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CRC HANDBOOK OF
THERMODYNAMIC
DATA of
AQUEOUS
POLYMER
SOLUTIONS
Christian Wohlfarth
CRC Press
Boca Raton London New York Washington, D.C.
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2004 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works

Version Date: 20130919
International Standard Book Number-13: 978-0-203-99820-5 (eBook - PDF)
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Foreword
The knowledge of thermodynamic data of aqueous polymer solutions is important for basic and
applied chemistry and chemical engineering, computational modelling and thermodynamic research. It has
many applications in the fields of biotechnology, membrane science and membrane technology,
environmental and green chemistry, food chemistry and food industry.
Among the existing publications in this field are C. Wohlfarth’s own book Vapor-Liquid
Equilibria of Binary Polymer Solutions (Elsevier, 1994) and his recent CRC Handbook of Thermo-
dynamic Data of Copolymer Solutions (CRC Press, 2001). Liquid-liquid equilibrium data can be found in
Albertson’s book Partition of Cell Particles and Macromolecules (Wiley, 1986), and more recently in
Zaslavsky’s book Aqueous Two-Phase Partitioning. Physical Chemistry and Bioanalytical Applications
(Dekker, 1995). All these data are fairly old and cover a limited number of properties and chemical
systems that represent only a minor portion in comparison with this new book. Commercial electronic
databases do not provide such data. This Handbook offers a new and complete collection on
thermodynamic data of aqueous polymer solutions.
This new book contains low- and high-pressure equilibrium data, vapor-liquid equilibria, liquid-
liquid equilibria, enthalpic and volumetric data, as well as second virial coefficients. This covers all the
necessary areas for researchers and engineers who work in this field. It will help users to retrieve quickly
all the relevant information from the original literature and also help researchers to plan new
measurements where data are missing.
The structure and the contents of this book are organized in a similar way as in the CRC
Handbook of Thermodynamic Data of Copolymer Solutions and this will facilitate the extraction of the
desired new data.
Last but not least, author C. Wohlfarth has been known for his experience in thermodynamics of
polymer solutions for more than 20 years.
I am sure that readers interested in the field of thermodynamic properties of polymer solutions
will benefit from this Handbook and will identify the work that has to be done in the future.
Dr. Henry V. Kehiaian
IUPAC Representative on ICSU Committee on

Data for Science and Technology (CODATA)
PREFACE
Knowledge of thermodynamic data of polymer solutions is a necessity for industrial and

laboratory processes. Such data serve as essential tools for understanding the physical behavior of
polymer solutions, for studying intermolecular interactions, and for gaining insights into the molecular
nature of mixtures. They also provide the necessary basis for any developments of theoretical
thermodynamic models. Scientists and engineers in academic and industrial research need such data and
will benefit from a careful collection of existing data. The CRC Handbook of Thermodynamic Data of
Aqueous Polymer Solutions provides a reliable collection of such data for such polymer solutions from the
original literature.
The Handbook is divided into seven chapters: (1) Introduction, (2) Vapor-Liquid Equilibrium
(VLE) Data of Aqueous Polymer Solutions, (3) Liquid-Liquid Equilibrium (LLE) Data of Aqueous
Polymer Solutions, (4) High-Pressure Phase Equilibrium (HPPE) Data of Aqueous Polymer Solutions, (5)
Enthalpy Changes for Aqueous Polymer Solutions, (6) PVT Data of Polymers and Solutions, and (7)
Second Virial Coefficients (A2) of Aqueous Polymer Solutions. Finally, appendices quickly route the user
to the desired data sets. Thus, the book covers all the necessary areas for researchers and engineers who
work in this field.
In comparison with low-molecular systems, the amount of data for aqueous polymer solutions is
still rather small. About 800 literature sources were perused for the purpose of this handbook, including
some dissertations and diploma papers. About 1000 data sets, i.e., 165 vapor-pressure isotherms, a
number of Henry’s constants, 500 LLE and a small number of HPPE data sets, a number of volumetric
and enthalpic data and some second osmotic virial coefficients, are reported. Additionally, tables of
systems are provided where results were published only in graphical form in the original literature to lead
the reader to further sources. Data are included only if numerical values were published or authors
provided their numerical results by personal communication (and I wish to thank all those who did so). No
digitized data have been included in this data collection. The Handbook is the first complete overview
about this subject in the world’s literature. The closing day for the data collection was May 31, 2003. The
Handbook results from parts of a more general database, Thermodynamic Properties of Polymer Systems,
which is continuously updated by the author. Thus, the user who is in need of new additional data sets is
kindly invited to ask for new information beyond this book via e-mail at wohlfarth@chemie.uni-halle.de.
Additionally, the author will be grateful to users who call his attention to mistakes and make suggestions
for improvements.
The CRC Handbook of Thermodynamic Data of Aqueous Polymer Solutions will be useful to
researchers, specialists, and engineers working in the fields of polymer science, physical chemistry,
chemical engineering, material science, biological science and technology, and those developing
computerized predictive packages. The Handbook should also be of use as a data source to Ph.D. students
and faculty in Chemistry, Physics, Chemical Engineering, Biotechnology, and Materials Science
Departments at universities.
Christian Wohlfarth
Merseburg, August 2003
About the Author
Christian Wohlfarth is Associate Professor for Physical Chemistry at Martin Luther University
Halle-Wittenberg, Germany. He earned his degree in Chemistry in 1974 and wrote his Ph.D. thesis on
investigations on the second dielectric virial coefficient and the intermolecular pair potential in 1977, both
at Carl Schorlemmer Technical University Merseburg. In 1985, he wrote his habilitation thesis, Phase
Equilibria in Systems with Polymers and Copolymers, at Technical University Merseburg.
Since then, Dr. Wohlfarth’s main research has been related to polymer systems. Currently, his
research topics are molecular thermodynamics, continuous thermodynamics, phase equilibria in polymer
mixtures and solutions, polymers in supercritical fluids, PVT-behavior and equations of state, and sorption
properties of polymers, about which he has published approximately 100 original papers. He has also built
a database, Thermodynamic Properties of Polymer Systems, and has written the books Vapor-Liquid
Equilibria of Binary Polymer Solutions and CRC Handbook of Thermodynamic Data of Copolymer
Solutions.
He is working on the evaluation, correlation, and calculation of thermophysical properties of pure

compounds and binary mixtures resulting in six volumes of the Landolt-Börnstein New Series. He is a
respected contributor to the CRC Handbook of Chemistry and Physics.
CONTENTS
1. INTRODUCTION
1.1. Objectives of the handbook...............................................................................................1
1.2. Experimental methods involved........................................................................................2
1.3. Guide to the data tables...................................................................................................20
1.4. List of symbols................................................................................................................24
1.5. References.......................................................................................................................26
2. VAPOR-LIQUID EQUILIBRIUM (VLE) DATA

OF AQUEOUS POLYMER SOLUTIONS
2.1. Partial water vapor pressures or water activities
for binary polymer solutions..............................................................................................29
2.2. Partial solvent vapor pressures or solvent activities
for ternary aqueous polymer solutions...............................................................................58
2.3. Classical mass-fraction Henry’s constants of water vapor
in molten polymers............................................................................................................74
2.4. References.........................................................................................................................78
3. LIQUID-LIQUID EQUILIBRIUM (LLE) DATA

3.1. Cloud-point and/or coexistence curves of quasibinary solutions....................................... 81
3.2. Table of systems where binary LLE data were published only in
graphical form as phase diagrams or related figures..........................................................97
3.3. Cloud-point and/or coexistence curves of quasiternary solutions
containing water and at least one polymer.......................................................................105
3.3.1. Nonelectrolyte solutions............ .................................................................... 105
3.3.2. Electrolyte solutions....................................................................................... 167
3.4. Table of systems where ternary LLE data were published only in
graphical form as phase diagrams or related figures........................................................283
3.5. Cloud-point and/or coexistence curves of quasiquaternary solutions
containing water and at least one polymer.......................................................................301
3.5.1. Nonelectrolyte solutions........... ..................................................................... 301
3.5.2. Electrolyte solutions....................................................................................... 315
3.6. Table of systems where quaternary LLE data were published only in
graphical form as phase diagrams or related figures....................................................... 328
3.7. Lower critical (LCST) and/or upper critical (UCST) solution temperatures
of aqueous polymer solutions.......................................................................................... 331
3.8. References.......................................................................................................................339
4. HIGH-PRESSURE PHASE EQUILIBRIUM (HPPE) DATA
4.1. Experimental data of quasibinary polymer solutions.......................................................365
4.2. Table of systems where binary HPPE data were published only
in graphical form as phase diagrams or related figures....................................................369
4.3. Experimental data of quasiternary solutions containing water
and at least one polymer..................................................................................................370
4.4. Table of systems where ternary HPPE data were published only
in graphical form as phase diagrams or related figures....................................................374
4.5. References .......................................................................................................................375
5. ENTHALPY CHANGES FOR AQUEOUS POLYMER SOLUTIONS

5.1. Enthalpies of mixing or intermediary enthalpies of dilution,
and partial enthalpies of mixing (at infinite dilution),
or polymer (first) integral enthalpies of solution ............................................................377
5.2. Partial molar enthalpies of mixing at infinite dilution of water
and enthalpies of solution of water vapor in molten polymers
from inverse gas-liquid chromatography (IGC)...............................................................413
5.3. Table of systems where additional information on enthalpy effects
in aqueous polymer solutions can be found.....................................................................416
5.4. References.......................................................................................................................424
6. PVT DATA OF POLYMERS AND SOLUTIONS

6.1. PVT data of some polymers and their aqueous solutions................................................431
6.2. Excess volumes and/or densities of aqueous polymer solutions......................................448
6.3. Table of systems where additional information on volume effects
in aqueous polymer solutions can be found.....................................................................471
6.4. References.......................................................................................................................473
7. SECOND VIRIAL COEFFICIENTS (A2)

