Molecular Characterization of Polymers

A Fundamental Guide : A Fundamental

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 MOLECULAR
CHARACTERIZATION
OF POLYMERS
A Fundamental Guide
 MOLECULAR
CHARACTERIZATION
OF POLYMERS
A Fundamental Guide

Edited by

MUHAMMAD IMRAN MALIK

H.E.J. Research Institute of Chemistry,
International Center for Chemical and Biological Sciences (ICCBS),
University of Karachi, Karachi, Pakistan

JIMMY MAYS
Department of Chemistry, University of Tennessee,
Knoxville, TN, United States

MUHAMMAD RAZA SHAH

H.E.J. Research Institute of Chemistry,
International Center for Chemical and Biological Sciences (ICCBS),
University of Karachi, Karachi, Pakistan
Elsevier
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 Contributors
Luca Baiamonte Department of Chemistry,
Colorado School of Mines, Golden, CO, United
States
Josef Brandt Department Anaylsis, Leibniz-
Institut f€
ur Polymerforschung Dresden e.V.,
Dresden, Germany
Taihyun Chang Department of Chemistry and
Division of Advanced Materials Science,
Pohang University of Science and Technology,
Pohang, South Korea
Mark D. Dadmun Department of Chemistry,
University of Tennessee, Knoxville; Chemical
Sciences Division, Oak Ridge National
Laboratory, Oak Ridge, TN, United States
Nadia Edwin Department of Health and
Biomedical Sciences, AdventHealth University,
Orlando, FL, United States
Anthony P. Gies The Dow Chemical Company,
Lake Jackson, TX, United States
David Gillespie Tosoh Bioscience LLC, King of
Prussia, PA, United States
Andrew Gorman School of Materials Science &
Engineering, Georgia Institute of Technology,
Atlanta, GA, United States
Alexander S. Gubarev Department of
Molecular Biophysics and Physics of Polymers,
Saint-Petersburg State University, Saint-
Petersburg, Russia
Shaw Ling Hsu Polymer Science and
Engineering Department, University of
Massachusetts (Amherst), Amherst, MA,
United States
Wayne Huberty Advanced Composites
Institute, Mississippi State University,
Starkville, MS, United States
Muhammad Imran H.E.J. Research Institute of
Chemistry, International Center for Chemical
ix
and Biological Sciences (ICCBS), University of
Karachi, Karachi, Pakistan
S. Kim Ratanathanwongs Williams Department
of Chemistry, Colorado School of Mines,
Golden, CO, United States
Albena Lederer Department Anaylsis, Leibniz-
Institut f€
ur Polymerforschung Dresden e.V.;
School of Science, Technische Universit€
at
Dresden, Dresden, Germany; Department of
Chemistry and Polymer Science, Stellenbosch
University, Matieland, South Africa
Wei Lu Tosoh Bioscience LLC, King of Prussia,
PA, United States
Muhammad Imran Malik H.E.J. Research
Institute of Chemistry, International Center for
Chemical and Biological Sciences (ICCBS),
University of Karachi, Karachi, Pakistan
Jimmy Mays Department of Chemistry,
University of Tennessee, Knoxville, TN, United
States
Toshikazu Miyoshi Department of Polymer
Science, The University of Akron, Akron, OH,
United States
Harald Pasch Department of Chemistry and
Polymer Science, University of Stellenbosch,
Stellenbosch, South Africa
Jigneshkumar Patel Intel Corporation
(Chandler), Chandler, AZ, United States
Georges M. Pavlov Institute of Macromolecular
Compounds, Russian Academy of Sciences,
Saint-Petersburg, Russia
Igor Perevyazko Department of Molecular
Biophysics and Physics of Polymers, Saint-
Petersburg State University, Saint-Petersburg,
Russia
Jawadur Rehman H.E.J. Research Institute of
Chemistry, International Center for Chemical
x Contributors
and Biological Sciences (ICCBS), University of
Karachi, Karachi, Pakistan
Sebastien Rouzeau Tosoh Bioscience LLC, King
of Prussia, PA, United States
Paul S. Russo School of Materials Science &
Engineering; School of Chemistry &
Biochemistry, Georgia Institute of Technology,
Atlanta, GA, United States
Salim Saifullah H.E.J. Research Institute of
Chemistry, International Center for Chemical
and Biological Sciences (ICCBS), University of
Karachi, Karachi, Pakistan
Muhammad Raza Shah H.E.J. Research
Institute of Chemistry, International Center for
Chemical and Biological Sciences (ICCBS),
University of Karachi, Karachi, Pakistan
William C. Smith Department of Chemistry,
Colorado School of Mines, Golden, CO, United
States
Ali Soleymannezhad Tosoh Bioscience LLC,
King of Prussia, PA, United States
Kiril A. Streletzky Department of Physics,
Cleveland State University, Cleveland, OH,
United States
Michael Toney Department of Chemistry,
Colorado School of Mines, Golden, CO, United
States
Xujun Zhang Wyatt Technology Corporation,
Santa Barbara, CA, United States
Weiwei Zhao Ningbo Materials Institute,
Ningbo, China
 Foreword

As we contemplate the centennial of macromolecular chemistry, we may be reasonably

