are these numbers reasonable? In CO-RESIN and CO-RADII a function of this type depends nonlinearly on a set of unknown parameters. Because of nonlinear dependence, the solution is approached by using an iterative method in which the parameters are given some initial values; by using an adaptive method, parameters are minimized and tested against some limit for convergence. The function is also tested. it is possible and often desirable, to have both function and parameter convergence. The nonlinear least squares method used in CO-RADII, and one section of CO-RESIN is a modified version of the 'Marquardt-Levenburg method.' In this approach a steepest descent method is used, when far from the minimum, and switches to an inverse Hessian method as the minimum is approached. This method switches back and forth as the parameters wander, and they often do, in a flat valley, or if the topology is complicated. GETTING STARTED The first thing a user should do is make a backup copy of this program. If you are using a portable computer without a hard drive, you should make a working disk for each program. Those with a hard drive should create a convenient sub-directory and allow a couple of megs for the program and file creation. As there are many possible disk formats and capacities, I will describe the files that must be made available for each program to function: CO-SOLVE-IT! CO-RADII CO-RESIN.EXE 1. CO-SOLUT.EXE 1. CO-RADII.EXE 1. CO-RESIN.EXE 2. SOLVENTS.IN 2. RADII.IN 2. SOLVENTS.IN 3. RESINS.IN 3. GRAPHICS.COM 3. RESINS.IN 4. PIGMENTS.IN 4. GRAPHICS.COM 5. RUN.BAT (optional) 6. GRAPHICS.COM copied from your version of MS-DOS For floppy systems, use 3 floppy disks and leave plenty of space available on each disk for files created by these programs, or for reports saved to disk. For Hard drive systems, copy all the files into a subdirectory from the distribution disk(s). i.e. A:>COPY *.* C:\COSOLVE (subdirectory is cosolve) Minimum system requirements: IBM PC,XT,AT,PS2 or compatible. 512 K ram - 640 K ram is desirable. A graphics card: CGA,HERC,EGA,VGA Printer (attached to lpt1 'prn') other ports are currently not supported. You can however, use the DOS copy command to print report files to other ports. Once a working disk is formatted and the files copied, to start CO-SOLVE-IT, you can, from the DOS prompt, type RUN and press Return. WINDOWS USERS: This program can be run as a DOS application and started in the customary way other DOS programs are run. RUNNING THE PROGRAM The program starts with a graphics display followed by a notice and disclaimer. I suggest that you read this one time so that you understand the terms and conditions set forth. The first files called for, (depending upon which program is run), are the input files. Theses file names appear in parentheses and tell you what files are to be entered and are NOT defaulted. Type in only the files names not the parentheses() Be sure to type in the file extensions too!. This will make it possible for you, as you get more experienced, to use data files of your own creation. Once these data files are entered, you will see the main menu. If you make an error typing in the names of the data files, you will be asked to try again. So, if you have gotten to the MAIN MENU you are on track. A word about data file location. The program automatically looks to the disk or directory containing the executable files. Data files are usually located in the same directory. You can, however, set a path, when entering the data files. For example, let's say that your program disk is A and your data files are to be located on disk B, or in some subdirectory. You, then, enter a path, when asked to enter the data files: i.e.- B:SOLVENTS.IN (press Return). The program now knows where to find data. Once you have gotten to the main menu, you are ready to go. Notice the Help Option. Some instructions are there, (brief explanations), as well as the most complete lists of solvents, resins and pigments. These lists are broken down into categories, some by chemical group, others by probable use. None of the lists are currently in alphabetical order. Once you select a list, you must go through the complete listing, before going back to the main menu. Because of the way the program is structured, when you complete an operation, you will be returned to the MAIN MENU. PLEASE NOTE: at the start of a session use OPTION X to clear old information out of the report files (REPORT.TXT). The rest of this documentation will be in the form of a description of every menu item. Some examples for reformations will be provided as well as a complete list of solvents and resins in alphabetical order at the end of this documentation. CO-SOLVE-IT! / MAIN MENU R.....Get a Resin or a Pigment, eg. Cymel 300 S.....Select Solvent(s) or Solvent(s), V.....View results on SCREEN Z.....Print to a File -do to keep P.....Print LAST run to the Printer. B.....Execute a BATCH print job. G.....Graph Solubility Maps * UTILITIES MENU * C.....Create a new SOLVENTS file A.....Add data to the SOLVENTS file. L.....List the solvent file to the screen F.....Find a SOLVENT H.....'HELP MENU' & (Resin & Solvent Lists) W.....Where the resins' list is found. X.....Erase the log file: report.txt E.....Execute Polymer/Solvents potpourri D.....DO CO-RESIN properties calculator Q.....Quit the program Your selection? PROGRAM STRUCTURE This program is structured to be menu driven. The main menu is where you are returned, after some function is completed. If errors occur, or you make an entry error, you should be returned to this menu. Some attempt has been made to detect errors and to recover from them. However, the detection of errors is still, and probably always will be, evolving and changing with the program. The very worst thing that can happen is that an error is trapped, and the program, for many reasons, has recovered, but has not re- initialized itself. If you should encounter a problem, press "CTRL BREAK" or "CTRL C", and break out. You may lose a run, but it was probably lost already. Under normal circumstances, it is always better to exit gracefully; but sometimes you do not have that option, you cannot hurt the program by breaking out to DOS. If you break out while the program is in a graphics mode and (at the dos prompt), characters are big or different, and if the screen scrolls funny and slow, you may need to go to your DOS directory and type MODE 80 to set a text mode again - However, if you do not do this, other programs may not set their screens up right. Better to go to DOS and perform MODE 80 (press Return). Again, none of the programs will be damaged. To exit (normally), press Q and then Return. All selections are made by entering the letter corresponding to the menu item you wish to select. 1. In CO-SOLVE-IT!, to start a run, first select OPTION X, to clear the old files out. 2. Select OPTION R - get a resin, enter the resin name exactly and press Return. The program will report back that the resin data is in memory. 