7.1. Experimental A2 data.......................................................................................................477
7.2. References.......................................................................................................................485
APPENDICES
Appendix 1 List of systems and properties in order of the polymers......................................487
Appendix 2 List of solvents in alphabetical order...................................................................505
Appendix 3 List of solvents in order of their molecular formulas...........................................507
INDEX.....................................................................................................................................................509
1. INTRODUCTION
1.1. Objectives of the handbook
Knowledge of thermodynamic data of aqueous polymer solutions is a necessity for industrial and
laboratory processes. Furthermore, such data serve as essential tools for understanding the physical
behavior of polymer solutions, for studying intermolecular interactions, and for gaining insights into the
molecular nature of mixtures. They also provide the necessary basis for any developments of theoretical
thermodynamic models. Scientists and engineers in academic and industrial research need such data and
will benefit from a careful collection of existing data. However, the database for polymer solutions is still
modest in comparison with the enormous amount of data for low-molecular mixtures, and the specialized
database for aqueous polymer solutions is even smaller. On the other hand, aqueous polymer solutions are
gaining increasing commercial interest because of their unique physical properties, and thermodynamic
data are needed for optimizing applications, e.g., separations of complex mixtures of biomolecules,
recovery of antibiotics, precipitation and purification of proteins, separation of lignins from cellulose in
the paper pulping process, extraction of radioactive metal ions like strontium, cesium, actinides or
lanthanides from aqueous systems, formation of membranes, spinning fibers into aqueous media, or
thermoseparating polymers.
Basic information on polymers can be found in the Polymer Handbook (1999BRA). Some data
books on polymer solutions appeared in the early 1990s (1990BAR, 1992WEN, 1993DAN, and
1994WOH), but most data for polymer solutions have been compiled during the last decade. Older liquid-
liquid equilibrium data for aqueous polymer systems were collected in some books dedicated to the
separation of biomolecules by aqueous two-phase systems (1985WAL, 1986ALB, and 1995ZAS). A data
book with information on copolymer solutions appeared in 2001 (2001WOH). No databooks or databases
dedicated specially to aqueous polymer solutions presently exist. Thus, the intention of the Handbook is to
fill this gap and to provide scientists and engineers with an up-to-date compilation from the literature of
the available thermodynamic data on aqueous polymer solutions. The Handbook does not present theories
and models for polymer solution thermodynamics. Other publications (1971YAM, 1990FUJ, 1990KAM,
1999KLE, 1999PRA, and 2001KON) can serve as starting points for investigating those issues. Theories
for aqueous two-phase systems are reviewed by Cabezas (1996CAB). The state of the art for surfactants
and polymers in aqueous solutions is summarized by Holmberg et al. (2003HOL).
The data within this book are divided into six chapters:
• Vapor-liquid equilibrium (VLE) data of binary or ternary aqueous polymer solutions

• Liquid-liquid equilibrium (LLE) data of (quasi) binary, ternary, or quaternary
aqueous polymer solutions
• High-pressure phase equilibrium (HPPE) data of aqueous polymer solutions
• Enthalpy changes for aqueous polymer solutions
• PVT data of polymers and their aqueous solutions as well as excess volumes and
densities
• Second virial coefficients (A2) of aqueous polymer solutions
Data from investigations applying to more than one chapter are divided and appear in the relevant
chapters. Data are included only if numerical values were published or authors provided their results by
personal communication (and I wish to thank all those who did so). No digitized data have been included
in this data collection, but some tables include systems data published in graphical form.
2 CRC Handbook of Thermodynamic Data of Aqueous Polymer Solutions
____________________________________________________________________________________
1.2. Experimental methods involved

Vapor-liquid equilibrium (VLE) measurements
Investigations on vapor-liquid equilibrium of polymer solutions can be made by various methods:
1. Absolute vapor pressure measurement

2. Differential vapor pressure measurement
3. Isopiestic sorption/desorption methods, i.e., gravimetric sorption, piezoelectric sorption,
or isothermal distillation
4. Inverse gas-liquid chromatography (IGC) at infinite dilution, IGC at finite concentrations,
and headspace gas chromatography (HSGC)
5. Steady-state vapor-pressure osmometry (VPO)
Experimental techniques for vapor pressure measurements were reviewed in 1975BON and
2000WOH. Methods and results of the application of IGC to polymers and polymer solutions were
reviewed in 1976NES, 1988NES, 1989LLO, 1989VIL, and 1991MU1. Reviews on ebulliometry and/or
vapor-pressure osmometry can be found in 1974TOM, 1975GLO, 1987COO, 1991MAY, and 1999PET.
The measurement of vapor pressures for polymer solutions is generally more difficult and more
time-consuming than that of low-molecular mixtures. The main difficulties can be summarized as follows:
Polymer solutions exhibit strong negative deviations from Raoult’s law. These are mainly due to the large
entropic contributions caused by the difference between the molar volumes of solvents and polymers as
was explained by the classical Flory-Huggins theory about 60 years ago. However, because of this large
difference in molar mass, vapor pressures of dilute solutions do not differ markedly from the vapor
pressure of the pure solvent at the same temperature, even at polymer concentrations of 10-20 wt%. This
requires special techniques to measure very small differences in solvent activities. Concentrated polymer
solutions are characterized by rapidly increasing viscosities with increasing polymer concentration. This
leads to a strong increase in time required to obtain real thermodynamic equilibrium caused by slow
solvent diffusion effects (in or out of a non-equilibrium-state polymer solution). Furthermore, only the
solvent coexists in both phases because polymers do not evaporate. The experimental techniques used for
the measurement of vapor pressures of polymer solutions have to take into account all these effects.
Vapor pressures of polymer solutions are usually measured in the isothermal mode by static
methods. Dynamic methods are seldom applied, e.g., ebulliometry (1975GLO and 1987COO). At least,
one can consider measurements by VPO to be dynamic ones, where a dynamic (steady-state) balance is
obtained. Limits for the applicable ranges of polymer concentration and polymer molar mass, limits for
the solvent vapor pressure and the measuring temperature and some technical restrictions prevent its
broader application, however. Static techniques usually work at constant temperature. The three different
methods (1 through 3 above) were used to determine most of the vapor pressures of polymer solutions in
the literature. All three methods have to solve the problems of establishing real thermodynamic
equilibrium between liquid polymer solution and solvent vapor phase, long-time temperature constancy
during the experiment, determination of the final polymer concentration, and determination of pressure
and/or activity. Absolute vapor pressure measurement and differential vapor pressure methods were
mostly used by early workers. Most recent measurements were done with the isopiestic sorption methods.
Gas-liquid chromatography as IGC closes the gap at high polymer concentrations where vapor pressures
cannot be measured with sufficient accuracy. HSGC can be considered as some combination of absolute
vapor pressure measurement with GLC.
The following text (a short summary from the author’s own review, 2000WOH) explains briefly
the usual experimental equipment and the measuring procedures.
1. Introduction 3
____________________________________________________________________________________
1. Absolute vapor pressure measurement
Absolute vapor pressure measurement can be considered the classical technique for this purpose,
because one measures directly the vapor pressure above a solution of known polymer concentration. The
literature gives a variety of absolute vapor pressure apparatuses developed and used by different authors.
Vapor pressure measurement and solution equilibration were often made separately. A polymer sample is
prepared by weighing, the sample flask is evacuated, degassed solvent is introduced into a sample flask
that is sealed thereafter. Samples are equilibrated at elevated temperature in a thermostatted bath for some
weeks. The flask with the equilibrated polymer solution is then connected with the pressure-measuring
device at the measuring temperature. The vapor pressure is measured after reaching equilibrium and the
final polymer concentration is obtained after correcting for the amount of evaporated solvent. Modern
equipment applies electronic pressure sensors and digital technique to measure the vapor pressure. Data
processing can then be made online by computers. A number of problems have to be solved during the
experiment. The solution is usually of an amount of some cm3 and may contain about 1g of polymer or
even more. Degassing is absolutely necessary. All impurities in the pure solvent have to be eliminated.
Equilibration of all prepared solutions is very time consuming (liquid oligomers do not need so much
time, of course). Increasing viscosity makes the preparation of concentrated solutions more and more
difficult with further increasing the amount of polymer. Solutions above 50-60 wt% can hardly be
prepared (depending on the solvent/polymer pair under investigation).
The determination of the volume of solvent vaporized in the unoccupied space of the apparatus is
difficult and can cause serious errors in the determination of the final solvent concentration. To
circumvent the vapor phase correction, one can measure the concentration directly by means, for example,
of a differential refractometer. The contact of solvent vapor with the Hg surface in older equipment may
cause further errors. Complete thermostatting of the whole apparatus is necessary to avoid condensation of
solvent vapor at colder spots. Since it is disadvantageous to thermostat Hg manometers at higher
temperatures, null measurement instruments with pressure compensation were sometimes used. Modern
electronic pressure sensors can be thermostatted within certain temperature ranges. If pressure
measurement is made outside the thermostatted equilibrium cell, the connecting tubes must be heated
slightly above the equilibrium temperature to avoid condensation.
The measurement of polymer solutions with lower polymer concentrations requires very precise
pressure instruments, because the difference to the pure solvent vapor pressure becomes very small with
decreasing amount of polymer. A common consistency test on the basis of the integrated Gibbs-Duhem
equation does not work for vapor pressure data of binary polymer solutions because the vapor phase is
pure solvent vapor. Thus, absolute vapor pressure measurements need very careful handling, plenty of
time and an experienced experimentator. They are not the methods of choice for highly viscous polymer
solutions, and they were seldom applied to aqueous polymer solutions.
2. Differential vapor pressure measurement
The differential method can be compared under some aspects with the absolute method, but it has
some advantages. The measuring principle is to obtain the vapor pressure difference between the pure
solvent and the polymer solution at the measuring temperature. Again, the polymer sample is filled, after
weighing, into a sample flask, the apparatus is evacuated, a desired amount of degassed solvent is distilled
into the sample flask to build the solution and the samples have to be equilibrated for a necessary duration
of time. The complete apparatus is kept at constant measuring temperature and, after reaching equilibrium,
the pressure difference is read from the manometer difference and the concentration is calculated after
correcting the amount of vaporized solvent in the unoccupied space of the equipment. The pure solvent
vapor pressure is usually precisely known from independent experiments.
____________________________________________________________________________________
Difference/differential manometers have some advantages in their construction: they are

comparatively smaller and their resolution is much higher (modern pressure transducers can resolve
differences of 0.1 Pa and less). However, there are the same disadvantages with sample/solution
preparation (solutions of grams of polymer in some cm3 volume, degassing, viscosity), long-time
thermostatting of the complete apparatus because of long equilibrium times (increasing with polymer
molar mass and concentration/viscosity of the solution), correction of unoccupied vapor space, impurities
of the solvent, connection to the Hg surface in older equipment, and the problem of obtaining real
thermodynamic equilibrium (or not) as explained above. Modern equipment uses electronic pressure
sensors instead of Hg manometers and digital technique to measure the vapor pressure. Also,
thermostatting is more precise in recent apparatuses. Problems caused by the determination of the
unoccupied vapor space could be avoided by measuring the absolute vapor pressure as well.
Again, the concentration can be determined independently by using a differential refractometer