certain that Hermann Staudinger never said “Polymer scientia est omnis divisa in partes tres,”
but if he had, he would have been right! The first part of polymer chemistry is synthesis:
what molecular structures can we make, how easily, and how reproducibly? The third part
comprises material properties: what is this polymer good for, how can we make it better, and
how can we combine multiple desirable properties in one material? The intermediate domain,
and the essential component in order to close the structure-property loop, is polymer
characterization: what did we make, exactly?
There is no doubt that polymer characterization is, in general, a formidable experimental
challenge. At the root of the problem is the unavoidable fact that all synthetic polymers are het-
erogeneous in their molecular structure. A simple calculation reveals that even a tank car full of
homopolymer will not contain two molecules that are precisely identical. Not only is there a
distribution of molar mass, but there is also heterogeneity in multiple variables, including,
for example, regioisomerism, stereochemistry, long- and short-chain branching, and copoly-
mer sequence and composition. Ideally, we would like to characterize all of these distributions,
at least to the level of a mean value and a variance. This goal is currently beyond the capabilities
of most laboratories, although experimental science continues to advance significantly.
It is no surprise that full molecular characterization demands a suite of experimental tools.
Each technique will provide valuable information, but none can be sensitive to all of the vari-
ables of interest. This creates a further challenge for the polymer scientist: how to decide which
techniques to use, and how to use them effectively? It is tempting to view each instrument as a
black box: insert some sample material, and out pops an answer (typically with a ridiculous
number of significant figures). As experimental scientists, we know this is dangerous; every
technique relies on a set of assumptions, which may or may not apply for the sample we care
about. We can consult a textbook, or, more likely, Wikipedia, and find a brief discussion of the
technique, and a statement of the working equations. While helpful, this is not sufficient.
A good practitioner needs to understand the assumptions, and also to be conversant with
the strengths and weaknesses, the opportunities and blind spots, of each characterization tool.
This is the void that Molecular Characterization of Polymers: A Fundamental Guide aims to fill.
The authors adopt a tutorial style, so that specific prior knowledge is not required. And, by
taking this approach, the reader is empowered to acquire a deeper understanding of the
theory underlying each approach. As noted before, there have been substantial recent ad-
vances in instrumental techniques, and thus this up-to-date treatment will be very valuable
for experienced practitioners as well.
Timothy P. Lodge
University of Minnesota, Minneapolis, MN, United States

xi
 Preface
It is very appropriate as we celebrate in
2020 the 100-year anniversary of Nobel Lau-
reate Hermann Staudinger’s “discovery” of
polymers, that we assemble this new book
on Molecular Characterization of Polymers: A
Fundamental Guide. This is because Stau-
dinger, beginning in 1920 until 1930, utilized
a series of ingenious molecular characterization
studies to prove the long chain nature of poly-
mers, their high molecular weights, and their
distribution of chain lengths (molecular
weight distribution, MWD) [1–3]. This work
earned Staudinger the Nobel Prize in Chem-
istry in 1953.
In the decades after Staudinger’s discov-
ery of polymers, the synthesis of polymers
of ever-increasing complexity led to the
“polymer age” of materials which continues
to this day, and new methods have been
continually developed in order to better
characterize polymers. However, even in
1975, the eminent polymer scientist Fred
Billmeyer stated “…characterization of poly-
mers is inherently more difficult than that of
other materials. Polymers are roughly equiv-
alent in complexity to, if not more complex
than, other materials, at every physical level
of organization from microscopic to macro-
scopic…” and “We would wish, ideally, to
characterize all aspects of polymer structure
in enough detail to predict its performance
from first principles. I seriously doubt that
this will ever be possible…” [4].
Billmeyer’s remarks stem from the fact
that synthetic polymers always exhibit a
distribution of chain lengths or MWD.
Homopolymers are further complicated by
xiii
tacticity, mode of monomer insertion (e.g.,
head-to-tail or head-to-head), chain con-
formation (flexibility), end groups, and
branching (long chain and/or short chain).
Copolymers are further complicated by
monomer sequence distributions and varia-
tions in comonomer content across the
MWD. All of these factors affect polymer
processing and the properties of the poly-
meric material, but polymer characterization
methods only yield average values and dis-
tributions of key molecular parameters. Even
today, nearly a half century since Billmeyer’s
statements, despite all the advances in char-
acterization techniques and computation, the
thorough and accurate molecular characteri-
zation of polymeric materials remains highly
challenging.
Another factor complicating the thorough
characterization of polymers is the need to
employ a combination of different character-
ization techniques, as well as some knowl-
edge on how the polymer was synthesized,
in order to rigorously characterize even the
simplest of polymers. Unfortunately, scien-
tists actively involved in characterizing poly-
mers, either in industry or in academia, are
usually specialists in one or two analytical
techniques and lack detailed knowledge in
a wide range of complementary polymer
characterization techniques, as well as poly-
mer synthesis methods and their impact on
polymer structure, that must be employed
in order to understand the polymer’s molec-
ular structure in detail. As examples, in
industry analytical chemists are often
confronted for the first time with
xiv
characterizing polymers and they may have
little or no experience in characterizing such
complex mixtures. Also, few polymer scien-
tists are rigorously trained in a wide range of
polymer characterization techniques.
Thus the primary purpose of this book is
to serve as a textbook for a course (academic
course or short course) on polymer charac-
terization in order to better train the next
generation of polymer characterization
experts. This book is thus written in a tutorial
style to serve as an introduction to the vari-
ous polymer characterization techniques.
We anticipate that this book, written in this
style, will also be useful to scientists in indus-
trial polymer analysis laboratories who
are applying a characterization technique
to polymers for the first time. In addition to
fundamentals, we have also included in each
chapter recent advances in the technique,
information on instrumentation, and recent
applications to make this book useful to sci-
entists with experience in a technique but
looking for updates on recent advances and
applications.
This book begins with several chapters on
chromatography of polymers. Chapter 1 in-
troduces basic principles of chromatography
of polymer, including size exclusion chroma-
tography (SEC), high performance liquid
chromatography (HPLC), and liquid chro-
matography at the critical condition. Data
reduction methods and column technologies
are discussed. Chapter 2 discusses
multidetector SEC of polymers, using detec-
tors such as light scattering and viscosity de-
tectors, for characterizing simple and
complex (copolymer, branched) polymers.
SEC remains the workhorse for characteriz-
ing polymer molecular weight distributions.
Chapter 3 discusses the use of temperature
gradient interaction chromatography for
characterization of branched polymers
and copolymers, end functionalized poly-
mers, and isotopically labeled polymers.
Preface
Chapter 4 describes basic principles and ap-
plications of field flow fractionation (FFF) to
polymers. Chapter 5 focuses on the industri-
ally important area of characterization of
polyolefins, which constitute half of the an-
nual polymer production worldwide. Be-
cause of their limited solubility, polyolefins
present special challenges in their character-
ization. Multidetector SEC of polyolefins is
discussed, along with crystallinity-based
techniques such as temperature rising elu-
tion fractionation and crystallization analysis
fractionation.
Chapter 6 describes the use of combina-
tions of fundamental hydrodynamic ap-
proaches (analytical ultracentrifugation,
intrinsic viscosity, translational diffusion,
and SEC) to characterize molecular weights,
dimensions, and conformation. These com-
bined techniques are especially useful with
complex polymers such as polyelectrolytes.
Chapter 7 describes the use of viscometry
to measure polymer size, molecular weight,
as well as gather insight into conformational
characteristics and branching. Methods for
detecting and quantifying long chain
branching, including viscometry, light scat-
tering, and multidetector SEC are described
in Chapter 8.
Chapter 9 is focused on recent advances in
mass spectrometry of polymers, focusing on
MALDI-TOF-MS and MS/MS. Chapters 10
and 11 describe the use of vibrational spec-
troscopy and NMR for structural characteri-
zation of polymers, including end groups,
composition, tacticity, etc. Chapters 12 and
13 describe the use of static and dynamic
light scattering to characterize polymer mo-
lecular weights, sizes, thermodynamic inter-
actions and conformations. Chapter 14
introduces LenS3, a new light scattering de-
tector that measures polymer molecular
weights and allows for radius of gyration
measurements in the sub-10-nm range. The
use of X-rays and neutrons for probing
 Preface
polymer structure and conformation, in bulk,
thin film, and in solution, is described in
Chapter 15 along with selected applications.
Chapter 16 covers microscopy of polymers,
with a basic introduction to SEM, TEM, and
AFM and recent applications to polymers.
We are grateful to all the authors who
made the timely assembly of this book possi-
ble even under the challenges imposed by
the Covid-19 pandemic.
Muhammad Imran Malika, Jimmy Maysb, and
Muhammad Raza Shaha
a
University of Karachi, Karachi, Pakistan
b
University of Tennessee, Knoxville, TN,
United States
xv
References
€
[1] H. Staudinger, Uber polymerisation, Ber. Deut.
Chem. Ges. 53 (1920) 1073–1085.
[2] H. Staudinger, Uber € die Konstitution der
Hochpolymeren, Ber. Deut. Chem. Ges. 61 (1928)
2427–2431.
[3] H. Staudinger, W. Heuer, Uber € hochpolymere
Verbindungen, 33. Mitteilung: Beziehungen
zwischen Viscosit€at und Molekulargewicht bei
Poly-styrolen, Ber. Deut. Chem. Ges. 63 (1930) 222–
234.
[4] F.W. Billmeyer, Trends in polymer characterization,
J. Polym. Sci. Symp. 55 (1975) 1–10.
 C H A P T E R