3. Next select OPTION S - select solvent(s). Enter the number of solvents in your blend. Enter the solvent's name twice, the first name appearing as a label in the graphs. Next, (for the search 2routine) SPELL EXACTLY the solvent's name. Searches are sequential and no wild cards or other conveniences are included with the solvent names in this version of the program. By the way, case is not important, i.e. MEK or mek or Mek ect. are permitted and the same goes for resins, pigments, ect. INSTRUCTIONS & HELP MENU 1. General Instructions. 2. Common Solvents 3. Common Coating Resin. 4. More Solvents & Ink Resins 5. Alkanes, Aromatics Ethers & Ketones 6. Refrigerants & Liquid Mixtures (oil ect.) 7. Halohydrocarbons, Esters, Nitrogen & Sulfur Compounds 8. Alcohols, E-Series Glycol Ether Trade Names, Acids - Phenols & Polyhydric Alcohols. 9. Resin List complete as of: 06/06/93 10. Pigments 11. Surfactant (lipophilic) 12. Exit - Main Menu. Your selection?(1-12) (OPTION 1 - OF THE INSTRUCTIONS AND HELP FILE) INSTRUCTIONS & HELP FILE ------------------------ (USE OPTION X - TO START A NEW SESSION) (YOU CAN APPEND REPORTS - IF YOU DO NOT USE - OPTION X) Enter the key corresponding to the command you wish to select. First, select the resin of interest. Enter the abbreviation for the resin EXACTLY as spelled in the documentation. Next, select the number of solvent(s) in your blend (up to 10), and PRESS ENTER. Now, enter the solvent(s). Each solvent is entered TWICE: the 1st time is for appearance sake. You want the 1st entry name to be meaningful to you (customary usage). The second entry is the solvent spelled out EXACTLY as it appears in the doc's. Now, enter the VOLUME fraction ('1.0' if one pure solvent); if (for example: you have a 75/25 blend of PTB/DPM), then the volume fraction for PTB would be: 0.75 and DPM would be: 0.25. When you have entered all of the solvents, press return to end this process. At this point, the radius for the solvent(s) is calculated and compared with that of the resin's radius. If the radius of the solvent(s) is less than that of the resin's, then the solvent(s) should solubilize the resin. Hansen solubility theory is approx. 85% accurate in predicting solubility. The smaller the radius of the solvent(s) relative to the resin's radius, the greater the solvency. Next, save the result (option z) and graph (option G) the results Note: before graphing and saving a report, you must first have made a run with a resin and solvent(s). Also, to use the program's graphics printing capabilities the 'DOS' program 'GRAPHICS.COM' must first have been run. (before 'CO-SOLVE-IT' was started) The easy way to do this is to copy 'GRAPHICS.COM' into the same same directory or diskette as your program files. The batch file "RUN.BAT" will then automatically run "GRAPHICS.COM". --- MENU KEY --- R - Select one resin that you want to test for solubility. Or test 1 pigment in a solvent or solvent blend. S - Solvent selection: You may enter up to 10 solvents. You enter the solvent's name (abbrev.) exactly as the solvent appears in the documentation. Then enter the solvent VOLUME fraction in the blend (i.e 1, if this is the only solvent or 0.5, if the solvent is 50% - USE VOLUME FRACTIONS) The Hansen values are then printed to the screen an is automatically logged to REPORT.TXT. If more than 1 solvent is to be entered, you repeat the process. V - VIEW results Z - LOG the VIEW : Log to file REPORT.TXT P - PRINT the VIEW of last run to the printer (lpt1) B - BATCH print the solvent(s), volume fraction and VIEWS to printer attached to lpt1, cumulative REPORT.TXT (Option S)- For the 10 solvents, you may include the pigments, surfactant and resins that are in the data file "solvents.in". Keep in mind that this program is mainly concerned with solvent(s)-resin solubility and does not pretend to do coatings or inks reformulations. In other words, this is a tool to test ideas, and has somewhat more reliability than just a guess. Also, remember that these entries are VOLUME FRACTIONS i.e. .3, .1,.6; all must add up to 1.0 which is equal to 100% of the total. Note: For the rest of this manual, solvent(s) is to be taken as: a solvent, solvent blends or mixtures of solvents, resins, surfactant and pigments, in any combination, found in the data file "solvents.in". After selecting a resin and solvent(s). (Option R and Option S). View the results (Option V). If this run is to be saved, select (OPTION Z), which saves each run to a text file, "REPORT.TXT". This file can be printed (OPTION B). Successive runs can be appended to report.txt, and these runs can be logged one after another. If you want to clear this file, select (OPTION X). (OPTION P) prints the last run made. (OPTION G) - allows a series of graphs to be displayed and viewed on the screen or printed to a printer connected to LPT1 (prn). At present only port 1 is supported. The program will soon be modified to allow other ports to be selected. In order to print graphs, the DOS program GRAPHICS.COM must be resident prior to running CO-SOLVE-IT!. Printer support is found in the DOS file GRAPHICS.PRO. Consult your DOS manual for an explanation on how to load your particular print drivers. CO-SOLVE-ITS! graphics print routine is essentially a screen dump and will not produce a graphics printout without having first loaded GRAPHICS.COM from DOS, before running CO-SOLVE-IT!. OPTION G - GRAPH INTERPRETATION Graphics can be a useful tool to visualize what is going on. Unfortunately, programming graphics is relatively difficult. What I've tried to do represents these concepts as graphics, I admit that this is an evolutionary process and I have tried many different approaches. In time, and with user feed back, I'll make these routines better and allow the user the opportunity to view the data graphically in a form that is meaningful to him. For now, what you get is a set of graphs (8). I will try to explain what was attempted with each graph. 1. The first graph is a statistical scatter plot of the Hansen and Polar axis (y-axis) versus the Hansen Hbond axis (x-axis). If you run a resin and a solvent, you will get coordinate points for the solvent you have chosen. This point is plotted and the axis are autoscaled to the size of your screen. Note that all IBM graphics cards are supported: CGA, HERC, EGA, VGA. My computer has a basic VGA card with 256 KB of video ram. CO-SOLVE-IT! will automatically detect your particular video card and should work alright. If you cannot get a graphics display, consult your computer manual and determine whether or not there is a software driver you can use to get graphics displays. Any one of the modes mentioned above will do. The higher the resolution, the better the graphics will appear. Let me know if your particular computer system will not produce a graphics display. If you cannot get graphics or have only a text oriented card, do not despair, graphs are useful, but the calculations are displayed in the text mode. 2. Graph 2 is a bar graph and is easy to interpret. It tries to show which solvent in the blend is more soluble relative to the resin. The graph autoscales and is a relative comparison between the resin and solvent(s). 