and a normalized relation between concentration and refractive index. Degassing of the liquids remains a
necessity. Time for establishing thermodynamic equilibrium could somewhat be shortened by intensive
stirring. In comparison with absolute vapor pressure measurements, differential vapor pressure
measurements with a high resolution for the pressure difference can be applied even for dilute polymer
solutions where the solvent activity is very near to 1 or the vapor pressure of the solution is very close to
the value for the pure solvent (1989HAY). They need more time than VPO measurements, however.
3. Isopiestic sorption/desorption methods
Isopiestic measurements allow a direct determination of solvent activity or vapor pressure in

polymer solutions by using a reference system (a manometer may not have to be applied). There are two
general principles for lowering the solvent activity in the reference system: concentration lowering or
temperature lowering. Isopiestic measurements have to obey the condition that no polymer can vaporize
(as might be the case for lower-molecular oligomers at higher temperatures).
Concentration lowering under isothermal conditions is the classical isopiestic technique,

sometimes also called isothermal distillation. A number of solutions (two is the minimum) are in contact
with each other via their common solvent vapor phase, and solvent evaporates and condenses (this is the
isothermal distillation process) between them as long as the chemical potential of the solvent is equal in
all solutions. At least one solution serves as reference system, i.e., its solvent activity vs. solvent
concentration dependence is precisely known. After an exact determination of the solvent concentration in
all equilibrated solutions (usually by weighing), the solvent activity in all measured solutions is known
from and equal to the activity of the reference solution. This method is almost exclusively used for
aqueous polymer solutions, where salt solutions can be applied as reference systems (e.g., 1990OCH,
1995GRO, 1996LIN). It is a standard method for inorganic salt systems.
Temperature lowering at specified isobaric or isochoric conditions is the most often used
technique for the determination of solvent vapor pressures or activities in polymer solutions. The majority
of measurements for nonaqueous polymer solutions are made using this kind of an isopiestic procedure
where the pure solvent is used as the reference system (see 1994WOH). The equilibrium condition of
equal chemical potential of the solvent in the polymer solution as well as in the reference system is
realized by keeping the pure solvent at a lower temperature (T1) than the measuring temperature (T2) of the
solution. In equilibrium, the vapor pressure of the pure solvent at the lower temperature is then equal to
the partial pressure of the solvent in the polymer solution, i.e., P1s(T1) = P1(T2). Equilibrium is again
established via the common vapor phase for both subsystems.
1. Introduction 5
____________________________________________________________________________________
The vapor pressure of the pure solvent is either known from independent data or measured
additionally in connection with the apparatus. The composition of the polymer solution can be altered by
changing T1 and a wide range of compositions can be studied (between 30-40 wt% and 85-90 wt%
polymer, depending on the solvent). Measurements above 85-90 wt% polymer are subject to increasing
errors because of surface adsorption effects.
A broad variety of experimental equipment is based on this procedure. This isopiestic technique
is the recommended one for most polymer solutions since it is advantageous in nearly all aspects of
measurement. It covers the broadest concentration range. Only very small amounts of polymer are needed
(about 30-50 mg with the classical quartz spring balance, about 100 µg with piezoelectric sorption
detector or microbalance techniques, see below). It is much more rapid than all other methods explained
above, because equilibrium time decreases drastically for such small amounts of polymer and polymer
solution (about 12-24 hours for the quartz spring balance, about 3-4 hours for piezoelectric or
microbalance techniques). The complete isotherm can be measured using a single loading of the
apparatus. Equilibrium is easier to obtain since comparatively small amounts of solvent have to diffuse
into the bulk sample solution. Equilibrium can be tested better by measuring sorption and desorption runs
which must lead to equal results for thermodynamic absorption equilibrium.
The classical concept is the sorption method using a quartz spring balance that measures the
extension of the quartz spring according to Hook’s law (linear relationship, no hysteresis). In this method
a weighed quantity of the (non-volatile) polymer is placed on the pan of the quartz spring balance within a
measuring cell. The determination of spring extension vs. mass has to be made in advance as a calibration
procedure. Reading of the spring extension is usually made by means of a cathetometer. The cell is sealed,
evacuated and thermostatted to the measuring temperature (T2) and the solvent is then introduced into the
measuring cell as solvent vapor. The solvent vapor is absorbed by the polymer sample to form the
polymer solution until thermodynamic equilibrium is reached. The solvent vapor is provided from a
reservoir of either pure liquid solvent thermostatted at a lower temperature (T1) or a reference liquid
solution of known concentration/solvent partial pressure as in the case of the isothermal distillation
procedure as described above.
The following problems have to be solved during the experiment. The equilibrium cell has to be
sealed carefully to avoid any air leakage over the complete duration of the measurements (to measure one
isotherm takes about 14 days). Specially developed thin Teflon sealing rings are preferred to grease. The
polymer sample has to stand the temperature. Changes by thermal aging during the experiment must be
avoided. The temperatures provided by the thermostats must not fluctuate more than ± 0.1 K.
Condensation of solvent vapor at points that become colder than T2 has to be avoided. As was stated by
different experimentalists, additional measurement of the vapor pressure inside the isopiestic sorption
apparatus seems to be necessary if there is some doubt about the real pressure or if no reliable pure
solvent vapor pressure data exist for the investigated temperature range. This direct pressure measurement
has the advantage that absolute pressures can be obtained and pressure fluctuations can be observed. More
modern equipment applies electronic pressure sensors instead of Hg manometers to avoid the problems
caused by the contact of solvent vapor with the mercury surface and to get a better resolution of the
measuring pressure.
Isopiestic vapor sorption can be made using an electronic microbalance (for aqueous polymer
solutions, e.g., 1998HWA) instead of the quartz spring balance. Electronic microbalances are commer-
cially available from a number of producers. Their main advantages are their high resolution and their
ability to allow kinetic measurements. Additionally, experiments using electronic microbalances can be
automated easily and provide computing facilities.
____________________________________________________________________________________
The major disadvantage with some kinds of microbalances is that they cannot be used at high
solvent vapor pressures and so are limited to a relatively small concentration range. However, since thin
polymer films can be applied, this reduces both the time necessary to attain equilibrium (some hours) and
the amount of polymer required, and equilibrium solvent absorption can be obtained also at polymer mass
fractions approaching 1 (i.e., for small solvent concentrations). Depending on their construction, the
balance head is situated inside or outside the measuring apparatus. Problems may arise when it is inside
where the solvent vapor may come into contact with some electronic parts. Furthermore, all parts of the
balance that are inside the apparatus have to be thermostatted to the measuring temperature to enable the
correct equilibration of the polymer solution or even slightly above measuring temperature to avoid
condensation of solvent vapor in parts of the balance. The allowed temperature range of the balance and
its sensitivity to solvent corrosion determine the accessible measuring range of the complete apparatus. A
magnetic suspension balance can be applied instead of an electronic microbalance. The magnetic
suspension technique has the advantage that all sensitive parts of the balance are located outside the
measuring cell because the balance and the polymer solution measuring cell are in separate chambers and
connected by magnetic coupling only.
The most sensitive solvent vapor sorption method is the piezoelectric sorption detector. The
amount of solvent vapor absorbed by a polymer is detected by a corresponding change in frequency of a
piezoelectric quartz crystal coated with a thin film of the polymer because a frequency change is the
response of a mass change at the surface of such a crystal. The frequency of the crystal decreases as mass
increases when the crystal is placed in a gas or vapor medium. The frequency decrease is fairly linear. The
polymer must be coated onto the crystal from a solution with some care to obtain a fairly uniform film.
Measurements can be made at dynamic (vapor flow) or static conditions. With reasonable assumptions for
the stability of the crystal’s base frequency and the precision of the frequency counter employed, the
piezoelectric method allows the detection of as few as 10 ng of solvent using a 10-MHz crystal. This
greatly reduces both the time necessary to attain equilibrium (3-4 hours) and the amount of polymer
required. Because very thin films are applied, equilibrium solvent absorption can be obtained also at
polymer mass fractions approaching 1 (i.e., for small solvent concentrations). Sorption-desorption
hysteresis has never been observed when using piezoelectric detectors. This demonstrates the effect of
reducing the amount of polymer from about 50 mg for the quartz spring sorption technique by an order of
103 for the piezoelectric detector. However, measurements are limited to solvent concentrations well
below the region where solution drops would be formed. On the other hand, measurements can also be
made at higher temperatures and pressures. Limits are set by the stability of the electrical equipment and
the construction of the measuring cell.
4. Gas-liquid chromatography (GLC)
GLC can be used to determine the activity coefficient of a solute in a (molten) polymer at
essentially zero solute concentration. This type of activity coefficient is known as an infinite-dilution
activity coefficient. Because the liquid polymer in the stationary phase acts as a solvent for the very small
amount of an injected solute sample, this technique is often called inverse gas-liquid chromatography
(IGC). However, IGC is not widely used for water (vapor), being the low-molecular solute.
The equipment does not differ in principle very much from that used in analytical GLC. For
operating at infinite dilution, the carrier gas flows directly to the column that is inserted into a
thermostatted oil bath (to get a more precise temperature control than in a conventional GLC oven). The
output of the column is measured with a flame ionization detector or alternately with a thermal
conductivity detector. Helium is used today as the carrier gas (nitrogen was used in earlier work). From
the difference between the retention time of the injected solvent sample and the retention time of a non-
interacting gas (marker gas), thermodynamic equilibrium data can be obtained. Most experiments were
done up to now with packed columns, but capillary columns were used too.
1. Introduction 7
____________________________________________________________________________________
The experimental conditions must be chosen so that real thermodynamic data can be obtained,
i.e., equilibrium bulk absorption conditions. Errors caused by unsuitable gas flow rates, unsuitable
polymer loading percentages on the solid support material and support surface effects as well as any
interactions between the injected sample and the solid support in packed columns, unsuitable sample size
of the injected probes, carrier gas effects, and imprecise knowledge of the real amount of polymer in the
column, can be sources of problems, whether data are nominally measured under real thermodynamic
equilibrium conditions or not, and have to be eliminated. The sizeable pressure drop through the column
must be measured and accounted for. Column preparation is the most difficult and time-consuming task
within the IGC experiment. Two, three or even more columns must be prepared to test the reproducibility
of the experimental results and to check any dependence on polymer loading and sometimes to filter out
effects caused by the solid support. In addition, various tests regarding solvent sample size and carrier gas
flow rate have to be done to find out correct experimental conditions. There is an additional condition for
obtaining real thermodynamic equilibrium data that is caused by the nature of the polymer sample.
Synthetic polymers are usually amorphous or semicrystalline products. Thermodynamic equilibrium data
require the polymer to be in a molten state, however. This means that IGC measurements have to be
performed for our purpose well above the glass transition temperature of the amorphous polymer or even
above the melting temperature of the crystalline parts of a polymer sample. On the other hand, IGC can be
applied to determine these temperatures. Only data at temperatures well above the glass transition
temperature lead to real thermodynamic vapor-liquid equilibrium data. As a rule, the experimental
temperature must exceed the glass transition temperature by about 50 K.
GLC can also be used to determine the partial pressure of a solute in a polymer solution at
concentrations as great as 50 wt% solute. In this case of finite concentration IGC, a uniform background
concentration of the solute is established in the carrier gas. Finite concentration IGC can be extended to
multicomponent systems. Data reduction is somewhat complicated, however. Applications to aqueous
polymer systems are not known.
VLE measurements for polymer solutions can be done by so-called headspace gas chroma-
tography (HSGC), which is practically a combination of static vapor pressure measurement with gas
chromatographic detection (1997KOL). Again, polymer solutions have to be prepared in advance and
have to be equilibrated at the measuring temperature for some weeks before measurement. HSGC
experiments were carried out with an apparatus consisting of a headspace sampler and a normal gas
chromatograph. The thermostatted headspace sampler samples a constant amount of gas phase and injects
this mixture into the gas chromatograph. After separation of the components of the gaseous mixture in a
capillary column, they are detected individually by a thermal conductivity detector. The signals are sent to
an integrator which calculates the peak areas proportional to the amount of gas in the sample volume and
consequently to the vapor pressure. Calibration can be done by measuring the signal of the pure solvent in
dependence on temperature and comparing the data with the corresponding vapor pressure vs. temperature
data. Measurements can be done between about 25 wt% and 85 wt% polymer in the solution (again
depending on temperature, solvent and polymer investigated). In order to guarantee thermodynamic
equilibrium in the sampler, solutions have to be conditioned for at least 24 h at constant temperature in the
headspace sampler before measurement. Additional degassing is not necessary and solvents have to be
purified only to the extent that is necessary to prevent unfavorable interactions in the solution. The
experimental error in the vapor pressures is typically of the order of 1-3%. One great advantage of HSGC
is its capability to measure VLE data not only for binary polymer solutions but also for polymer solutions
in mixed solvents since it provides a complete analysis of the vapor phase in equilibrium. Examples for
aqueous polymer solutions are given by Barth and Wolf (2000BA1, 2000BA2).
The data reduction for infinite dilution IGC starts with the usually obtained parameters of
retention volume or net retention volume which have to be calculated from the measured retention times
and the flow rate of the carrier gas at column conditions.
____________________________________________________________________________________
Vnet = Vr − Vdead (1)
where:
Vnet net retention volume
Vr retention volume
Vdead retention volume of the inert marker gas, dead retention, gas holdup
These net retention volumes are reduced to specific retention volumes, Vg0, by division of
equation (1) with the mass of the liquid (here the liquid is the molten polymer). They are corrected for the
pressure difference between column inlet and outlet pressure, and reduced to a temperature T0 = 273.15 K.
0 V   T0  3( Pin / Pout ) 2 − 1
Vg =  net   3
(2)
 mB   T  2 ( Pin / Pout ) − 1
where:
Vg0 specific retention volume corrected to 0oC = 273.15 K
mB mass of the polymer in the liquid phase within the column
Pin column inlet pressure
Pout column outlet pressure
T measuring temperature
T0 reference temperature = 273.15 K
Theory of GLC provides the relation between Vg0 and thermodynamic data for the low-molecular
component (solvent A) at infinite dilution:
∞ ∞
 PA  RT0  PA  RT0
 L = 0 or  L = 0 (3)
 xA  Vg M B  wA  Vg M A
where:
MA molar mass of the solvent A
MB molar mass of the liquid (molten) polymer B
PA partial vapor pressure of the solvent A at temperature T
R gas constant
xAL mole fraction of solvent A in the liquid solution
wAL mass fraction of solvent A in the liquid solution
The activity coefficients at infinite dilution read, if we neglect interactions to and between carrier
gas molecules (which are normally helium):
 RT   ( B − V L )( P − PAs ) 
γ A∞ =  0 0 s  exp  AA A  (4)
V M P  RT
 g B A   
∞
 RT   ( B − VA L )( P − PA s ) 
Ω A =  0 0 s  exp  AA  (5)
V M P  RT
 g A A   
1. Introduction 9
____________________________________________________________________________________
where:
BAA second virial coefficient of the pure solvent A at temperature T
PAs saturation vapor pressure of the pure liquid solvent A at temperature T
VAL molar volume of the pure liquid solvent A at temperature T
γA activity coefficient of the solvent A in the liquid phase with activity aA = xAγA
ΩA mass fraction-based activity coefficient of the solvent A in the liquid phase with
aA = wAΩA
The standard state pressure P has to be specified. It is common practice by many authors to
define zero pressure as standard pressure since pressures are usually very low during GLC measurements.
Then, equations (4 and 5) change to:
 RT   P s A (VA L − BAA ) 
γ A∞ =  0 0 s  exp   (6)
V M P  RT
 g B A   
∞
 RT0   PA s (VA L − BAA ) 
ΩA = 0 exp 
 V M P s   (7)
 g A A   RT 
One should keep in mind that mole fraction-based activity coefficients γA become very small
values for common polymer solutions and reach a value of zero for MB →∞, which means a limited
applicability at least to oligomer solutions. Therefore, the common literature provides only mass fraction-
based activity coefficients for (high-molecular) polymer/(low-molecular) solvent pairs. The molar mass
MB of the polymeric liquid is an average value (Mn) according to the usual molar-mass distribution of
polymers. Additionally, it is a second average if mixed stationary liquid phases are applied.
Furthermore, thermodynamic VLE data from GLC measurements are provided in the literature as
values for (PA/wA)∞, see equation (3), i.e., classical mass fraction-based Henry’s constants (if assuming
ideal gas phase behavior):
∞
 P  RT
H A, B =  AL  = 0 0 (8)
 wA  Vg M A
Since Vnet = Vr − Vdead, the marker gas is assumed to not be retained by the polymer stationary
phase and will elute at a retention time that is usually very small in comparison with those of the samples
investigated. However, for small retention volumes, values for the mass fraction-based Henry’s constants
should be corrected for the solubility of the marker gas (1976LIU). The apparent Henry’s constant is
obtained from equation (8) above.
−1
app
 M A H Aapp
,B