1
Basic principles of size exclusion and
liquid interaction chromatography
of polymers
Muhammad Imran Malika and Harald Paschb
a
H.E.J. Research Institute of Chemistry, International Center for Chemical and Biological
Sciences (ICCBS), University of Karachi, Karachi, Pakistan bDepartment of Chemistry and
Polymer Science, University of Stellenbosch, Stellenbosch, South Africa

Polymers are inherently complex multicomponent materials having several simple and
distributed properties. Simple properties include total weight of the polymer, residual mono-
mer/oligomer, gel content, etc. Distributed properties are those in which different molecules
of the same sample have dissimilar values. The important distributed properties of polymers
include molar mass, chemical composition, sequence length, end group functionality, molec-
ular topology, etc. The performance properties of polymers are highly dependent upon these
distributed properties. The performance of polymers for any particular application can be im-
proved significantly by carefully monitoring, adjusting, and understanding their molecular
distributions. An important tool for the determination of distributed molecular properties of
polymers is separation science.
The size, chemical composition, sequence of repeat units, and architecture are some impor-
tant parameters that need to be considered when analyzing any polymer. The constitution,
configuration, and conformation of macromolecules are also critical for regulating any poten-
tial application. Polymers having similar molar masses and chemical compositions can have
completely different properties depending upon the sequence, constitution, configuration,
and conformation of their repeat units. Polymers having any distribution beyond only molar
mass are termed as complex polymers.
The concept of molecular heterogeneity can be utilized to describe the structural complex-
ity of synthetic polymers, see Fig. 1.1. Different types of heterogeneities of polymer chains
might superimpose each other and a given polymer sample may exhibit a molar mass dis-
tribution, a chemical composition distribution, individual block length distributions,

Molecular Characterization of Polymers 1 Copyright # 2021 Elsevier Inc. All rights reserved.
https://doi.org/10.1016/B978-0-12-819768-4.00007-5
2 1. Basic principles of size exclusion and liquid interaction chromatography of polymers

Chain Length End Group

Polymer Concentration

Block Length Architecture

Molar Mass
FIG. 1.1 Molecular heterogeneity of complex polymers. Reproduced from H. Pasch, Hyphenated techniques in liquid
chromatography of polymers, Adv. Polym. Sci. 150 (2000) 1–66, with permission from Springer Nature. Copyright 2000.

a functionality type distribution (end group distribution), and a molecular architecture