3. The next 3 graphs are solubility maps that print one point: the coordinates of the solvent(s) versus each Hansen parameter. I have seen similar published maps with resin data sheets; this is an attempt to emulate this process. Perhaps, the best use of these graphs is to overlay a number of them, (manually), and map a number of solvent systems for a given resin. 4. The next 3 graphs are single point, (the average coordinates for a solvent blend), representations in "Hansen Space". Here the x-y axis are located at the resin in "Hansen space" (translated) to the resin and a series of concentric ellipses are drawn to simulate distance from the origin to the end of the "sphere of solubility". This is similar to the layers in an onion: somewhere lies the component vector sum of the solvent(s). I have cut the onion in several planes. The basic idea is to try and visualize which parameter is the greatest contributor to a resin's solubility. CO-RESIN works in similar ways. However, some of the graphs are swell vs Hansen parameters. CO-RADII uses the statistical scatter plot graph. ( same routine as is found in the main program of CO-SOLVE-IT!). Here, as before each individual solvent is plotted. Again, following the graph, there are two data set analysis screens. It is very difficult to predict what graphing method is going to be liked by all. I am here to please, and any suggestions are welcome. AN EXAMPLE - REMOVING A HYDROCARBON SOIL This is an example of how CO-SOLVE-IT! may be used to simulate solvents for cleaners use. Once done in simulation, blends of solvents may be tested. In this example, no experimental data are used; what is depicted is the modeling process. The model only suggests possible solvents to be tried out, and indicates which solvent properties are important. In this example, a "hypothetical" hydrocarbon soil is exposed to a number of different solvents for a given length of time and at a given temperature. The amount of soil removed is then a function of solvent properties (Depicted in the graph). An equation is generated that can be used to predict what solvents and solvent blends may be the most efficient cleaning agents. On the next page, is a graph of the polar and hydrogen bonding axis versus the weight loss of the hydrocarbon soil. To control the test conditions, the temperature and the time that the solvent is exposed to the soil is the same for each solvent. The graph, on the next page, is a surface plot for a number of different solvents. The data file was created by CO-SOLVE-IT! and stored on disk. This data file was then imported into a graphing program called: PS-PLOT(tm) (now known as PSI-PLOT(tm)). << GRAPH & TABLE WOULD BE HERE >> AN EXAMPLE OF SOLVENT SYNERGY In the following example, an epoxy resin (D.E.R 331 DOW (tm)) is found, in simulation, not to be soluble in either methanol (MEOH) or xylene. The question then is: can these two solvents in a blend dissolve this resin? CO-SOLVE-IT! was run for these two solvents, (below), and does predict: neither solvent alone will dissolve this resin. Next, other blends of MEOH and XYLENE were run, a sort of computer simulated ladder study. The results are summarized in a couple of tables and in graphics. This is a particularly good example of how simulations can uncover effects not readily discernable, and with a minimum confidence of 85% or so. Solvent :MEOH volume fract. (0.000-1.000) 1 Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent Interaction Radius = 18.239213 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 is NOT soluble in the solvent(s). ------------------------------------------------------------- Solvent :XYLENE volume fract. (0.000-1.000) 1 Resin Solubility Report Date :19930812 ======================= Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent Interaction Radius = 16.728763 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 is NOT soluble in the solvent(s). ------------------------------------------------------------ Solvent :MEOH volume fract. (0.000-1.000) .1 Solvent :XYLENE volume fract. (0.000-1.000) .9 Resin Solubility Report Date :19930812 ======================= Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent(s) Blend Properties H-Bond : Polar : Dispersion : R-Radius -------- ------- ------------ ------ 5.183 2.168 17.292 14.980112 Solvent Interaction Radius = 14.980112 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 IS soluble in the solvent(s). ------------------------------------------------------- Solvent :MEOH volume fract. (0.000-1.000) .2 Solvent :XYLENE volume fract. (0.000-1.000) .8 Resin Solubility Report Date :19930812 ======================= Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent(s) Blend Properties H-Bond : Polar : Dispersion : R-Radius -------- ------- ------------ ------ 7.266 3.336 16.984 13.703017 Solvent Interaction Radius = 13.703017 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 IS soluble in the solvent(s). Solvent :MEOH volume fract. (0.000-1.000) .3 Solvent :XYLENE volume fract. (0.000-1.000) .7 Resin Solubility Report Date :19930812 ======================= Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent(s) Blend Properties H-Bond : Polar : Dispersion : R-Radius -------- ------- ------------ ------ 9.349 4.504 16.676 12.779152 Solvent Interaction Radius = 12.779152 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 IS soluble in the solvent(s). ------------------------------------------------------- Solvent :MEOH volume fract. (0.000-1.000) .4 Solvent :XYLENE volume fract. (0.000-1.000) .6 Resin Solubility Report Date :19930812 ======================= Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent(s) Blend Properties H-Bond : Polar : Dispersion : R-Radius -------- ------- ------------ ------ 11.432 5.672 16.368 12.288446 Solvent Interaction Radius = 12.288446 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 IS soluble in the solvent(s). ------------------------------------------------------- Solvent :MEOH volume fract. (0.000-1.000) .45 Solvent :XYLENE volume fract. (0.000-1.000) .55 Resin Solubility Report Date :19930812 ======================= Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent(s) Blend Properties H-Bond : Polar : Dispersion : R-Radius -------- ------- ------------ ------ 12.4735 6.256 16.214 12.223642 Solvent Interaction Radius = 12.223642 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 IS soluble in the solvent(s). ------------------------------------------------------- Solvent :MEOH volume fract. (0.000-1.000) .5 Solvent :XYLENE volume fract. (0.000-1.000) .5 Resin Solubility Report Date :19930812 ======================= Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent(s) Blend Properties H-Bond : Polar : Dispersion : R-Radius -------- ------- ------------ ------ 13.515 6.84 16.06 12.282924 Solvent Interaction Radius = 12.282924 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 IS soluble in the solvent(s). Solvent :MEOH volume fract. (0.000-1.000) .6 Solvent :XYLENE volume fract. (0.000-1.000) .4 Resin Solubility Report Date :19930812 ======================= Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent(s) Blend Properties H-Bond : Polar : Dispersion : R-Radius -------- ------- ------------ ------ 15.598 8.008 15.752 12.763216 Solvent Interaction Radius = 12.763216 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 IS soluble in the solvent(s). Solvent :MEOH volume fract. (0.000-1.000) .7 Solvent :XYLENE volume fract. (0.000-1.000) .3 Resin Solubility Report Date :19930812 ======================= Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent(s) Blend Properties H-Bond : Polar : Dispersion : R-Radius -------- ------- ------------ ------ 17.681 9.176 15.444 13.678241 Solvent Interaction Radius = 13.678241 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 IS soluble in the solvent(s). ------------------------------------------------------- Solvent :MEOH volume fract. (0.000-1.000) .8 Solvent :XYLENE volume fract. (0.000-1.000) .2 Resin Solubility Report Date :19930812 ======================= Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent(s) Blend Properties H-Bond : Polar : Dispersion : R-Radius -------- ------- ------------ ------ 19.764 10.344 15.136 14.948378 Solvent Interaction Radius = 14.948378 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 IS soluble in the solvent(s). ------------------------------------------------------- Solvent :MEOH volume fract. (0.000-1.000) .9 Solvent :XYLENE volume fract. (0.000-1.000) .1 Resin Solubility Report Date :19930812 ======================= Resin/Pigment :D.E.R 331 Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :6.10 Polar :16.40 Dispersion :15.00 Radius of Interaction :16.70 Solvent(s) Blend Properties H-Bond : Polar : Dispersion : R-Radius -------- ------- ------------ ------ 21.847 11.512 14.828 16.491782 Solvent Interaction Radius = 16.491782 Resin/Pigment Radius of Interaction = 16.7 The resin/pigment D.E.R 331 IS soluble in the solvent(s). TABLE DEPICTS THE SOLVENT'S RADIUS, AND THE RECIPROCAL VALUE <> The blends used are (by volume): 100% XYLENE, MEOH/XYLENE(10/90), MEOH/XYLENE(20/80), MEOH/XYLENE(30/70), MEOH/XYLENE(40/40), MEOH/XYLENE(45/55), MEOH/XYLENE(50/50), MEOH/XYLENE(55/45), MEOH/XYLENE(60/40), MEOH/XYLENE(70/30), MEOH/XYLENE(80/20), MEOH/XYLENE(90/10), MEOH/XYLENE(95/5), 100% MEOH A HYPOTHETICAL EXAMPLE OF A LACQUER For example, let us assume that we have a general purpose white lacquer, what follows is the vehicle formulation. COMPONENTS VOL. FRACTION Titanium Dioxide .405 EBA .162 MEK .108 TOLUENE .108 n-BUTYL BENZYL PHTHALATE .216 These fractions were taken from the formulation, converted to volume fractions and normalized to 1. The resin in the formulation is: PMMA (polymethyl methacrylate) The object is to test whether the original formulation will solubilize the resin. The next step is to try replacement solvents. Perhaps, let's try EBA as a first replacement. After CO-SOLVE-IT! is run, the following report was generated: RESIN: PMMA Solvent :TIO2 RN57 volume fract. (0.000-1.000) .405 Solvent :EBA volume fract. (0.000-1.000) .162 Solvent :MEK volume fract. (0.000-1.000) .108 Solvent :TOLUENE volume fract. (0.000-1.000) .108 Solvent :N-BUTYL BENZYL PHTHALATE volume fraction = .216 On the following pages are a CO-SOLVE-IT! run. Notice that a run was made for each individual solvent and plasticizer. This was done to complete the characterization. Also notice that EBA does dissolve PMMA better than does PMA by itself. However, in conjunction with the other solvents, this resin should (in theory) be soluble. The pigment was included just for fun.If you were only concerned with resin-solvent solubility, this would not be necessary. ORIGINAL FORMULATION (as given above) Resin Solubility Report Date :19930804 ======================= Resin/Pigment :PMMA Resin's/Pigment Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :7.50 Polar :10.50 Dispersion :18.60 Radius of Interaction :8.60 Solvent(s) Blend Properties H-Bond : Polar : Dispersion : R-Radius -------- ------- ------------ ------ 10.68984 8.1081 16.2108 6.2232926 Solvent Interaction Radius = 6.2232926 Resin/Pigment Radius of Interaction = 8.6 The resin/pigment PMMA IS soluble in the solvent(s). ---------------------------------------------------- (The original solvents and pigment, as expected should be soluble in the resin.) SOLVENT-BASED RESIN/SOLVENT SOLUBILITY 08-04-93 USING HANSEN PARAMETERS Radii of Interaction in Hansen Space Vol. Fraction Solvent(s) Resin Soluble? YES RESIN:----> PMMA .270 EBA 3.16 8.60 .180 TOL .180 MEK .360 n-Butyl benzyl phthalate Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°° Resins Radius---> °°°°°°°° RESIN:----> PMMA .270 PMA 3.88 8.60 .180 MEK .180 TOL .360 n-Butyl benzyl phthalate Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°° Resins Radius---> °°°°°°°° SOLVENT-BASED RESIN/SOLVENT SOLUBILITY 08-04-93 USING HANSEN PARAMETERS Radii of Interaction in Hansen Space Vol. Fraction Solvent(s) Resin Soluble? (yes/no) RESIN:----> PMMA 1.00 Di-n-butyl phthalate 4.21 8.60 yes Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°°° Resins Radius---> °°°°°°°° RESIN:----> PMMA 1.00 n-Butyl benzyl phthalate 4.54 8.60 Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°°° Resins Radius---> °°°°°°°° SOLVENT-BASED RESIN/SOLVENT SOLUBILITY 08-04-93 USING HANSEN PARAMETERS Radii of Interaction in Hansen Space Vol. Fraction Solvent(s) Resin Soluble? (yes/no) RESIN:----> PMMA .270 PMA 5.22 8.60 (yes) .180 MEK .180 TOL .360 Di-n-butyl phthalate Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°°°° Resins Radius---> °°°°°°°° RESIN:----> PMMA 1.00 EBA 5.43 8.60 yes Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°°°° Resins Radius---> °°°°°°°° SOLVENT-BASED RESIN/SOLVENT SOLUBILITY 08-04-93 USING HANSEN PARAMETERS Radii of Interaction in Hansen Space Vol. Fraction Solvent(s) Resin Soluble? (yes/no) RESIN:----> PMMA .460 PMA 6.04 8.60 (yes) .180 TOL .360 Di-n-butyl phthalate Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°°°°° Resins Radius---> °°°°°°°° RESIN:----> PMMA .640 PMA 6.40 8.60 (yes) .360 Di-n-butyl phthalate Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°°°°° Resins Radius---> °°°°°°°° SOLVENT-BASED RESIN/SOLVENT SOLUBILITY 08-04-93 USING HANSEN PARAMETERS Radii of Interaction in Hansen Space Vol. Fraction Solvent(s) Resin Soluble? (yes/no) RESIN:----> PMMA 1.00 PMA 8.66 8.60 (no) Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°°°°°°° Resins Radius---> °°°°°°°° RESIN:----> PMMA 1.00 DPMA 9.67 8.60 no Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°°°°°°°° Resins Radius---> °°°°°°°° SOLVENT-BASED RESIN/SOLVENT SOLUBILITY 08-04-93 USING HANSEN