H A, B = H A, B 1 +  (9)
 M ref H A,ref 
Mref is the molar mass of the marker gas. The Henry’s constant of the marker gas itself,
determined by an independent experiment, need not be known very accurately, as it is usually much larger
than the apparent Henry’s constant of the sample.
____________________________________________________________________________________
5. Vapor-pressure osmometry (VPO)
Vapor-pressure osmometry is, from its name, comparable to membrane osmometry by allowing
the vapor phase to act like a semipermeable membrane, but it is based on vapor pressure lowering or
boiling temperature elevation. Since the direct measure of vapor pressure lowering of dilute polymer
solutions is impractical because of the extreme sensitivity that is required, VPO is in widespread use for
low-molecular and oligomer solutions (i.e., Mn less than 20,000 g/mol) by employing the thermoelectric
method where two matched temperature-sensitive thermistors are placed in a chamber that is
thermostatted to the measuring temperature and where the atmosphere is saturated with solvent vapor. If
drops of pure solvent are placed on both thermistors, the thermistors will be at the same temperature (zero
point calibration). If a solution drop is placed on one thermistor, a temperature difference ∆T, which is
caused by condensation of solvent vapor onto the solution drop, occurs. The obtained temperature
difference is very small, about 10−5 K.
Because solvent transfer effects are measured, VPO is a dynamic method. This leads to a time-
dependent measurement of ∆T. Depending on technical details of the equipment, sensitivity of the
temperature detector, measuring temperature, solvent vapor pressure and polymer concentration in the
solution drop, a steady state for ∆T can be obtained after some minutes. The value of ∆T st is the basis for
thermodynamic data reduction; see below. If measuring conditions do not allow a steady state, an
extrapolation method to ∆T at zero measuring time can be employed for data reduction. Sometimes a
value is used that is obtained after a predetermined time. However, this may lead to some problems with
knowing the exact polymer concentration in the solution. The extrapolation method is somewhat more
complicated and needs experience of the experimenter but gives an exact value of polymer concentration.
Both methods are used within solvent activity measurements where polymer concentrations are higher and
condensation is faster than in common polymer characterization experiments.
Experience has shown that careful selection of solvent and temperature is critical to the success
of the VPO experiment. Nearly all common solvents, including water (e.g., 1999ELI), can be used with
VPO. Usually, there are different thermistor sensors for organic solvents and for water. The measuring
temperature should be chosen so that the vapor pressure of the solvent will be greater than 6,000 Pa, but
not so high as to lead to problems with evaporation from the chamber. Solvent purity is critical, and
volatile impurities and water must be avoided. Greater sensitivity can be achieved by using solvents with
low enthalpies of vaporization. This means that not all desirable polymer/solvent pairs and not all
temperature (pressure) ranges can be investigated by VPO. Additionally, VPO has some inherent sources
of error. These can be attributed to the possible existence of surface films, to differences in diffusion
coefficients in solutions, to appreciably different solution concentrations, to differences in heat
conductivity, to problems with drop size and shape, to the occurrence of reactions in the solution, and to
the presence of volatile solutes. Of course, most errors can be avoided to a good measure by careful
laboratory practice and/or technical improvements, but they must be taken into account when measuring
solvent activities.
The data reduction of vapor-pressure osmometry (VPO) uses the stationary temperature
difference as the starting point for determining solvent activities. There is an analogy to the boiling point
elevation in thermodynamic equilibrium. Therefore, in the steady-state period of the experiment, the
following relation can be applied if one assumes that the steady state is sufficiently near the vapor-liquid
equilibrium and linear non-equilibrium thermodynamics is valid:
RT 2
∆T st = − kVPO ln a A (10)
∆ LV H 0 A
1. Introduction 11
____________________________________________________________________________________
where:
aA activity of solvent A
kVPO VPO-specific constant (must be determined separately)
R gas constant
T measuring temperature (= temperature of the pure solvent drop)
∆T st temperature difference between solution and solvent drops in the steady state
∆LVH0A molar enthalpy of vaporization of the pure solvent A at temperature T
Liquid-liquid equilibrium (LLE) measurements
There are two different situations for the liquid-liquid equilibrium in polymer/solvent systems:
(i) the equilibrium between a dilute polymer solution (sol) and a polymer-rich solution (gel), and
(ii) the equilibrium between the pure solvent and a swollen polymer network (gel).
Only case (i) is considered here. To understand the results of LLE experiments in
polymer/solvent systems, one has to take into account the strong influence of distribution functions on
LLE, because fractionation occurs during demixing, with respect to molar mass distribution (and to
chemical distribution if copolymers are involved). Fractionation during demixing leads to some effects by
which the LLE phase behavior differs from that of an ordinary, strictly binary mixture, because a common
polymer solution is a multicomponent system. Cloud-point curves are measured instead of binodals; and
per each individual feed concentration of the mixture, two parts of a coexistence curve occur below (for
upper critical solution temperature, UCST, behavior) or above the cloud-point curve (for lower critical
solution temperature, LCST, behavior), i.e., produce an infinite number of coexistence data.
Distribution functions of the feed polymer belong only to cloud-point data. On the other hand,
each pair of coexistence points is characterized by two new and different distribution functions in each
coexisting phase. The critical concentration is the only feed concentration where both parts of the
coexistence curve meet each other on the cloud-point curve at the critical point that belongs to the feed
polymer distribution function. The threshold (maximum or minimum corresponding to UCST or LCST
behavior) temperature (or pressure) is not equal to the critical point, since the critical point is to be found
at a shoulder of the cloud-point curve. Details were discussed by Koningsveld (1968KON, 1972KON).
Thus, LLE data have to be specified in the tables as cloud-point or coexistence data, and coexistence data
make sense only if the feed concentration is given. This is not always the case, however.
Experimental methods can be divided into measurements of cloud-point curves, of real