distribution. Important information required for the comprehensive characterization of
complex polymers are the molar mass distributions within each type of heterogeneity.
Synthetic polymers always have a dispersity with regard to molar mass that originates
from the presence of polymer chains having different lengths. Molar masses of polymers
may be expressed as different averages, e.g., number-average molar mass (Mn), weight-
average molar mass (Mw), etc. The broadness of the molar mass distribution can be expressed
by the molar mass dispersity (Ð) that is the ratio of weight-average and number-average mo-
lar masses (Mw/Mn). Size exclusion chromatography (SEC) is one of the most important
methods for the analysis of molar mass distributions of polymers [1].
Different functional groups at the polymer chain end or along the polymer chain introduce
another heterogeneity that is particularly important for oligomers and telechelic polymers.
The properties and reactivities of oligomers and telechelic polymers differ with regard to
the number and nature of the functional groups. Spectroscopic techniques can only provide
average numbers, whereas well-designed chromatographic separation methods can reveal
the functionality distribution as a function of other heterogeneities, e.g., the molar mass
distribution [2].
The involvement of more than one monomer in a polymerization reaction complicates the
situation and the resulting polymer may have a chemical composition distribution
superimposing the molar mass distribution. Spectroscopic techniques such as NMR and FTIR
can provide an average chemical composition of the sample. However, no information on the
distribution of chemical composition as a function of molar mass can be obtained. Moreover,
spectroscopic techniques can typically not differentiate between copolymers and mixtures of
their respective homopolymers. Interaction chromatographic techniques can provide more
 1.1 Liquid chromatography of polymers 3
insight into the complex composition of copolymers. There can be several additional hetero-
geneities in copolymers such as the bulk molar mass distribution, the distribution of repeat
units in the copolymer, the lengths of different segments in case of segmented copolymers, the
presence of any type of homopolymer in the bulk sample, etc. The above-mentioned factors
make the comprehensive characterization of polymers a multifaceted task. For the analysis of
the chemical composition as a function of molar mass, multidetector approaches may be re-
quired (see Chapter 2 for detailed discussion). The independent analysis of each type of het-
erogeneity requires independent separation techniques that are selective regarding specific
types of distributions. In order to get access to one type of heterogeneity as a function of other
heterogeneities, coupling of independent chromatographic techniques or hyphenation of
chromatographic separation with spectroscopic techniques is imperative.
To summarize, a minimum of two independent methods are required for the analysis of
complex polymers each with a certain selectivity for one type of heterogeneity. In this context,
different modes of HPLC of polymers such as SEC, liquid chromatography at critical condi-
tions (LCCC), and interaction chromatography (IC) or liquid adsorption chromatography
(LAC) can be coupled to each other. Coupling of a chromatographic separation with spectro-
scopic techniques can also be a fascinating approach in order to obtain the distribution of one
property as a function of another distribution.

1.1 Liquid chromatography of polymers

The basic principle of any chromatographic process is based on the selective distribution of
the analyte molecules between the mobile and the stationary phase. The separation process
of chromatography can be described by
Ve ¼ Vi + Vp Kd (1.1)
where Ve, Vi, Vp, and Kd represent the elution (retention) volume of the analyte, the interstitial
volume of the column, the pore volume of the packing, and the distribution coefficient, re-
spectively. The distribution coefficient is the ratio of the analyte concentration in the mobile
and the stationary phase. Kd is related to the variations in Gibbs free energy Δ G that depends
on analyte partitioning between interstitial and pore volume [3].
ΔG ¼ ΔH  TΔS ¼ RT ln Kd (1.2)
The logarithmic plot of the distribution coefficient allows the determination of the entropic
(ΔS) and enthalpic (ΔH) contributions (van t’ Hoff plot):
ΔS ΔH
ln Kd ¼  (1.3)
R RT
Different effects that contribute to the change in Gibbs free energy are (1) the decrease
in conformational entropy that originates from limited dimensions inside the pores of the
stationary phase, and (2) changes in enthalpy that originate from the (adsorptive) interaction
of macromolecules with the stationary phase.
SEC separates macromolecules with regard to their hydrodynamic volume in dilute solu-
tion. The stationary phase in SEC is a swollen gel having a characteristic pore size
4 1. Basic principles of size exclusion and liquid interaction chromatography of polymers

distribution. The macromolecules may have less or more access to the pores depending on
their hydrodynamic sizes. Very large molecules cannot enter the pores and are excluded, elut-
ing at the interstitial volume Vi. Very small molecules have full access to the pores of the sta-
tionary phase and elute at the void volume of the column which is the sum of interstitial and
pore volume (Vo ¼ Vi + Vp). Hence, the separation range of SEC is 0 < KSEC < 1.
In ideal SEC, the distribution coefficient depends only on entropy changes without any
involvement of enthalpic interactions; however, in real SEC this is difficult to achieve. On
the other hand, the distribution coefficient in the case of IC totally depends on the interaction
strength of the analyte molecules with the stationary phase. This is perfectly true only for
small molecules. Longer chains of polymers may not have access to the whole pore volume,
hence, entropic factors must be assumed to contribute in addition to enthalpic contributions.
In case of polymers, often mixed modes of chromatography are operative and methods are
defined by the predominance of entropic or enthalpic interactions. Entropic interactions are
predominant in case of the size exclusion mode, i.e. T Δ S > Δ H corresponds to negative value
of Δ G, while separation in the interaction mode is dominated by enthalpic interactions, i.e.
Δ H > T Δ S corresponds to positive value of Δ G. Interaction forces exactly compensate
entropy losses at the transition point of the exclusion and interaction modes, i.e. Δ H ¼ T Δ S
corresponds to zero value of Δ G. This mode of liquid chromatography of polymers is often
termed as liquid chromatography at critical conditions.
Hence, Gibbs free energy at the chromatographic critical point is constant (Δ G ¼ 0) and the
value of the distribution coefficient equals 1, Kd ¼ 1, independent of the molar mass of the
polymer and the pore size of the stationary phase. A narrow range between size exclusion
and interaction modes of LC that is sensitive to changes in temperature and mobile phase
composition is related to the chromatographic critical point. This transition from one mode
of separation to the other was reported for the first time by Belenkii et al. [4] and Tennikov
et al. [5]. They demonstrated sudden changes in the elution behavior by slight variations in
the composition of the mobile phase. Hence, the transition point between the SEC and IC
modes can be realized by carefully adjusting the mobile phase composition and the temper-
ature. This specific transition point is labeled as the chromatographic critical point (CCP) and
the corresponding mode of liquid chromatography is termed as liquid chromatography at
critical conditions (LCCC).
A presentation of the transition between the three modes of liquid chromatography of
polymers is shown in Fig. 1.2. In SEC, retention decreases with increasing molar mass
whereas retention increases with molar mass in IC or LAC. At LCCC, the exclusion and in-
teraction effects are compensated rendering a molar mass independent elution of a particular
polymer at a constant elution volume. These separation modes can be combined in various
ways to realize separations of polymers with regard to different distributions such as molar
mass, chemical composition, and functionality. SEC, the most frequently used method for
polymer analysis, separates polymers with regard to their hydrodynamic size in dilute solu-
tion, and several approaches are in place to obtain chemical composition information as a
function of molar mass that include multiple concentration detector systems, and universal
calibration with viscometric and light scattering detection (see Chapter 2 for detailed discus-
sion). One must keep in mind, however, that SEC separation is based on size and the chemical
compositions obtained by different approaches are only average values related to a given SEC
fraction.
 1.2 Theory of polymer chromatography 5

FIG. 1.2 Dependence of elution volume on molar mass in different modes of liquid chromatography of polymers.