PARAMETERS Radii of Interaction in Hansen Space Vol. Fraction Solvent(s) Resin Soluble? (yes/no) RESIN:----> PMMA 1.00 TOL 9.96 8.60 no Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°°°°°°°° Resins Radius---> °°°°°°°° RESIN:----> PMMA 1.00 MEK 16.24 8.60 no Graphical Representation of the Calculations ____________________________________________ If SOLVENTS radius LESS THAN (<) RESINS radius, solvent should solubilize the resin. Solvents Radius-> °°°°°°°°°°°°°°°° Resins Radius---> °°°°°°°° CO-RESIN'S MAIN MENU CO-RESIN / COMMAND MENU K.....Menu - Polymer Hansen Regression Program S.....Select those Solvent(s) which Swell the Resin. V.....View Results on the Screen Z.....Print to a File, after solvent mix run. P.....Print to the Printer B.....Execute a BATCH print job. G.....Graph the results J.....3D Graph of Resin/Solvent(s) interaction as a function of 2 parameters. * UTILITIES MENU * C.....Create a new Resin file A.....Add data to the 'NEW' Resin file L.....List the resin file to the screen F.....Find a SOLVENT H.....Help - Instructions & Solvent/Resin Lists X.....Erase the log file: resin.txt Y.....do RESIN statistics, calculate k&C values. O.....Input k values, calculate RESIN parameters and print out report to disk file. Q.....Quit the program Your selection? Instructions: Enter the key corresponding to the command you wish to select. Next, if you wish to determine an unknown resin's radius of interaction, enter at least 7 solvents which are known to solubilize the resin. Once all of the information is entered, press return to end this process. At this point the radius for the resin and the resin's Hansen parameters are approximated.(by method 1). If the radius vector cannot be determined, (singular or saddle points are encountered), then the report routine, (Option v) will tell the user to try a different solvent combination. Try adding or deleted a solvent first. Note that minimum user information is being supplied, the user should keep in mind these are only estimates of resin parameters, and should be treated as such if used in future simulations. You may then print to the screen, file or the printer. --- MENU KEY --- K- Start the program "CO-RADII" S - Solvent selection: Enter up to 65 solvent/Solution. viscosities.(End of help file has suggested TEST MIX) Enter the solvent name, (abbrev.), exactly as the solvent appears in the documentation. Also, enter the resin and solvent mix (solution) viscosity. The Hansen values are then printed to the screen and are automatically logged to RESIN.TXT. Repeat the process; at least 5 solvents must be entered. V - VIEW selection: See the result printed to the screen. Z - LOG the VIEW : Log to file RESIN.TXT - to keep result. P - PRINT the VIEW to the printer (lpt1 or prn) B - BATCH print the solvent(s) and resin parameters to printer attached to lpt1, cumulative RESIN.TXT G - Graph the results. There is a set of graphs and solution maps that show how the solvents interact with the resin. --- UTILITIES MENU - KEY C - Create a new solvents data file, of your own. A - Add solvents and hansen parameters to the file that you create. L - LIST the solvents data base to the screen. This is one way to check a solvents accepted abbrev. Be prepared to scroll through all 500+ solvents. F - FIND a solvent, not used in calculations. Another way to check the spelling of the solvents abbrev. H - HELP FILE & SOLVENT/RESIN LISTS the file you are reading. O - Input the 'k' values and determine intrinsic visc. of the different solvents. After that press any key and a number of viscosity maps will be graphed. Print screen from keyboard to hard copy. Appropriate printer drivers must have been loaded first from DOS- MS DOS 'graphics.com' CO-RESIN uses two methods to determine the resin Hansen parameters and the radius of interaction. The first uses a summation of the solvents radius vector and projects this radius vector on a surface in 3-Hansen Space. The magnitude of this vector is the radius. The 3-parameters are the projections of these surface coordinates. - USE CAUTION -INTENDED TO ROUGH OUT A NUMBER WHEN DATA IS NOT AVAILABLE. The second method requires a minimum of 5 solvents, (the preferred minimum number is: 7 mixes), and relates the INTRINSIC viscosity of the resin to the 3-component model. This method writes a file to disk containing the solvent's parameters and the intrinsic viscosity. Next, a powerful program called NONLIN does nonlinear regression analysis and prints the results to a file. PRINTING A GRAPH - To print a graph you must first have loaded (from DOS) the command: 'GRAPHICS.COM' and the appropriate printer drivers for your printer. Your printer must be attached to lpt1. REMEMBER to turn the printer on & 'ON LINE'. Then select the print option when asked. At present all graphs in the series will be printed. Q -QUIT the program and go to the operating system. PAGE DOWN FOR SOLVENT/RESIN TEST MIX INSTRUCTIONS TEST MIX PREPARATION 1. Make a solution of 100% solids resin (or calculated solids, adjusting for solvents). All test solutions should be at the same concentration. The CONCENTRATION is: in grams/100 ml (solvent). The range should be 5-10%, but, 'ALL' test solutions for a given resin are at the same concentration say i.e. (10.0%); accuracy counts. All solutions should be at approximately the same temperature. (Temperature of solutions EQUAL TO OR GREATER THAN 25C) Measure the solvent/resin solution temperature. (deg. C) Measure the viscosity in consistent units. Such as: centipoise, poise or seconds. You will need to look up (for now) the solvents viscosity. -SOLVENT viscosity @ 25 deg. C ENTER: Temperature in degree C. Solvent viscosity @ 25 deg. C Solution viscosity @ test temp. deg.C Solute concentration for each.(g/100 ml) Swell Calculation Routine ------------------------- In this module you must enter the 'k' values obtained from a set of solvents (minimum of 7) and a test resin. The 'k' values are printed to the screen after you have entered the set of solvents and a resin and have run -Option Y - 'swell statistics'. You must determine experimentally the viscosity of the resin solvent mix at constant conditions. The 'k' values need only be entered once for a given resin. These values are then used to 'guess' the relative 'swell' that a new or different solvent might have on the resin of interest. Note: These values are computed when the ascii file generated by CO- RESIN is processed by NONLIN (tm). The idea is to try and find out, for unknown solvents or solvent blends, what effect these blends have on the resin. How much does blend X swell a test polymer. You might give these ideas a try with emulsions and systems containing water. Water is a tough challenge. If its concentration is the same for all samples, try running this program with water included and excluded. By the way, this program was not tested against experiment; it really should be, but I do not own a laboratory. EXAMPLE INPUT DIALOGUE What is the name of the resin ? hydrocarbon resin How many solvents in the test mix? (min.