coexistence data, and of critical points.
Due to distinct changes in a number of physical properties at the phase transition border, a
number of methods can be used to determine cloud-points. In many cases, the refractive index change is
determined because refractive indices depend on concentration (with the rare exception of isorefractive
phases) and the sample becomes cloudy when the highly dispersed droplets of the second phase appear at
the beginning of phase separation. Simple experiments observe cloud-points visually. More sophisticated
equipment applies laser techniques and light scattering, where changes in scattering pattern or intensity are
recorded as a function of decreasing/increasing temperature or pressure. The point where first deviations
from a basic line are detected is the cloud-point. Since demixing or phase homogenization requires some
time (especially for highly viscous solutions), special care is to be applied to obtain good data. Around the
critical point, large fluctuations occur (critical opalescence) and scattering data have to be measured at a
90o scattering angle. The determination of the critical point is to be made by independent methods; see
below. Various other physical properties have been applied for detecting liquid-liquid phase separation,
____________________________________________________________________________________
i.e., viscosity, ultrasonic absorption, thermal expansion, dielectric constant, differential thermal analysis
(DTA) or differential scanning calorimetry (DSC), UV- or IR-spectroscopy, and size exclusion chroma-
tography/gel permeation chromatography (SEC, GPC).
To measure real coexistence data is more difficult than to determine cloud-points. This is mainly
due to very long equilibrium times (sometimes weeks), which are necessary for obtaining
thermodynamically correct data in highly viscous solutions. On the other hand, aqueous two-phase
polymer solutions often contain some percent of polymer only and therefore have rather low viscosities
facilitating demixing. The common experimental method is to cool homogeneous solutions in ampoules
very slowly to the desired temperature in the LLE region, and equilibrium is reached after both phases are
sharply separated and clear. After separating both phases, concentrations and distribution functions are
measured. Highly viscous polymer solutions at higher concentrations can be investigated by a modified
ultracentrifuge where the equilibrium is quickly established during cooling by action of gravitational
forces. After some hours, concentrations, phase volume ratios and concentration differences can be
determined.
Special methods are necessary to measure the critical point. Only for solutions of monodisperse
polymers, the critical point is the maximum (or minimum) of the binodal. Binodals of polymer solutions
can be rather broad and flat. Then, the exact position of the critical point can be obtained by the method of
the rectilinear diameter:
I II
(ϕ B − ϕ B ) crit T
− ϕ B ∝ (1 − crit )1−α (11)
2 T
where:
ϕBI volume fraction of the polymer in coexisting phase I
ϕBII volume fraction of the polymer in coexisting phase II
ϕBcrit volume fraction of the polymer at the critical point
T crit critical temperature
α critical exponent
For solutions of polydisperse polymers, such a procedure cannot be used because the critical
concentration must be known in advance to measure its corresponding coexistence curve. Two different
methods were developed to solve this problem: the phase-volume-ratio method (1968KON) where one
uses the fact that this ratio is exactly equal to one only at the critical point, and the coexistence
concentration plot (1969WOL) where an isoplethal diagram of values of ϕBI and ϕBII vs. ϕ0B gives the
critical point as the intersection of cloud-point and shadow curves. Details will not be discussed here.
Treating polymer solutions with distribution functions by continuous thermodynamics is reviewed in
1989RAE, 1990RAE.
High-pressure phase equilibrium (HPPE) measurements
The experimental investigation of high-pressure fluid phase equilibria in polymer solutions is

confronted with the same problems discussed above insofar as the investigated phase equilibria
correspond with a VLE-, LLE-, or VLLE-type behavior, which are the only cases considered here. The
experimental equipment follows on the same techniques, however, extended to high pressure conditions,
using high-pressure cells and autoclaves for turbidimetry, light scattering, viscometry, and others.
1. Introduction 13
____________________________________________________________________________________
There are only a small number of investigations on high-pressure phase equilibria in aqueous
polymer systems. Recent experiments on aqueous systems were made by Rebelo et al. (2001GOM,
2002REB). Sometimes supercritical fluids are involved, i.e., gases/vapors above their critical temperature
and pressure (CO2 and some other fluids). There are some recent reviews on phase behavior of polymers
in systems involving supercritical fluids (1994MCH, 1997KIR, and 1999KIR) that summarize today’s
state of investigation. However, no dedicated reviews about aqueous polymer systems at high pressures
exist.
Measurement of enthalpy changes in polymer solutions
Experiments on enthalpy changes in binary polymer solutions can be made within common
microcalorimeters by applying one of the following three methods:
1. Measurement of the enthalpy change caused by solving a given amount of the solute
polymer in an (increasing) amount of solvent, i.e., the solution experiment
2. Measurement of the enthalpy change caused by mixing a given amount of a concentrated
polymer solution with an amount of pure solvent, i.e., the dilution experiment
3. Measurement of the enthalpy change caused by mixing a given amount of a
liquid/molten polymer with an amount of pure solvent, i.e., the mixing experiment
Care must be taken for polymer solutions with respect to the resolution of the instrument, which
has to be higher than for common solutions with larger enthalpic effects. Usually employed calorimeters
for such purposes are the Calvet-type calorimeters based on heat-flux principle. Details can be found in
1984HEM and 1994MAR.
In particular, one has to distinguish between the following effects for polymer solutions. The
(integral) enthalpy of mixing or the (integral) enthalpy of solution of a binary system is the amount of heat
that must be supplied when nA mole of pure solvent A and nB mole of pure polymer B are combined to
form a homogeneous mixture/solution in order to keep the total system at constant temperature and
pressure.
∆Mh = nAHA + nBHB − (nAH0A + nBH0B) (12a)

∆solh = nAHA + nBHB − (nAH0A + nBH0B) (12b)
where:
∆Mh, ∆solh (integral) enthalpy of mixing or solution
H A, H B partial molar enthalpy of solvent A or polymer B
H0A, H0B molar enthalpy of pure solvent A or pure polymer B
n A, n B amount of substance of solvent A or polymer B
The enthalpy effect might be positive (endothermic solution/mixture) or negative (exothermic

solution/mixture) depending on the ratio nA/nB, i.e., the concentration of the total system. Unfortunately, in
some of the older literature, the definition of the sign of the so-called (integral) heat of solution is
reversed, compared with the enthalpy, occasionally causing some confusion.
The value of the (integral) enthalpy of solution is dependent on the degree of crystallinity for
semicrystalline polymers and, usually to a lesser extent, on the thermal history of glassy polymers. The
(integral) enthalpy of mixing is independent of any crystalline or glassy aspects of the polymer. Thus, the
(integral) enthalpy of mixing can be obtained without difficulties only for liquid/molten polymers mixed
____________________________________________________________________________________
with a solvent. Otherwise, the melting enthalpy of the crystallites and/or the glass enthalpy have to be
determined additionally by independent measurements. As such a procedure is rather difficult and might
cause substantial errors, it is common to measure the (integral) intermediary enthalpy of dilution, i.e., the
enthalpy effect obtained if solvent A is added to an existing homogeneous polymer solution. The
intermediary enthalpy of dilution is the difference between two values of the enthalpy of mixing/solution
corresponding to the concentrations of the polymer solution at the beginning and at the end of the dilution
process. The term integral is often added to these enthalpy changes to describe changes where finite
amounts of substances are mixed. Especially, the integral enthalpy of solution/mixing for a polymer B is
given in a number of literature sources by applying the following two definitions:
• per mole polymer B:
int
∆solHB = ∆solh/nB = ∆solH/xB (13a)
int
∆MHB = ∆Mh/nB = ∆MH/xB (13b)
• per gram polymer B (where the intensive ∆Hs are the specific ones):
int
∆solHB = ∆solh/mB = ∆solH/wB (13c)
int
∆MHB = ∆Mh/mB = ∆MH/wB (13d)
where:
int
∆solHB integral enthalpy of solution of polymer B
int
∆ MH B integral enthalpy of mixing of polymer B
mB mass of polymer B
wB mass fraction of polymer B
xB mole fraction of polymer B
As stated above, the difference between int∆solHB and int∆MHB is determined by any enthalpic
effects caused from solid-liquid phase transition of the crystallites and/or from glass transition and is zero
for liquid/molten polymers.
The term differential is sometimes added to enthalpy changes where infinitesimal (i.e., very
small) amounts were added to a very large amount of either solution or pure component. These enthalpy
changes are usually called partial (molar or specific) enthalpies of solution/mixing:
∆solHB = (∂∆ sol h / ∂nB ) P ,T ,n j = HB − H0B (14a)