1.2 Theory of polymer chromatography

Retention of an analyte on the stationary phase in HPLC is expressed in terms of the

distribution coefficient as follows:
Ve  Vi
K¼ (1.4)
Vp
The distribution coefficient may assume different values in different modes of liquid
chromatography. In this context, de Gennes introduced a function that is termed the interac-
tion parameter, c [6, 7]. The value of interaction parameter depends on the mobile phase
composition (for a given polymer-stationary phase system) and temperature. The unit of
the interaction parameter is inverse length (nm1).

1.2.1 Size exclusion chromatography

In SEC, the value of the interaction parameter c is negative while the distribution coefficient
assumes values between zero and one (0 < K < 1). SEC separation is controlled by entropy
changes induced by differently sized species moving through the chromatographic column.
The elution volume of SEC in ideal conditions is given by Eq. (1.5) [8]
 
4 R
VSEC ¼ Vi + Vp 1  pffiffiffi (1.5)
πD
6 1. Basic principles of size exclusion and liquid interaction chromatography of polymers

where R is the radius of gyration of the analyte while D is the pore diameter of the stationary
phase. The radius of gyration expressed in terms of length and number of repeat units is
given as
rffiffiffi
n
R¼a (1.6)
6
where a is the length and n is the number of the repeat units.
Separation in SEC is realized with regard to molecular dimensions regardless of compo-
sition and functionality.

1.2.2 Interaction chromatography or liquid adsorption chromatography

IC is based on the strength of interaction of the analyte molecules with the stationary phase.
The value of c is positive whereas the distribution coefficient has values larger than one (k > 1)
that increases exponentially with the number of repeat units.
Retention in IC is often described in terms of Martin’s rule [9, 10].
ln k ¼ A + Bn (1.7)
The dimensionless factor k is deduced from the elution volume of the solute and holdup
volume (different from void volume) of the column. An excellent review with regard to
holdup volume of the column is presented by Rimmer et al. [11]. In this context, Gorbunov
and Skvortsov developed a theory of chromatography for flexible homopolymers that can
interact with the stationary phase [12, 13]. According to this theory, the elution volume of
a nonfunctional polymer chain in IC is given by
 
4 R 2Vp 2Vp
Ve ¼ Vi + Vp 1  pffiffiffi  + exp ðcRÞ2 ½1 + erf ðcRÞ (1.8)
πD cD cD
wherein D is the pore diameter of the stationary phase, R is the radius of gyration of the mac-
romolecule, c is the interaction parameter, and erf(cR) is the error function. It is pertinent to
mention here that the value of c is independent of D, Vp, Vi, or R (i.e., the degree of polymer-
ization n).
The term erf(cR) approaches unity at sufficiently strong interaction (typical for IC) and,
therefore, Eq. (1.8) can be rewritten as
 
4 R 2Vp 2Vp
Ve ¼ Vi + Vp 1  pffiffiffi  + exp ðcRÞ2 (1.9)
πD cD cD
or
 2 2
4Vp c a
Ve ¼ Vo∗ + exp n (1.10)
cD 6
where V∗o is the accessible volume for the polymer chain.
 
4R 2Vp 2Vp
Vo∗ ¼ Vi + Vp 1  pffiffiffi  ¼ VSEC  (1.11)
D π cD cD
 1.2 Theory of polymer chromatography 7
Obviously, the accessible volume is smaller than the void volume (Vo ¼ Vi + Vp). The acces-
sible volume in IC can be obtained by plotting the elution volumes of oligomers Vn with n
repeat units versus the difference in elution volume of consecutive peaks (Δ Vn ¼ Vn  Vn1)
Vn ¼ Vo∗ + γΔVn (1.12)
The accessible volume is represented by the intercept of the plot, and slope γ ¼ e /(eB  1)
B

can be used to calculate the interaction parameter c, wherein B ¼ (c2a2)/6 is the slope in
Martin’s rule (see Eq. 1.7)
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1 γ
c¼ 6 ln (1.13)
a γ1
It can be noticed that the number n of the individual peaks is not required for the
determination of the accessible volume and the interaction parameter, provided sufficiently
strong interaction is present. Moreover, Gorbunov et al. developed a software for the deter-
mination of interaction parameters in all modes of LC [14]. The approach is based on a set of
measurements of nonfunctional polymer standards of known molar mass. Eq. (1.10) can also
be rewritten in terms of the retention factor k∗
 2 2
Ve  Vo∗ 4Vp c a
k∗ ∗
¼ ∗
exp n (1.14)
Vo cDV 0 6
The logarithmic form of the equation corresponds to Martin’s rule.
 
4Vp c 2 a2
lnk ¼ ln
∗ + n (1.15)
cDV ∗0 6
Martin’s rule can also be rewritten for nonfunctional chains as
2Sp ðcaÞ2
ln k∗ ¼ ln + n (1.16)
cV ∗0 6
The pore surface can also be determined from the intercept of Martin’s plot once the
interaction parameter is determined using the earlier equations. However, the identification
of the peaks is required for the determination of the pore surface. For mono-functional chains,
an additional parameter q is required [15]. The specific end group parameter q measures the
difference of free energy of adsorption of end group and repeat unit [16]. A facile method
for the determination of q has been elaborated by Nguyen and Trathnigg [17].
In IC, retention of mono-functional chains with an adsorbing end group can be written as
!
4 Vp c 2 a2
ln k∗m ¼ ln ∗
ð1 + qcÞ + n (1.17)
cD V0, m 6

V∗0,m is the accessible volume for mono-functional chains that is smaller than the accessible
volume for nonfunctional chains.

∗ ¼ V∗ 
Vp 2 q
V0,m pffiffiffi (1.18)
0
D π Rc
8 1. Basic principles of size exclusion and liquid interaction chromatography of polymers

The value of k increases exponentially with the number of repeat units. Straight lines
with the same slopes are obtained in a plot of lnk vs n in both cases, having rather different
intercepts.
IC allows for separation of oligomers of nonfunctional polymers as well as mono-
functional polymers with a rather weakly adsorbing end group. Stronger interaction of the
end group results in poor resolution of individual oligomers.