=7) 7 Enter the temperature in degrees C (25-->70) : 27 What Solvent? tol Enter the solvents viscosity at 25 deg. C :.7 Enter the viscosity for this solution (constant solids) :100 Enter the solute concentration - (5-10% conc.) in (g/100 ml soln.) :10 Solvent: TOL Hansen Hydrogen: 3.27 Hansen Polar: 1.64 Hansen Dispersion: 19.43 Total Solubility: 19.77 Solvent viscosity at 25 deg. C: .7 Solvent corrected viscosity at 27 deg.C: .64135434 SOLUTION - viscosity at 27 deg.C: 100 Solute concentration in (g/100 ml): 10 INTRINSIC viscosity is: 15.492005 What Solvent? EXAMPLE REPORT (RESIN.TXT) Solvent :tol Solvent :xyl Solvent :turpentine Solvent :ptb Solvent :a100 Solvent :a150 Solvent :vmpn Solvent :ptb Solvent :dptb Solvent :o-dichlorobenzene Resin Properties Report Date :19930810 ======================= Resin :hydrocarbon resin Resin's Properties: (Hansen H-Bond, Polar, Dispersion, Radius of interaction) H-Bond : 5.093 Polar : 2.716 Dispersion : 17.545 Solvent Interaction parameter = 18.470039 Resin's Radius of Interaction = 7.6105129 EXAMPLE OF "SWELL DIALOGUE" Enter K0: .44786 Enter Ka: -.8167 Enter Kb: .7929 Enter Kc: -1.085 How many solvent runs are to be made ?7 Enter the solvent name: dpm Enter the solvent's Hansen Disp. parameter: 15.13 Enter the solvent's Hansen Polar parameter: 3.14 Enter the solvent's Hansen Hbond parameter: 13.7 Enter the solvent name: pm Enter the solvent's Hansen Disp. parameter: 15.34 Enter the solvent's Hansen Polar parameter: 6.75 Enter the solvent's Hansen Hbond parameter: 15.75 Enter the solvent name: xyl Enter the solvent's Hansen Disp. parameter: 20.04 Enter the solvent's Hansen Polar parameter: 1.84 Enter the solvent's Hansen Hbond parameter: 2.45 Enter the solvent name: tol Enter the solvent's Hansen Disp. parameter: 19.43 Enter the solvent's Hansen Polar parameter: 1.64 Enter the solvent's Hansen Hbond parameter: MENU FOR THE PROGRAM CO-RADII RESIN CALCULATION MODULE ------------------------ (enter the appropriate letter) S.....Select Solvents from given set. V.....Print to the Screen Z.....Print to a File -do to keep result.(radii.txt) B.....Execute a BATCH print job. G.....Graph the results -------UTILITIES MENU------- C.....Create a new SOLVENTS file A.....Add data to the SOLVENTS file L.....List the solvent file to the screen F.....Find a SOLVENT X.....Erase log files. H.....Help--->instructions Q.....Quit the program Your selection? CO-RADII -- INPUT DIALOGUE To what extent does the solvent solubilize the resin? Enter: 10 - completely miscible Enter: 8 - hazy solution, almost completely soluble. Enter: 5 - partially soluble, clumps or particles. Enter: 2 - softens resin, not very soluble. Enter: 1 - not at all soluble. Test Solvents Mix ----------------- 1-propanol PnB o-dichlorobenzene EB EBA Toluene Acetone 1-Octanol MEK 2-Nitropropane Xylene DMAC PMA MIBK Isophorone What Solvent? tol Enter the solubility factor for this solvent. :10 SAMPLE OF CO-RADII - REPORT TO THE SCREEN Resin Solubility Report Date :19930811 ======================= Resin : ____________________________________________________________ Resin's Properties: (Hansen H-Bond, Polar, Dispersion, Radius of Interaction) H-Bond :11.25 Polar :3.70 Dispersion :14.90 Radius of Interaction : 7.3343203 SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" 1,3-butanediol 1,4-dioxane 1-1 dichloroethane 1-1 dichloroethylene 1-1-1 trichloroethane 1-1-2 Trichlorotrifluoroethane 1-1-2-2 Tetrabromoethane 1-1-2-2 tetrachloroethane 1-1-Dimethylhydrazine 1-2 dichloroethane 1-2 Dichlorotetrafluoroethane 1-2 dimethylbenzene 1-2-3-propanetriol 1-2-ethanediol 1-3-5 trimethylbenzene 1-3-Benzenediol 1-3-Butanediol 1-3-Dimethyl-1-butanol 1-Bromonaphthalene 1-butanamine 1-butanoic acid 1-butanol 1-chloropropane 1-Decanol SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" 1-Methylnaphthalene 1-Octanol 1-Pentanol 1-Pentanol 1-propanol 2-2-4 Trimethylpentane 2-butanol 2-butanone 2-Ethoxyethyl acetate 2-Ethyl-1-butanol 2-Ethyl-1-hexanol 2-furancarboxaldehyde 2-Methyl-1-propanol 2-methylbutane 2-nitropropane 2-nitropropane 2-Octanol 2-propanol 2-propanone 2-propenenitrile 2-Pyrrolidone 3-Chloropropanol 3-methylphenol 3-PLY CHLORINATED POLYETHYLENE SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" A100 A150 ACET Acetaldehyde Acetic acid Acetic anhydride acetone Acetonitrile acetophenone Acetyl chloride Acrylonitrile Allyl alcohol ALUMINUM PULVER BLACK 80 Aniline Anisole ARALDIT 488 ASPHALT ASPHALTENE ASTM FUEL A ASTM FUEL B ASTM FUEL C ASTM OIL 1 ASTM OIL 2 SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" ASTM OIL 3 AUTO BRAKE FLUID AUTO TRANS. FLUID BAKELITE PKHH Benzaldehyde Benzene benzenemethanol Benzoic acid Benzonitrile Benzyl alcohol Benzyl Chloride BETA-PINENE RESIN Biphenyl Bis(2-chloroethyl)ether Bis-(m-phenoxyphenol)ether BISPHENOL A EPOXY ESTER BISPHENOL A EPOXY RESIN BISPHENOL A TRIMELLITIC EPOXY ESTER BLOCKED ISOCYANATE-PHENOL BRILLIANT SKY BLUE 3862 bromobenzene Bromochloromethane bromoethane SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" bromoform butanol Butoxy ethanol Butoxy ethoxy ethanol Butyl Acetate Butyl Carbitol Butyl Cellosolve BUTYLBENZYL PHTHALATE Butyraldehyde Butyronitrile BZOH C318 Carbitol CARBON BLACK PRINTEX V 5519-1 Carbon Disulfide carbon tetrachloride castor oil Cellosolve CELLULOSE ACETATE BUTYRATE CAB-171-2 CELLULOSE ACETATE BUTYRATE CAB-272 CELLULOSE AVICEL PH101 CELLULOSE PROPIONATE chlorobenzene SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" Chlorodifluoromethane chloroform chloromethane CHLOROSULFONYL POLYETHYLENE cis-Decahydronaphthalene COAL RESIN #510 CYCK Cyclohexane Cyclohexane cyclohexanol Cyclohexanone Cyclohexyl Chloride Cyclohexylamine DAA DB DBA DBE DE DEA decalin DER 684 Di-(-isobutyl) ketone SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" Di-(2-chloroisopropyl)ether Di-(2-methoxyethyl)ether Di-n-butyl phthalate Di-n-butyl sebacate Di-n-propylamine diacetone alcohol Dibenzyl ether DIBK Dibutyl stearate dichlorodifluoromethane Dichlorofluoromethane dichloromethane Diethyl carbonate Diethyl Ether Diethyl Ketone Diethyl phthalate DIETHYL PHTHALATE Diethyl sulfate Diethyl Sulfide Diethylamine diethylene glycol Diethylene Glycol Diethylenetriamine SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" Diethylketone DIISODECYL PHTHALATE dimethoxymethane dimethyl formamide dimethyl phthalate Dimethyl phthalate Dimethyl sulfone dimethyl sulfoxide Dimethylsulfoxide Dioctyl phthalate DIPE dipropylene glycol Dipropylene Glycol DM DMAC DMF DMSO Dowanol DPM* Dowanol PM* Dowanol PMA* Dowanol PnB* Dowanol TPM* DPB SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" DPE DPM DPMA DPnB DPTB EAK EB EBA EBZ EE EEA EEH EEP eg monoethyl ether acetate EGDAC EHAC EHOH EM EMA EP Epichlorohydrin ETAC Ethanethiol SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" ethanoic acid ethanol Ethanolamine ethenylbenzene Ethoxy ethanol Ethoxy ethoxyethanol Ethoxy ethyl