∆MHB = (∂∆ M h / ∂nB ) P ,T ,n j = HB − H0B (14b)
with a unit of J/mol. However, for polymer solutions, ∆solHB or ∆MHB is often expressed as the enthalpy
change per unit mass of polymer added which can be obtained from the following derivative:
∆solHB = (∂∆ sol h / ∂mB ) P ,T ,m j (14c)

∆MHB = (∂∆ M h / ∂mB ) P ,T ,m j (14d)
where:
∆solHB partial molar (or specific) enthalpy of solution of the polymer B
∆ MH B partial molar (or specific) enthalpy of mixing of the polymer B
1. Introduction 15
____________________________________________________________________________________
with a unit of J/g. Similar to these definitions one can find results related to one mole of monomers (or
base units). The derivative is then made by applying the base mole fraction of the polymer. The partial
(molar or specific) enthalpy of solution of the polymer B is equal to the so-called differential enthalpy of
solution at finite concentrations which is, for finite concentrations, different from the int∆solHB or int∆MHB
data as defined above. For example, in the case of a binary mixture, one obtains the relation:
∆MHB = ∆MH + (1 − xB)(∂∆MH/∂xB) (15)
which results in different values to int∆MHB. In the case of adding an infinitesimal amount of polymer to
the pure solvent, the partial (molar or specific) enthalpy of solution of the polymer B is properly identified
as the partial enthalpy of solution of the polymer at infinite dilution, ∆solHB∞, or the partial enthalpy of
mixing of the polymer at infinite dilution, ∆MHB∞. Its value at infinite dilution of the polymer is equal to
the so-called first integral enthalpy of solution (unfortunately, sometimes referred to more simply as the
enthalpy of solution of the polymer, but, as discussed above, identical values can only be obtained for
infinite dilution). In practice, the partial (molar or specific) enthalpy of solution of the polymer B is
measured by mixing isothermally a large excess of pure solvent and a certain amount of the polymer to
form a homogeneous solution.
The state of the polymer before dissolution can significantly affect the enthalpy of solution. An
amorphous polymer below its glass transition temperature Tg often dissolves with the release of heat. The
enthalpy of solution of a glassy polymer is usually dependent on temperature and, to some extent, on the
thermal history of the glass-forming process. An amorphous polymer above Tg can show endothermic or
exothermic dissolution behavior depending on the nature of the solvent and the interaction energies
involved as is the case for any enthalpy of mixing. The dissolving of a semicrystalline polymer requires an
additional amount of heat associated with the disordering of crystalline regions. Consequently, its
enthalpy of solution is usually positive and depends on the degree of crystallinity of the given polymer
sample.
The mathematical definition for the partial molar enthalpies of solution/mixing is given for the
solvent A by
∆solHA = (∂∆ sol h / ∂nA ) P ,T ,n j = HA − H0A (16a)

∆MHA = (∂∆ M h / ∂nA ) P ,T ,n j = HA − H0A (16b)
where:
∆solHA partial molar enthalpy of solution of the solvent A
∆ MH A partial molar enthalpy of mixing of the solvent A ( = differential enthalpy of dilution)
nA amount of substance of solvent A
again with a unit of J/mol. It is equal to the so-called differential enthalpy of dilution as a consequence of
adding an infinitesimal amount of solvent to the solution/mixture. The integral enthalpy of dilution for the
solvent is equivalent to the integral molar enthalpy of mixing for the solvent A as defined by:
int
∆MHA = ∆Mh/nA (17)
and, in the case of adding a very small amount of solvent to the pure polymer, the partial molar enthalpy
of solution at infinite dilution of the solvent is obtained. Partial molar enthalpies of mixing (or dilution) of
the solvent are included in this data collection only for cases where they were obtained from calorimetric
experiments.
____________________________________________________________________________________
Generally, it is known that such partial molar enthalpies of mixing (or dilution) of the solvent can
also be determined from the temperature dependence of the activity of the solvent:
∆MHA = R [∂ ln a A / ∂ (1/ T )]P (18)
However, agreement between enthalpy changes measured by calorimetry and results determined
from the temperature dependence of solvent activity data is often of limited quality. Therefore, such data
are not included here. From engineering and also from scientific aspects, the partial molar enthalpy of
mixing at infinite dilution of the solvent in the liquid/molten polymer ∆MHA∞ is of value. Therefore, data
for ∆MHA∞ determined by inverse gas-liquid chromatography (IGC) have been included here.
∞
∆MHA∞ = R [∂ ln Ω A / ∂ (1/ T )]P (19)
where:
∆ M H A∞ partial molar enthalpy of mixing at infinite dilution of the solvent A
ΩA∞ mass fraction-based activity coefficient of the solvent A at infinite dilution
Additionally, the enthalpies of solution at infinite dilution ∆solHA(vap)∞ of water vapor in molten
polymers determined by IGC have been included since IGC is the useful method for such data.
0
∆solHA(vap)∞ = − R [∂ ln Vg / ∂ (1/ T )]P (20)
where:
∆solHA(vap)∞ first integral enthalpy of solution of the vapor of solvent A
(with ∆solHA(vap)∞ = ∆MHA∞ − ∆LVH0A)
Vg0 specific retention volume corrected to 0oC
PVT/density measurement for polymer melt and solution
There are two widely practiced methods for the PVT measurement of polymers and polymer
solutions:
1. Piston-die technique
2. Confining fluid technique
which were described in detail by Zoller in papers and books (e.g., 1986ZOL, 1995ZOL). Thus, a short
summary is sufficient here.
In the piston-die technique, the material is confined in a rigid die or cylinder, which it has to fill
completely. A pressure is applied to the sample as a load on a piston, and the movement of the piston with
pressure and temperature changes is used to calculate the specific volume of the sample. Experimental
problems concerning solid samples need not be discussed here, since only data for the liquid/molten
(equilibrium) state are taken into consideration for this handbook. A typical practical complication is
leakage around the piston when low-viscosity melts or solutions are tested. Seals cause an amount of
friction leading to uncertainties in the real pressure applied. There are commercial devices as well as
laboratory-built machines which have been used in the literature.
1. Introduction 17
____________________________________________________________________________________
In the confining fluid technique, the material is surrounded at all times by a confining (inert)
fluid, often mercury, and the combined volume changes of sample and fluid are measured by a suitable
technique as a function of temperature and pressure. The volume change of the sample is determined by
subtracting the volume change of the confining fluid. A problem with this technique lies in potential
interactions between fluid and sample. Precise knowledge of the PVT properties of the confining fluid is
additionally required. The above-mentioned problems for the piston-die technique can be avoided.
For both techniques, the absolute specific volume of the sample must be known at a single
condition of pressure and temperature. Normally, these conditions are chosen to be 298.15 K and normal
pressure (101.325 kPa). There are a number of methods to determine specific volumes (or densities) under
these conditions. For polymeric samples, hydrostatic weighing or density gradient columns were often
used.
The tables in Chapter 6 provide specific volumes neither at or below the melting transition of
semicrystalline materials nor at or below the glass transition of amorphous samples, since PVT data of
solid polymer samples are non-equilibrium data and depend on sample history and experimental
procedure (which will not be discussed here).
Measurement of densities for aqueous polymer solutions at ordinary pressure is usually made
today by U-tube vibrating densimeters. Such instruments are commercially available. Calibration is made
with pure water when aqueous polymer solutions are investigated. Excess volumes are determined by
VEspez = Vspez − (wAV0A, spez + wBV0B, spez) (21a)