1.2.3 Liquid chromatography at critical conditions

Entropic and enthalpic terms compensate each other in liquid chromatography at critical
conditions. At this so-called chromatographic critical point (CCP), the values of the distribu-
tion coefficient and the interaction parameter equal to one and zero, respectively. The com-
pensation of enthalpic interaction and entropic exclusion renders molar mass-independent
elution of nonfunctional chains at the void volume of the column. An additional term qa is
required to describe the influence of an interacting end group a on retention. The elution vol-
ume of chains with an adsorbing end group at their chromatographic critical point is larger
than the void volume, however, independent of molar mass [16, 18].
Va  Vi + Vp ð1  qa Þ  V0 + qa Vp (1.19)
The contribution of the end group on retention at the critical point allows for separation of
mono-functional chains with regard to the interaction strength of the end group independent
of molar mass. However, a very different behavior is observed with di-functional chains (with
adsorbing groups at both ends) [16, 19]. The elution volume of chains with symmetrical
groups at both ends is given by
 
q2a D
Vaa  Vi + Vp 1 + 2qa + pffiffiffi (1.20)
πR
The equation indicates that di-functional chains are separated with regard to the radius of
gyration R of the critical polymer chain. Asymmetrical di-functional polymer chains (bearing
different groups at the chain ends) hold the same relation,
 
qa qb D
Vab  Vi + Vp 1 + qa + qb + pffiffiffi (1.21)
πR
where a and b are end groups.
Di-functional chains elute later than mono-functional polymeric chains; however, their
elution volume is not only dependent on contributions of the end groups a and b but also
contain an additional term that is the ratio of the pore diameter D of the stationary phase
and the radius of gyration R of the polymer molecules [16, 19]. Consequently, elution of
di-functional polymer chains with adsorbing end groups follows SEC order.
There is another special situation where the end group adsorbs while the repeat units are in
SEC mode. This regime of liquid chromatography of polymers is termed as liquid exclusion
adsorption chromatography (LEAC) [20]. Under these conditions, the interaction parameter
of the repeat unit c is negative while the interaction parameter of the end group cB is positive.
This condition renders elution of mono-functional chains in SEC order beyond the void
 1.3 Thermodynamics of polymer chromatography 9
volume of the column. The mathematical relation for the elution volume VAB of short
mono-functional polymer chains under the described conditions is given by
 pffiffiffi 
π pffiffiffiffiffiffi
VAB  VB 1  cB RA ¼ VB ð1  C nA Þ (1.22)
2
where A is the repeat unit while B is the end group.
The elution volume decreases with increase in the number of repeat units (and hence
radius of gyration). The method can be used for oligomer separations of mono-functional
polymer chains containing 10–15 repeat units in SEC order beyond the void volume of the
column. This is essentially an isocratic separation that allows a RI detector to be employed,
resulting in accurate quantification [21].

1.3 Thermodynamics of polymer chromatography

The distribution coefficient depends on changes in Gibbs free energy that correspond to
variations in entropy and enthalpy, see Eqs. (1.2) and (1.3). Separation in the size exclusion re-
gime is governed by the entropic term whereas interaction is an enthalpic process. However,
entropic or enthalpic contributions are not easy to avoid completely especially in the case
of macromolecules. Both enthalpic and entropic terms compensate each other at the critical
mode of liquid chromatography of polymers which means Δ G ¼ 0, as Δ H ¼ T Δ S.
As described previously, SEC and IC mechanisms may show different dependences on
temperature. The distribution coefficient solely depends on entropic changes in ideal SEC
(no enthalpic interactions) rendering no dependence on temperature. In LCCC, entropic
and enthalpic effects are counterbalanced, hence, any change in temperature would require
a different mobile phase composition to retain the critical behavior. Consequently, retention
in IC depends both on enthalpy and entropy changes. Retention of any polymer on a given
stationary phase depends on the mobile phase composition and the temperature. However,
the extent and direction of this dependence varies.
The changes in entropy and enthalpy can be determined from the van’t Hoff plot, ln K vs
1/T. Various approaches that primarily differ in the calculation of the distribution coefficient
are used for the determination of thermodynamic parameters [22, 23].
Direct proportionality between the distribution coefficient K and the retention factor
k ¼ (Ve  V0)/V0 is often applied in this regard
ΔH° ΔS°
lnk ¼  + + lnφ (1.23)
RT R
wherein term lnφ corresponds to mobile and stationary phase ratio (generally not known),
principally indicating the pore volume and interstitial volume. Hence, the slope and
intercept in a plot of ln K vs 1/T represent the thermodynamic parameters Δ H°/R and
(Δ S∗/R) ¼ (Δ S°/R) +lnφ. However, there is no direct correlation between the distribution
coefficient K and the retention factor k as is clear from equations
Ve  V0
k¼ (1.24)
V0
10 1. Basic principles of size exclusion and liquid interaction chromatography of polymers

Ve  Vi Ve  Vi
K¼ ¼ (1.25)
Vp V0  Vi
The relationship between the distribution coefficient K and the retention factor k can be
devised as
Vp
k ¼ ð K  1Þ (1.26)
V0
Contrary to a typical assumption, there is no direct proportionality between K and k. The
assumption that K ¼ kφ is an approximation and holds only for K ≫ 1. The exact relation con-
tains the distribution coefficient K; however, the determination of characteristic volumes Vi,
Vp, and V0 are required.
It is pertinent to mention here that the determination of the value of void volume is not
trivial. Numerous articles address the issue of the accurate determination of the void volume,
the dead volume, and the holdup volume [11, 24], having different definitions relevant to par-
ticular situations [11, 25–27]. The void volume is usually taken as the total amount of solvent
in the column that can be determined gravimetrically. On the other hand, the holdup volume
is considered as the elution volume of an unretained compound that can be determined by
various methods [11, 24]. The interstitial volume can be determined by inverse SEC. It is ac-
tually the elution volume of a completely excluded polymer from the pores of the stationary
phase. However, these values are very much dependent on the mobile phase and may assume
dissimilar values in different mobile phases.