acetate Ethyl acetate Ethyl bromide Ethyl chloroformate Ethyl cinnamate Ethyl formate Ethyl lactate ethylbenzene Ethylene Carbonate Ethylene cyanohydrin Ethylene diamine Ethylene dibromide ethylene dichloride Ethylene dichloride ethylene glycol Ethylene Glycol ETOH SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" ETPR FANALROSA G SUPRA PULVER RED FORAFLON 4000LD PCUK FRANCE FORM FORMALDEHYDE 1,1-DIMETHYLPHENOL Formamide Formic acid Freon 11 Freon 113 Freon 114 Freon 12 Freon 21 Freon 22 Furan Furfural Furfuryl alcohol FURFURYL ALCOHOL RESIN g-butyrolactone gamma-butyrolactone GBL Glycerol HANSAGELB 10G YELLOW HELIOGENBLAU B PULVER BLUE 15 SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" HELIOGENBLAU LG PULVER BLUE 16 HELIOGENGRUN GN GREEN 7 Hexamethyl phosphoramide hexane Hexylene Glycol HOAC HOOKER DUREZ 14383 HYDROCARBON RESIN HYPALON IAMOH IBIB IBUAC IBUOH IPRAC IPROH Isoamyl acetate isobutanol Isobutyl acetate Isobutyl isobutyrate ISOCYANURATE ISOCYANATE RESIN ISOK ISOL BENZIDINE YELLOW G2537 ISOL BENZIDINE YELLOW GAPR9500 SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" ISOL FAST YELLOW ISOL RUBY RED BKS7520 ISOLBONARED 7522 RED ISOLFAST RED 2G 2516 ORANGE isooctane Isopentane isophorone Isopropyl palmitate LEXAN LS2 LIM LINSEED OIL LIPOSURFACT ALKYL-ARYL LIPOSURFACT CYCLOHEXYL LIPOSURFACT ETHYL LIPOSURFACT HYDROXY STEARATE LIPOSURFACT ISONOYL PHENYL LIPOSURFACT ISOOCTYL PHENYL LIPOSURFACT ISOPROPYL LIPOSURFACT ISOTRIDECYL LIPOSURFACT LAURATE LIPOSURFACT lauryl LIPOSURFACT N-BUTYL LIPOSURFACT N-HEXADECYL SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" LIPOSURFACT OLEATE LIPOSURFACT OLEYL LIPOSURFACT PALMITATE LIPOSURFACT STEARATE LS m-Cresol MAK MC MEK MEOH Mesityl Oxide Mesitylene methanoic acid methanol Methoxy ethanol Methoxybenzene methyl acetate methyl alcohol Methyl Carbitol Methyl Cellosolve Methyl Chloride methyl ether methyl isobutyl ketone SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" Methyl oleate Methyl Salicylate Methylacetate Methylal methylbenzene Methylcyclohexane methylene chloride Methylene dichloride Methylene diiodide Methylisobutylketone MHK MIAK MIBK MIL-H-5606 PETR. MIL-H-8446 SILICATE MIL-L-7808 ESTER MIPK MMB MMBA MNPK MONOLITE FAST BLUE 4 Morpholine MOTOR OIL SAE 20W SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" MPEAC MS MTBE n-amyl alcohol n-Butane n-butanol n-Butyl acetate n-Butyl benzyl phthalate n-Butyl chloride n-Butyl lactate n-Butylamine n-butyric acid n-Decane n-Dodecane n-Eicosane n-Heptane n-Hexadecane n-Hexadecane n-Hexane n-methyl-2-pyrrolidone N-Methyl-2-pyrrolidone N-N-Dimethylacetamide N-N-Dimethylformamide SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" n-Nonane n-Octane n-Octanoic acid n-Pentadecane n-Pentane n-Propyl chloride n-Propylamine Naphthalene NBUAC NBUOH NBUPR NEATS FOOT OIL NEBONY 100 INDENE-CYCLOPENTADIENE RESIN NHEP NHEX nitrobenzene Nitrobenzene nitroethane Nitromethane NMP Nonyl Phenol Nonyl phenoxy ethanol NP NPEPR SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" NPRAC NPROH NPRPR o-dichlorobenzene o-dichlorobenzene o-Methyloxyphenol o-Xylene octadecanoic acid Oleic acid Oleyl alcohol OMS p-Diethylbenzene PAA PARTIALLY BUTYLATED MELAMINE RESIN PB PC PE PEA PEERLESS CARBON BLACK PENTAERYTHRITOL MALEATED ROSIN RESIN PENTAERYTHRITOL MALEATED ROSIN RESIN B PENTAERYTHRITOL ROSIN ESTER A PERC SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" perchloroethylene Perfluoro-n-heptane Perfluorodimethylcyclohexane Perfluoromethylcyclohexane PERMANENT BORDEAUX FRR RED 12 PERMANENT ORANGE G 13 PERMANENT RED FGR RED 112 PERMANENT VIOLET RL SUPRA 23 PERMANENTGELB H 10 YELLOW 81 PG PG* Phenol PHENOLIC RESOL RESIN PHOSPHATE HYDRAULIC PHTHALOCYANINE BLUE BG PLASTOPAL H UREA-FORMALDEHYDE BASF PM PMA PMA/GBL/NMP(50/30/20) PMA/NMP(70/30) PMA/NMP(75/25) PMA/THF/GBL/NMP(30/30/20/20) PMA/THF/NMP(33/33/33) PnB SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" PnP POLY 1-BUTEN-4-OL POLY ALLYL ALCOHOL POLY AMIDOHYDRAZIDE POLY BROMOPHENYLENE OXIDE DIMETHYL PHOSPHONATE POLY CARBONATE POLY CROTONAMIDE POLY-ALLYL 1-METHYL-2-HYDROXYETHYL ETHER POLY-ALLYL 2-HYDROXY-2-PHENYLETHYL ETHER POLY-ALPHA-BROMO-N-HYDROXYMETHYL ACRYLAMIDE POLY-ALPHA-PHENYLETHYL ISOCYANIDE POLY1-CHLORO-2,3-EPOXYPROPANE POLY1-HEXEN-3-OL POLY1-NONYL-2-PENTENOL POLY1-OCTEN-3-OL POLY2-BROMOALLYL ALCOHOL POLY2-CHLOROALLYL ALCOHOL POLY2-ETHYL-1-PENTEN-3-OL POLY2-ETHYL-1-PROPEN-3-OL POLY2-HYDROXYBUTYL ACRYLATE POLY2-HYDROXYETHYL ACRYLATE POLY2-HYDROXYETHYL VINYL ETHER POLY2-HYDROXYPROPYL ACRYLATE SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" POLY2-METHYL-1-BUTEN-4-OL POLY2-METHYL-2-PROPEN-1-OL POLY2-METHYL-3-BUTYLACRYLAMIDE POLY3,3-DIETHYLOXETANE POLY3-HYDROXBUTYL VINYL ETHER POLY3-METHYL-1-BUTEN-3-OL POLY3-METHYL-1-PENTEN-3-OL POLY3-TERT-BUTYLOXETANE POLY4-CHLOROCROTONAMIDE POLY4-HYDROXYBUTYL ACRYLATE POLY4-HYDROXYBUTYL VINYL ETHER POLY5-HYDROXYPENTYL ACRYLATE POLYAXYETHYLATED SORBITAN MONOOLEATE POLYCINNAMIDE POLYDIACETONE ACRYLAMIDE POLYDICHLOROSTYRENE POLYDIMETHYLSILOXANE POLYEPICHLOROHYDRIN POLYESTER CRYPLEX 1473-5 POLYESTER DYNAPOL L206 POLYESTER TYPE ALIPHATIC & SESQUITERPENE ACIDS POLYESTER-MELAMINE POLYFLUOROSILICONE POLYGLYCOLAMINE SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" POLYMETHACRYLAMIDE POLYMETHACRYLMORPHOLIDE POLYN N-BIS HYDROXYETHYLACRYLAMIDE POLYN,N-BIS[2-CYANOETHYL]ACRYLAMIDE POLYN,N-DI-N-BUTYL ACRYLAMIDE POLYN,N-DIBENZYLACRYLAMIDE POLYN,N-DICYCLOHEXYLACRYLAMIDE POLYN,N-DIISOPROPYL CROTOAMIDE POLYN,N-DIPHENYLACRYLAMIDE POLYN,N-DODECYL ACRYLAMIDE POLYN,N-METHYLENE BISCROTONAMIDE POLYN-1,1-BISHYDROXYMETHYLETHYL METHYLACRYLAMIDE POLYN-1,1-DIBUTYLAMYL ACRYLAMIDE POLYN-1-BUTYL-1,3-DIMETHYLBUTYL CINNAMIDE POLYN-1-BUTYL-1-METHYLHEPTYL CINNAMIDE POLYN-1-ETHYL-1,3-DIMETHYLBUTYL ACRYLAMIDE POLYN-1-ETHYL-1-BUTYLAMYL ACRYLAMIDE POLYN-1-ETHYL-1-METHYLBUTYL CINNAMIDE POLYN-1-ETHYL-2-HYDROXYETHYL METHACRYLAMIDE POLYN-1-HEXYL-2-HYDROXY-1-METHYLETHYL ACRYLAMIDE POLYN-1-METHYL-1-BUTYL-3-METHYLBUTYLACRYLAMIDE POLYN-2-CYANOETHYL ACRYLAMIDE POLYN-2-CYANOETHYL-N-METHYL METHACRYLAMIDE SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" POLYN-2-OXOPROPYL ACRYLAMIDE polyN-ACETOXYMETHYL METHACRYLAMIDE POLYN-ACRYL-d-1-ALANINE POLYN-AMYL ACRYLAMIDE POLYN-BENZYL ACRYLAMIDE POLYN-BENZYL METHACRYLAMIDE POLYN-BENZYL-N-2-HYDROXYETHYL-METHACRYLAMIDE POLYN-CHLOROPHENYL METHACRYLAMIDE POLYN-CYCLOHEXYL ACRYLAMIDE POLYN-ETHYL METHACRYLAMIDE POLYN-ETHYL-2-ETHOXYCROTONAMIDE POLYN-ISOBUTOXYMETHYL ACRYLAMIDE POLYN-ISOOCTYLACRYLAMIDE POLYN-ISOPROPOXYMETHYL ACRYLAMIDE POLYN-ISOPROPYLACRYLAMIDE POLYN-METHACRYLUREA POLYN-METHOXYMETHACRYLAMIDE POLYN-METHOXYMETHYLMETHACRYLAMIDE POLYN-METHYL METHACRYLAMIDE POLYN-METHYL-3-ETHOXYACRYLAMIDE POLYN-METHYL-N-PHENYLACRYLAMIDE POLYN-METHYLACRYLAMIDE POLYN-N-BUTYL-2-ETHOXY ACRYLAMIDE SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" POLYN-N-HEPTYLACRYLAMIDE POLYN-N-OCTADECYLACRYLAMIDE POLYN-P-METHOXYPHENYLMETHACRYLAMIDE POLYN-P-METHYLBENZYLACRYLAMIDE POLYN-tert-AMYL