or
VE = (xAMA + xBMB)/ρ − (xAMA/ρA + xBMB/ρB) (21b)
where:
VE, VEspez molar or specific excess volume at temperature T
V0A, spez specific volume of pure solvent A at temperature T
V0B, spez specific volume of pure polymer B at temperature T
ρ density of the mixture at temperature T
ρA, ρB density of pure solvent A or pure polymer B at temperature T
Determination of second virial coefficients A2
There are a couple of methods for the experimental determination of the second virial coefficient:
colligative properties (vapor pressure depression, freezing point depression, boiling point increase,
membrane osmometry), scattering methods (classical light scattering, X-ray scattering, neutron scattering),
sedimentation velocity and sedimentation equilibrium. Details of the special experiments can be found in
textbooks (1972HUG, 1974TOM, 1975CAS, 1975FUJ, 1975GLO, 1987ADA, 1987BER, 1987COO,
1987KRA, 1987WIG, 1991CHU, 1991MAY, 1991MU2, 1992HAR, and 1999PET).
The vapor pressure depression of the solvent in a binary polymer solution, i.e., the difference
between the saturation vapor pressure of the pure solvent and the corresponding partial pressure in the
solution, ∆PA = PAs − PA, is expressed as:
∆PA  1 2 
= VAL cB  + A2 cB + A3cB + ... (22)
PA  Mn 
____________________________________________________________________________________
where:
A2, A3, ... second, third, ... osmotic virial coefficients at temperature T
cB (mass/volume) concentration at temperature T
Mn number-average relative molar mass of the polymer
∆P A PAs − PA, vapor pressure depression of the solvent A at temperature T
PA partial vapor pressure of the solvent A at temperature T
PAs saturation vapor pressure of the pure liquid solvent A at temperature T
VAL molar volume of the pure liquid solvent A at temperature T
The freezing point depression, ∆SLTA, is:
 1 2 
∆ SLTA = ESL cB  + A2 cB + A3cB + ... (23)
 Mn 
and the boiling point increase, ∆LVTA, is:
 1 2 
∆ LV TA = ELV cB  + A2 cB + A3cB + ... (24)
 Mn 
where:
ELV ebullioscopic constant
ESL cryoscopic constant
∆SLTA freezing point temperature difference between pure solvent and solution, i.e., SLTA0 − SLTA
∆LVTA boiling point temperature difference between solution and pure solvent, i.e., LVTA − LVTA0
The osmotic pressure, π , can be described as:
π  1 2 
= RT  + A2cB + A3cB + ... (25)
cB  Mn 
In the dilute concentration region, the virial equation is usually truncated after the second virial
coefficient which leads to a linear relationship. A linearized relation over a wider concentration range can
be constructed if the Stockmayer-Casassa relation between A2 and A3 is applied:
2
AM 
A3 M n =  2 n  (26)
 2 
0.5 0.5
π  RT   A2 M n 
  =  1 + 2 c2  (27)
 c2   Mn 
Scattering methods enable the determination of A2 via the common relation:
KcB 1
= + 2 A2Q ( q )cB + ... (28)
R( q) M w Pz ( q)
1. Introduction 19
____________________________________________________________________________________
with
4π θ
q= sin (29)
λ 2
where:
K a constant that summarizes the optical parameters of a scattering experiment
Mw mass-average relative molar mass of the polymer
Pz(q) z-average of the scattering function
q scattering vector
Q(q) function for the q-dependence of A2
R(q) excess intensity of the scattered beam at the value q
λ wavelength
θ scattering angle
Depending on the chosen experiment (light, X-ray or neutron scattering), the constant K is to be
calculated from different relations. For details see the corresponding textbooks (1972HUG, 1975CAS,
1982GLA, 1986HIG, 1987BER, 1987KRA, 1987WIG, and 1991CHU).
Thermodynamic data from the ultracentrifuge experiment can be obtained either from the
sedimentation velocity (sedimentation coefficient) or from the sedimentation-diffusion equilibrium since
the centrifugal forces are balanced by the activity gradient. The determination of sedimentation and
diffusion coefficients yields the virial coefficients by:
D  1 
( )
  1 − υ B ,spez ρ A = RT 
 s
2
+ 2 A2cB + 3 A3cB + ...  (30)
 MB 
where:
D diffusion coefficient
s sedimentation coefficient
υ B , spez partial specific volume of the polymer
Sedimentation-diffusion equilibrium in an ultracentrifuge also gives a virial series:
(
ω 2 hD 1 − υB , spez ρ A )  ∂∂ lnhc B
  1
 = RT 
2 
+ 2 A2 cB + 3 A3cB + ...  (31)
 D   MB 
where:
hD distance from the center of rotation
ω angular velocity
Both equations are valid for monodisperse polymers only, i.e., for one definite single component
B. For all polydisperse polymers, different averages were obtained for the sedimentation and the diffusion
coefficients which depend on the applied measuring modes and the subsequent calculations. The averages
of MB correspond with averages of D and s and are mixed ones that have to be transformed into the
desired common averages. For details, please see reviews 1975FUJ, 1991MU2, and 1992HAR.
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Cleat and Pulley Fastenings to Adjust Clothesline
The following kink will relieve the housewife of the trouble of
sagging clotheslines, and hubby of constantly being asked to tighten
up the line. The cost should not be over 25 cents, as all that is
needed is a pulley cleat and hook, all of which may be had at any
ten-cent store. When the line gets slack, it is pulled tight through the
pulley and tightened up in the cleat.—S. H. Johnson, Westville,
Conn.
Convenient Type of Mail Box for Home Use
The Mail Box is Lengthened So That It Reaches through the Wall to the
Inside, Where a Door is Placed through Which the Mail can be Removed
A person having a mail box set flush in the outside wall of his
home can, with a little alteration, make it accessible from inside the
house: After removing the back side of the box a tin extension
should be soldered to the box giving it sufficient length to reach
through the wall in which an opening of the proper size has been cut.
The enlarged container is completed by adding a glass door to the
inner end which enables one to ascertain its contents at a glance.—
A. Pertle, Chicago, Ills.
Block Plane Converted for Use on Circular Work
Few amateur craftsmen can afford to own a circular plane, yet this
tool is decidedly necessary for such round work as table tops, half-
round shelves, segments, and the like. Any ordinary block plane will
accomplish such work if equipped as illustrated. A piece of half-
round hard wood is cut the width of the plane and attached with
countersunk machine screws, as indicated. The block elevates the
rear end of the plane, causing it to follow the curve of the work on
which it is used.
Pressure Spray Made of Old Oilcan
Old Material Makes a Spray That Is as Good as the Manufactured Product, at

Less Cost
In making a spraying outfit for garden use, or similar purposes, a 3

or 5-gal. kerosene can and tire pump may be satisfactorily
employed. The latter is attached rigidly at the rear of the container
with iron straps, as shown. A ball check valve is fitted in the top of
the receptacle and connection is made between it and the pump with
the pump hose. A 6-ft. length of ¹⁄₄-in. rubber tubing is wired to the
drain cock. An 8-in. piece of ¹⁄₄-in. brass pipe is filed down and wired
in the spray end of the hose to serve as a nozzle.—P. P. Avery,
Garfield, N. J.
Keeping Tools Bright and Free from Rust
Bright-finished tools can be preserved against rust by coating with
linseed oil, and allowing the oil to dry as a film. If more body is
desired, oxide of iron, very finely powdered, should be mixed with
the oil. Another antirust coating is made by dissolving ¹⁄₂ oz.
camphor in 1 lb. melted lard. The mixture is skimmed, and fine
graphite added to make an iron color. Clean the tools and smear with
this mixture. Let the tools stand 24 hours, and rub clean with soft
cloth.
A good method of removing rust is to cover the metal parts with
sweet oil, rubbing it in well. Let stand 48 hours; then rub with finely
powdered, unslaked lime. Next immerse the article for a few seconds
in a solution of ¹⁄₂ oz. potassium cyanide in a wine glass of water.
Then clean with a paste of potassium cyanide, castile soap, whiting,
and water, using a toothbrush. Potassium cyanide is a strong poison,
and should be used carefully.—E. Standiford, Youngstown, Ohio.
Repairing Leaks in Pipes
Frequently a cast or malleable-iron pipe fitting will leak through its
side, the water oozing, drop by drop, from a pinhole—ordinarily due
to a sand hole in the casting. Sometimes the leak can be stopped by
hammering the affected spot with the ball end of a hammer. If this
fails, it is necessary to replace the fitting. Where the leak is around a
thread, screwing the pipe or fitting tighter constitutes the only, and
usually effective, corrective.—L. A. Merton, St. Louis, Mo.
Corn Popper Made from Coffee Can and Broom
Handle
A Corn Popper Made from a Coffee Can, or Similar Tin Receptacle, and a
Piece of a Broom Handle
With an old coffee can, or similar tin receptacle, and a piece of a

broom handle, 2¹⁄₂ or 3 ft. long, it is easy to make a corn popper that
is preferable in many ways to a wire one. Take a strip of wood a little
shorter than the height of the can to be used, and after boring two
holes in it to prevent its splitting, nail it to the end of the handle. The
latter is then fastened to the side of the can with two wire staples, as
shown. Holes are made in the can top to admit air to the corn while it
is popping.—James Crouse, Dixon, Ky.
An Easily Constructed Ball-Bearing
Anemometer
By THOMAS A. REYNOLDS
An anemometer is an instrument which measures the velocity of the

wind. The anemometers used by the weather bureau consist of
four hemispherical cups mounted on the ends of two horizontal rods
which cross at right angles and are supported on a freely turning
vertical axle. Since the concave sides of the cups offer more
resistance to the wind than do the convex sides the device is caused
to revolve at a speed which is proportional, approximately, to that of
the wind. The axle, to which the rotary motion is transmitted from the
cups, is connected to a dial mounted at the foot of the supporting
column. This dial records automatically the rotations. The
reproduction of such a registering mechanism would be rather
complicated. Hence, in the arrangement to be described none will be
employed. Therefore, one of these improvised anemometers, when
mounted on a high building, will indicate by the changing rapidity of
its revolutions only the comparative, not the real, velocity of the wind.
This Anemometer is Made from Galvanized Sheet Iron, a Bicycle Hub,
and a Few Iron Straps. Practice in Observing Its Motion will Enable One
to Estimate Fairly Closely the Wind’s Velocity
In constructing the instrument, straight, dished vanes will be used