1.4 Equipment and materials

Separations by different modes of liquid chromatography of polymers pose several chal-

lenges that can be addressed by state-of-the-art HPLC instrumentation. Typically, a flexible
pump (for isocratic and gradient separations), a column oven (for stable temperature
conditions), and a reliable set of detectors (for quantitative information with regard to differ-
ent molecular parameters) are required.
The main components of any HPLC instrument include a solvent delivery system, a sam-
ple injector, a set of detectors, and a data acquisition system. Columns are the core of any
separation system that contain stationary phases of different nature, which are selected
according to the targeted separation.

1.4.1 Solvent delivery and injector

One of the most important requirements of any HPLC system is a constant and reproduc-
ible supply of mobile phase. Several types of pumps are employed for a reliable mobile phase
delivery in HPLC. These include syringe pumps (works like a syringe for pulseless flow) and
reciprocating pumps that exist in various modifications as single pistons, parallel dual pis-
tons, and dual pistons in series. General requirements of HPLC/SEC with regard to the pump
include a flow rate precision of 0.2%, a pressure output of 6000 psi, a pressure pulsation of less
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Fig. 17.—Dressing Case.
 Fig. 18.—Combination Dressing Case and Table.

Waste Cans.—All soiled dressings and sponges should be

immediately thrown into an enameled iron pail furnished for the
purpose. At no time must soiled dressings or sponges be thrown
upon the floor, where they are walked over, soiling the floor and, by
drying, contaminating the air of the room. Cans for this purpose are
made of steel, enameled, of the form shown in Fig. 19.
The contents of the can must be taken from the room after each
operation and burned. The can should be flushed with carbolic
solution, and returned to the operating room.
 Fig. 19.—Waste Can.

SUTURES AND STERILIZATION

(Ligatures)
Silkworm Gut and Silk.—In plastic surgery silkworm gut and silk
are used extensively. Rarely is ordinary catgut resorted to, because
it is absorbed before thorough union takes place, besides being a
source of infection, either primarily from imperfect sterilization or by
taking it up from the secretions of the deeper layer of skin not
affected by external antiseptics.
The sterilization of silk is accomplished by boiling it for one hour in
a 1-20 carbolic solution and then keeping it in a 1-50 similar solution
(Czerny). Or it may be boiled in water for one hour and retained in a
1-1,000 alcoholic solution of corrosive sublimate. Ordinarily it may,
however, be simply subjected to boiling and steamed in the
autocleve. Silkworm gut is treated in the same manner. It has greater
tensile strength than silk, and for that reason the thinner varieties are
to be preferred to ordinary silk.
Catgut.—It is far more difficult to prepare catgut, but, since it is
necessary for ligation, the following methods may be considered
best:
The commercial catgut as made from the intestines of sheep, is
wound snugly upon a rod of glass and thoroughly brushed with soft
soap and hot water. It is then rinsed free of soap, wound upon small
glass spools, and placed for forty-eight hours in a one-per-cent
alcoholic bichlorid solution, composed of bichlorid of mercury, 10
parts; alcohol, 800 parts; distilled water, 200 parts. The turbid fluid
produced by first immersion is changed. Before using, the spools are
placed in a glass vessel contain containing a 1-2,000 sublimate
alcohol (Schaffer), made up as follows:

Bichlorid of mercury gr. vj;

Alcohol ℥x;
Distilled water ℥iiss.

These glass cases are obtainable for the purpose and contain a
second perforated compartment for the ligatures passing through
rubber valves placed into the openings (Haagedorn).
Catgut is generally prepared by soaking in oil of juniper for one
week and then retaining it in absolute alcohol (Kocher), or a 1-1,000
alcoholic sublimate solution.
Another method for strengthening catgut, as well as to prevent its
too rapid absorption, is to chromatize it. This is done as follows:
The catgut is placed in sulphuric ether for forty-eight hours, then
treated for another forty-eight hours in a ten-per-cent solution of
carbolized glycerin, followed by a five-hour subjection to a five-per-
cent aqueous solution of chromic acid (Lister). It is allowed to remain
in the latter forty-eight hours, then placed in an antiseptic, dry, tightly
closed receptacle, and finally soaked in 1-20 carbolic solution before
using.
 The formaldehyd method of Kossman is to immerse the gut in
formaldehyd for twenty-four hours, then washing with a solution of
chlorid and carbonate of sodium and retaining it in the same solution.
The catgut in this procedure swells and its strength is much impaired
in this way.
Any of the above methods are not above criticism, however, rigid
as they may seem, bacterial growths having been obtained with
nearly all of them.
The dry-air method (Boeckman, Reverdin) is reliable, but the
subjection of catgut to dry air at a temperature of 303° F. for two
hours results in making it tender and less pliable.

Fig. 20.—Clark Kumol Apparatus.

 The Kumol method (Kronig) is considered the most reliable, even
under the severest tests. This mode of sterilization is accomplished
as follows: A specially devised apparatus of brass, with a cast-
bronze top, both thoroughly nickel-plated, is used. The apparatus of
J. G. Clark, as shown in Fig. 20, will be found excellent. The kumol is
retained in a seamless cylinder, 8 by 8 inches, which is surrounded
on the sides and bottom by a sand bath; the flame, impinging on the
bottom, heats the sand, thereby insuring an even heat to the inner or
sterilizing cylinder. The catgut, in rings, is placed in a perforated
basket hanging in the cylinder, which can be raised or lowered at
will; after drying for two hours at 80° C., the basket is dropped, and
the catgut immersed in the kumol, at 155° C., for one hour; the
kumol is then drawn off through a long rubber tube, and the catgut
dried at 100° C., for two hours; it is then transferred to sterile glass
tubes plugged with cotton.
Prepared catgut of the various sizes can now, however, be
purchased in the market, and that offered by the better firms of
chemists is quite reliable and may be safely used for all plastic
surgery about the face. It is supplied in glass tubes, either in given
lengths, as in the Fowler type, in which the hermetically sealed tube
is U-shaped or on glass spools placed in glass tubes, not sealed, but
closed by a rubber cap, through which the desired length of ligature
is drawn and then cut off.
 CHAPTER IV
PREFERRED ANTISEPTICS