METHACRYLAMIDE POLYN-tert-BUTYL CINNAMIDE POLYOXETANE POLYOXYMETHYLENE POLYVINYL BUTYRAL POLYVINYL SILICONE POLYVINYLIDENE FLUORIDE POLYVINYLIDENE FLUORIDE RESIN POLY[ALLYL 2,3-DIHYDROPROPYL ETHER] PP Propanediol Propionitrile propylene carbonate propylene glycol Propylene-1-2-carbonate PTB Pyridine Quinoline R11 SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" R113 R114 R115 R12 R13 R13B1 R142B R152A R21 R22 R40 RED IRON OXIDE REFLEX BLAU resorcinol ROSIN ESTER GUM SATURATED POLYESTER SBUAC SBUOH SHELLAC SPERM OIL SS140 SS70 Stearic acid SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" Styrene Succinic anhydride TBA TBUAC TBUPR TCE TCENE tetrachloromethane tetrachloromethane tetrahydrofuran TetrahydrofuranCRC tetrahydronaphthalene tetralin Tetramethylurea TEX THF THF/DPM/NMP/GBL(30/30/20/20) TIO2 RN57 TOL TOL/MEK(60/40) toluene TPM trans-Decahydronaphthalene SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" Tri-n-butyl phosphate tribromomethane Trichlorobiphenyl trichloroethylene trichloroethylene trichlorofluoromethane trichloromethane TRICRESYL PHOSPHATE Tricresyl phosphate Tridecyl alcohol Triethyl phosphate Triethylene Glycol Triethylene Glycol Trimethyl phosphate TRIOCTYL PHOSPHATE TRIPHENYL PHOSPHATE TRIXILENYL PHOSPHATE TS5 TURPENTINE UREA-FORMALDEHYDE RESIN VMP VMPN WAT SOLVENTS, RESINS, SURFACTANT AND PIGMENTS IN "SOLVENTS.IN" water WATER-GLYCOL HYDRAULIC FLUID X813 X81K X8600 X8700 X8800 X8900 XYL xyl/meoh*50/50 Xylene (LATE ADDITIONS) TPnB DPnP RESINS AND PIGMENTS DATABASE (RESINS.IN) IN ALPHABETICAL ORDER Alkydal F41 ALUMINUM PULVER BLACK 80 Bisphenol A epi Bisphenol A polySulfone BRILLIANT SKY BLUE 3862 Bunahuls CB10 Butvar B76 CARBON BLACK PRINTEX V 5519-1 Cellidore Cellolyn 102 Cellulose nitrate H-23 Ceriflex IR305 Color Jet Co-113 cymel 300 D.E.N novolac 438 D.E.R 331 Desmorphen 850 Drugloss Bla Durez 14383 Epikote 1001 Ester gum BL FANALROSA G SUPRA PULVER RED HANSAGELB 10G YELLOW HELIOGENBLAU B PULVER BLUE 15 RESINS AND PIGMENTS DATABASE (RESINS.IN) IN ALPHABETICAL ORDER HELIOGENBLAU LG PULVER BLUE 16 HELIOGENGRUN GN GREEN 7 Hycar 1052 ISOL BENZIDINE YELLOW G2537 ISOL BENZIDINE YELLOW GAPR9500 ISOL FAST YELLOW ISOL RUBY RED BKS7520 ISOLBONARED 7522 RED ISOLFAST RED 2G 2516 ORANGE Lucite 2042 Lutonal IC/123 MONOLITE FAST BLUE 4 Mowilith 50 PAN Parlon P-10 PEERLESS CARBON BLACK PEMA Pentalyn 255 Pentalyn 830 PERMANENT BORDEAUX FRR RED 12 PERMANENT ORANGE G 13 PERMANENT RED FGR RED 112 PERMANENT VIOLET RL SUPRA 23 RESINS AND PIGMENTS DATABASE (RESINS.IN) IN ALPHABETICAL ORDER PERMANENTGELB H 10 YELLOW 81 Phenodur 373U PHTHALOCYANINE BLUE BG Piccolyte S-1000 Piccopale 110 Piccoumarone 450-L Plastopal Plexal C34 Plexal P65 PMMA Poly(methyl methacrylate) poly(p-chlorostyrene) Polyacrylonitrile Polyamide polyamide 6,6,poly(hexamethylene adipa.) polybromophenylene oxide(dimethyl)phosph polybutadiene polymethacrylamide Polysar 5630 Polystyrene LG PVAC PVC RED IRON OXIDE RESINS AND PIGMENTS DATABASE (RESINS.IN) IN ALPHABETICAL ORDER REFLEX BLAU Rhoplex WL-91 Sericol MV 043 Sericol Polyplast PY-043 Sericol red Seristar D2528 Super Beckacite 1001 Suprasec F5100 Thermojet Hvid TIO2 RN57 tsrink070193 Versamid 930 Versamid 965 Vipla KR Radii.in - DATABASE o-dichlorobenzene mibk isophorone 1-octanol dmac xylene 2-nitropropane mek acetone toluene eba eb pma pnb 1-propanol RADII - DATABASE (INTENTIONALLY LEFT BLANK) REFERENCES 1. - The Three Dimensional Solubility Parameter - Key to Paint Component Affinities, Charles M. Hansen, Journal of Paint Technology, vol. 39, no. 505, Feb. 1967 2. - Solubility Parameters, Allan F. M. Barton, Chemical Reviews, 1975, vol. 75, no. 6 3. - The Challenge of the Solubility Parameter Concept, Harry Burrell, Journal of Paint Technology, vol. 40, no. 520, May 1968 4. - New Values of the Solubility Parameters from Vapor Pressure Data, K.L. Hoy, Journal of Paint Technology, vol. 42, no. 541, Feb. 1970 5. - Some Factors Affecting the Solubility of Polymers, P. A. Small, Journal of Applied Chemistry,3,Feb. 1953 6 - Dissolving Power of Solvents and Solvent Blends for Polymers, P.L. Huyskens & M.C. Haulait-Pirson, Journal of Coatings Technology, vol. 57, no. 724, May 1985 7. - Phenomenon of Cosolvency and Solution Parameters of Polyamide Resins, G. Narender & M. Yaseen, Indian Institute of Chemical Technology, Journal of Coatings Technology, vol. 61, no. 773, June 1989 8. - Application of Intrinsic Viscosity Data for Determination of Solubility Parameters and Molecular Weights of Alkyds, H. Ahmad & M. Yaseen, Journal of Coatings Technology, vol. 50, no. 640, May 1978 9. - Suspension Interaction of Pigments in Solvents: Characterization of Pigment Surfaces in Terms of Three- Dimensional Solubility Parameters of Solvents, K.M.A. Shareef, M. Yaseen, M. Mahmood Ali, P.J. Reddy, Journal of Coatings Technology, vol. 58, no. 733, Feb. 1986 10. - Using the Hansen Solubility Parameter Theory in Reformulating Solvent-Based Coatings., Wesley L. Archer, American Paint and Coatings Journal, March 2, 1992. 11. - Statistics for the User in Coatings, Robert D. Athey Jr., American Paint & Coatings Journal, Sept. 14, 1992 12. - Handbook of Solubility Parameters and Other Cohesion Parameters, Allan F. M. Barton, CRC Press 1985, Handbook of Polymer Parameters, CRC Press. 13. - Numerical Recipes in Pascal - The Art of Scientific Computing, Cambridge University Press, 1989 14. - Intro. to Paint Chemistry & Principles of Paint Tech., G.P.A Turner, C&H, 1988 ACKNOWLEDGEMENTS Even for this modest effort, my association with many other people has contributed to this program. To those many others my thanks. For those who contribute with their criticism and suggestions, my gratitude and appreciation. There are two people I would like to mention: First, my wife for putting up with the many hours in front of the tube, and for helping to proof read this document (a difficult task for someone with no technical interests). All remaining errors in the program and document are exclusively my own. I would also like to thank my daughter, a first year chemistry student, she named the program and engaged me in discussions about chemistry, she has a curious and clever approach to ordinary problems. Special thanks to the following Software Companies: Mix Software, Inc. - makers of: "POWER C (tm)" Philip Serrod, author of: "NONLIN (tm)" (4410 Gerald Place, Nashville, TN 37205) True Basic, Inc. - makers of: "True Basic (tm)" Polysoft (now called Poly Software International) - makers of: "PS-PLOT" (now called PSI-PLOT), technical plotting program (High quality graphs in the doc's. were made using "PS-PLOT") Application Techniques, Inc. - makers of: "Pizazz Plus(tm)" (I used this program to capture some screens) Expressware Corp. - makers of: "File Express (tm)" (This is a fine database program, made my life much easier.) All of the above products were used to develop these programs, they are all very fine products. A novice programmer, as I am, needs all the support one can get!