instead of hollow cups. The vanes operate almost as effectively and
may be combined more readily into a sturdy rotating unit. A bicycle
front hub is utilized to constitute a wear- and noise-proof bearing
having minimum friction. Each of the four wings is formed from a
piece of galvanized iron, measuring 4¹⁄₂ by 10 in., which has one end
cut to a curve as shown. To each wing is fastened, with tinners’
rivets, a 4-in. length of ³⁄₄ by ¹⁄₁₆-in. strap iron. Form each of the
strips into a trough-shaped vane, measuring 2¹⁄₄ in. from edge to
edge—this being the distance between the spoke flanges of a
bicycle hub. Some cylindrical object of suitable diameter will serve as
a form for bending. Place the ends of the support strips between the
spoke flanges and rivet them securely. The rivets pass through the
spoke holes. Some trying out may be required to insure a
symmetrical arrangement of the parts. Solder the curved end of each
wing to the inner surface of the adjacent wing. Place a tin cap—a
salve-box lid will do—under the upper locknut on the hub to exclude
rain from the bearing.
The supporting upright may be a heavy wooden rod, or a piece of
iron pipe. A yoke of 1 by ¹⁄₈-in. strap iron, held to the top of the
upright with screws, is provided for the attachment of the hub. The
locknut on the hub clamps it to the yoke. Apply a coat of metal paint
to the iron parts which are exposed. Mount the device sufficiently
high to give the wind free access to it from all directions. The curve
at one end of each wing is an irregular one. Hence, its accurate
construction involves a knowledge of sheet-metal pattern drawing.
However, if it is made of a form similar to that shown it will fit
sufficiently well to permit a good soldered joint.
¶Boards exposed to the weather should be laid with the heart side
down, as determined by examining the end grain.
Fig. 2
Fig. 3
Fig. 1
Sharpened Poles, Two Feet Long, are Used with This Pile Driver in
Building Foundations, Wharves, and Other Structures of Piling. The
Details of the Headblock and the Nipper Device are Shown in Figs. 2 and
3
A Small Working Pile Driver
By EDWARD A. KRUEGER
[These directions will enable boys of varying skill with tools to make a pile
driver, as a toy or model. Several simple methods of making the parts in the
home workshop, with materials easily obtainable, are suggested.—Editor.]
Thebridges,
construction of small docks, wharves, piers, and foundations or
buildings, and other structures, by the driving of piling is
interesting out-of-door play, in which boys will find much fun. A pile
driver for this work is shown in the page plate, Fig. 1. The hammer is
raised by means of a winch, and is dropped automatically when it
reaches the cap of the derrick, as indicated in Fig. 3. The drum is
then released, and the weighted double-hook nipper drops down,
picking up the hammer on the next upstroke. A single-hook nipper,
that can be made easily of wire, is also shown in the detail sketch,
Fig. 6. The small boy who cannot make the nippers or the winch,
may tie the rope directly to the hammer, drawing it up by hand, and
dropping it as desired. The hammer need not be fitted to the guides,
but merely arranged to drop between them, and the derrick can be
made of only a few main pieces. The larger parts of the hammer and
nipper weight are best made of lead, babbitt, or white metal, as
these may be cut or melted readily. Iron, brass, or copper, solid or in
plates, may be used, if means for shaping them are at hand.
The making of the derrick may be undertaken first. Make two
pieces for the bed A, ⁷⁄₈ by ⁷⁄₈ by 17 in.; two hammer guides B, ⁷⁄₈ by
⁷⁄₈ by 33¹⁄₈ in.; one bed piece, C, ³⁄₈ by ⁷⁄₈ by 20 in.; two bed pieces,
D, ³⁄₈ by ⁷⁄₈ by 5¹⁄₄ in.; two posts, E, ¹⁄₂ by ¹⁄₂ by 34¹⁄₂ in.; two braces,
F, ³⁄₈ by ³⁄₄ by 26¹⁄₂ in. Cut these pieces slightly over their finished
lengths as given, allowing for trimming and fitting. Make strips, ¹⁄₄ by
¹⁄₂ in., for the bracing on the sides of the derrick and the ladder
bracing on the back.
Notch the lower ends of guides B, ¹⁄₈ by ⁷⁄₈. and the lower ends of
posts E, on an angle, ¹⁄₈ in. deep, to fit pieces A. Join the parts of the
bed, as shown in the page plate, pieces A being set 3¹⁄₂ in. apart,
fastening them with bolts or screws. Make braces G, of sheet metal,
and bolt them in place. Fit the posts E into place, and fasten them at
the bed and the top. Put on several ladder braces temporarily, to
steady the frame. Fit the braces F carefully, and bolt them in place.
Remove the piece C and the braces F, and nail the horizontal
bracing to the sides of the frame. Then fit and nail the diagonal
braces. The bolted construction is convenient in “knocking down” the
derrick for storing it. Reassemble the parts, and make the cap for the
headblock.
The headblock and cap are shown in detail in Figs. 2 and 3. Make
two pieces, H, ¹⁄₄ by 1⁵⁄₁₆ by 1³⁄₄ in.; one piece, J, ¹⁄₄ by 1 by 1³⁄₁₆ in.;
two braces, K, ¹⁄₄ by 1¹³⁄₃₂ by 1³⁄₄ in. Make the two beveled pieces of
the cap ⁷⁄₈ by 1³⁄₄ by 1¹⁄₂ in., and provide a wooden strip or metal
plate for the front and rear edges, as shown. Fasten strips of sheet
metal to the bevel of the notch, to protect it from wear by the striking
of the nipper hooks. Make the sheave 1¹⁄₂ in. in diameter and ³⁄₈ in.
thick, with a groove for the rope. Assemble the parts, as shown.
The details of the winch are shown in Figs. 4 and 5, and the
method of assembling the parts, in Fig. 1. The drum may also be
driven without gears by fixing the crank directly to the shaft. Gears
may be obtained from old machines, or purchased from dealers in
model supplies. Make the supports L and M, Fig. 4, ³⁄₄ by 4 by 6⁵⁄₈
in., cutting patterns of paper, if desired.
Fig. 4
The Supports of the Winch are Made of ³⁄₄-Inch Wood, Bolted to the Bed
The gear, Fig. 5, is 3¹⁄₂ and the pinion ³⁄₄ in. in diameter. The drum
is of wood, 2 in. in diameter and 3⁵⁄₁₆ in. long. Its ends are 3¹⁄₂-in.
metal disks, fastened with screws. The shaft is a ³⁄₈-in. bolt, 5³⁄₈ in.
long, and bears in holes bored in the supports, as shown in the
details of these parts. The crank N, Fig. 5, is made of a ³⁄₁₆-in. rod,
bent as shown, and fitted with a washer to fit next to the pinion. The
gear is set by means of the pawl O, which is bent from a strip of ¹⁄₁₆-
in. sheet metal. The brace P is bent from a ¹⁄₁₆ by ³⁄₄ by 1⁵⁄₈-in. strip
of sheet metal, and riveted to the pawl. Assemble the parts,
fastening the gear to the drum end, and bolt the supports into place.
Put the pinion into mesh with the gear at its proper place, and
carefully mark the hole for the crank. Square the end of the crank
and the hole in the pinion, and fit them to a driving fit. Fix the rope to
the drum, and reeve it through the head block. The derrick is then
ready for the hammer and the weighted nipper.
Fig. 5
Details of the Drum, Its Driving Mechanism, and Fittings
The hammer, shown in Fig. 6, may be made easily from a solid

block of lead, 1¹⁄₄ by 2⁵⁄₈ by 2⁵⁄₈ in. Cut ³⁄₁₆ by ⁷⁄₈-in. grooves in the
vertical edges to fit the guides. Make the circular ³⁄₁₆ by 1⁵⁄₈-in.
hammer plate Q of iron or brass, and fasten it with screws. Rivet the
wire lifting strap R, as shown.
Fig. 6
A Simple Method of Making the Tripping Device, and Details of the Hammer
The single-hook nipper, shown in Fig. 6, is made as follows:

Flatten a piece of ³⁄₁₆-in. wire at the middle, and drill a ³⁄₃₂-in. hole for
the bolt. Shape the lower end into a pointed hook, and bend the
upper end to form the trip arm. This strikes the notch in the cap of
the derrick, releasing the hammer. The rope is wired to the hook as
shown. The nipper weight is made of a solid piece of lead, 1¹⁄₄ by 2⁵⁄₈
in., by 1 in. high, grooved at the ends to fit the guides. Cut a slot
through it, for the hook, as shown in Fig. 6, and bolt the latter into
place. The double-hook nipper is better mechanically, and may be
made of two pieces of wire, or cut from sheet metal.
Test the action of the nippers, and bend or file the hooks to
operate properly. The pile driver may then be painted, and work on
“jobs” begun. If it is used at the water, fix metal guards at the lower
ends of the guides, to prevent the hammer from falling into the water.
Split Needle Causes Echo on Talking Machine
An amusing stunt is to split the end of a fiber talking-machine
needle carefully about ¹⁄₄ in., so as to make two points, slightly
separated. The needle is then placed on the machine, preferably on
an old record, so that the points play the record successively,
producing an echo. If the work is carefully done, and the points are
separated slightly, both reproductions will be fairly clear.—Frank
Murphy, Faribault, Minn.

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of Polymer Solutions, Three Volume Set

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No claim to original U.S. Government works

International Standard Book Number-13: 978-0-203-99820-5 (eBook - PDF)

Dr. Henry V. Kehiaian

IUPAC Representative on ICSU Committee on

Knowledge of thermodynamic data of polymer solutions is a necessity for industrial and

He is working on the evaluation, correlation, and calculation of thermophysical properties of pure

2. VAPOR-LIQUID EQUILIBRIUM (VLE) DATA

3. LIQUID-LIQUID EQUILIBRIUM (LLE) DATA

5. ENTHALPY CHANGES FOR AQUEOUS POLYMER SOLUTIONS

6. PVT DATA OF POLYMERS AND SOLUTIONS

7. SECOND VIRIAL COEFFICIENTS (A2)

1.1. Objectives of the handbook

• Vapor-liquid equilibrium (VLE) data of binary or ternary aqueous polymer solutions

1.2. Experimental methods involved

Investigations on vapor-liquid equilibrium of polymer solutions can be made by various methods:

1. Absolute vapor pressure measurement

1. Absolute vapor pressure measurement

2. Differential vapor pressure measurement

Difference/differential manometers have some advantages in their construction: they are

Again, the concentration can be determined independently by using a differential refractometer

3. Isopiestic sorption/desorption methods

Isopiestic measurements allow a direct determination of solvent activity or vapor pressure in

Concentration lowering under isothermal conditions is the classical isopiestic technique,

4. Gas-liquid chromatography (GLC)

Vnet = Vr − Vdead (1)

5. Vapor-pressure osmometry (VPO)

Liquid-liquid equilibrium (LLE) measurements

Experimental methods can be divided into measurements of cloud-point curves, of real

High-pressure phase equilibrium (HPPE) measurements

The experimental investigation of high-pressure fluid phase equilibria in polymer solutions is

Measurement of enthalpy changes in polymer solutions

∆Mh = nAHA + nBHB − (nAH0A + nBH0B) (12a)

The enthalpy effect might be positive (endothermic solution/mixture) or negative (exothermic

• per mole polymer B:

∆solHB = (∂∆ sol h / ∂nB ) P ,T ,n j = HB − H0B (14a)

∆solHB = (∂∆ sol h / ∂mB ) P ,T ,m j (14c)

∆MHB = ∆MH + (1 − xB)(∂∆MH/∂xB) (15)

∆solHA = (∂∆ sol h / ∂nA ) P ,T ,n j = HA − H0A (16a)

∆MHA = R [∂ ln a A / ∂ (1/ T )]P (18)

PVT/density measurement for polymer melt and solution

VEspez = Vspez − (wAV0A, spez + wBV0B, spez) (21a)

Determination of second virial coefficients A2

The freezing point depression, ∆SLTA, is:

and the boiling point increase, ∆LVTA, is:

The osmotic pressure, π , can be described as:

Scattering methods enable the determination of A2 via the common relation:

Sedimentation-diffusion equilibrium in an ultracentrifuge also gives a virial series:

Old Material Makes a Spray That Is as Good as the Manufactured Product, at

In making a spraying outfit for garden use, or similar purposes, a 3

With an old coffee can, or similar tin receptacle, and a piece of a

An anemometer is an instrument which measures the velocity of the

In constructing the instrument, straight, dished vanes will be used

The hammer, shown in Fig. 6, may be made easily from a solid