ANTISEPTIC SOLUTIONS
These are solutions used for the destruction of and to arrest the
progress of microörganisms that have found their way into wounds—
the cause of sepsis, as exhibited by fever, suppuration, and
putrefaction. These preparations are called antiseptics and are used
to render parts aseptic. They vary much in their destructive power,
effect on tissue, and toxic properties. The reader is referred to a
work on bacteriology for the specific knowledge of such on germ life.
The antiseptic treatment of wounds was founded by Joseph Lister,
1865-70, then called Listerism. His one chemical agent to
accomplish this was carbolic acid, but many such and more effective
agents have been added since that time, all differing in their specific
properties and each having, for the same reason, its particular use.
The following group of antiseptics has been chosen with a view of
giving the best selection, to which the author has added a short
description of each, so that the surgeon may choose one or the
other, as the occasion may demand. As a rule, an operator cultivates
the use of a certain line of antisepsis, especially in this branch of
surgery, experience being the best guide; yet it is hoped he may find
certain aid from those referred to, their particular use being pointed
out from time to time, as the author has had occasion to prefer one
or the other.
Alcohol (absolute).—This is a well-known antiseptic, but, because
of its ready evaporation, is especially used for the hands, as
described, and to cover sharp-edged instruments after sterilization.
Aluminum Acetate (Bürow, H. Maas).—A powerful, nontoxic
antiseptic. Is used only in two- to five-per-cent solution. According to
Primer, it arrests the development of schizomycetes, and in twenty-
four hours destroys their propagation. It readily removes offensive
odors of wounds; its great objections are that it injures the
instruments, and, because of its astringent nature, roughens the skin
of the hands. This, however, makes it particularly useful for sponging
to arrest capillary oozing.
Boric Acid (Lister).—Not a powerful, but nonirritating, antiseptic.
For this reason it is used extensively in cleansing mucous
membranes, and, when associated with salicylic acid, as in the well-
known Thiersch solutions, composed of salicylic acid, 2 gms.; boric
acid, 12 gms.; water, 1,000 gms., is much used in skin-grafting
operations. It is not very soluble in cold, but readily in hot, water and
alcohol. The saturated solution is prepared by adding ℥j to the pint of
boiling water.
Benzoic Acid.—Nonirritating, moderate antiseptic (Kraske); is
prepared in 1-250 solutions. Soluble in hot water and alcohol, but
sparingly in cold water.
Carbolic Acid (Phenylic Acid).—Not a powerful, but a much-used
antiseptic. The purest acid should be used. It appears as a colorless
crystalline solid, liquefied by the addition of five per cent water. If
more water is added the solution becomes turbid, clearing when 1-
2,000 is reached.
It is readily soluble in glycerin, alcohol, ether, and the fixed volatile
oils. Solutions in alcohol and oils have no antiseptic effect (Koch).
The 1-20 aqueous solution is recommended by Lister.
The aqueous solutions used in surgery are 1-20 and 1-40. The
weaker is used for the operator’s hands, to cover instruments, as
already mentioned, and to impregnate sponges. The stronger
solution is used for the carbolic spray, to cleanse the unbroken skin
about the site of operation, and to disinfect wounds. Either solution,
when applied to an open wound, whitens the raw surface,
coagulates the albumen, and causes considerable irritation, which
subsides quickly and is followed by numbness.
 Such solutions, by virtue of their irritant nature, increase the
serous discharge from a wound for about twenty-four hours, for
which proper drainage must be provided, as by its collection it would
add to the danger by increasing inflammation and suppuration, and,
by absorption, even produce toxic effect generally.
When a cold solution is used it should be prepared by vigorous
stirring to separate the globules of the acid. Hot water insures perfect
distribution. After an infected wound is washed with it, the solution
should not again be used, nor should any of the acid be permitted to
remain in the spaces about the wound. It will be found that many
patients cannot tolerate such dressings, and that others must be
substituted.
Large surfaces should never be exposed to carbolic solutions,
because the skin absorbs them readily, followed by untoward results.
Dangerous symptoms have been known to result from the internal
administration of seven drops of the acid, and fatal termination has
followed its use as a surgical dressing (Bartley).
Mild acid poisoning is first noted in the urine, which turns olive
green. If the agent is continued, the urine appears dark and turns
almost black on standing. The coloring is due to the presence of
indican. If the absorption is not prevented beyond this there is dull
frontal aching, tinnitus aurium, dizziness, fainting, severe and
uncontrollable vomiting. Untoward symptoms are noted by
albuminuria, total absence of sulphates in the urine, a contracted
and inactive pupil, elevation of temperature, unconsciousness,
muscular contraction, and death.
The treatment consists in immediately removing the cause and
employing another antiseptic. Support the patient with stimulants,
freely given. Cracked ice and brandy to allay the vomiting. Small
doses of sodium sulphate, frequently repeated, as a means of
converting the acid into nonpoisonous sulphocarbolate (Bauman).
Albumen and milk internally. Magnesium sulphate, five per cent.
Chromic Anhydrid.—Improperly called chromic acid. Made by
adding one and one half parts sulphuric acid, c. p., to one part of
concentrated solution of dichromate of potash. Appears in saffron-
colored crystals. It acts as a caustic upon tissue, and, although a
splendid antiseptic, cannot be used for such purposes, but is well
adapted for the preparation of catgut, as mentioned.
Creolin.—Is an antiseptic prepared from coal by dry distillation,
and is used to stimulate granulations, being much more powerful
than carbolic acid. It is nonirritant and practically nontoxic. Used in
two-per-cent aqueous solutions, in which it appears as a turbid but
effective mixture. It is well suited for cleansing the hands, a five-per-
cent solution having none of the irritating or anesthetic effect of
carbolic acid. Owing to the opacity of the aqueous solution, it is not
suitable for the immersion of instruments for operation.
Eucalyptol (W. Schultz).—A nonpoisonous volatile oil of
considerable antiseptic power. Soluble in alcohol, and used in three-
per-cent solution. It is claimed to quickly reduce the temperature in a
wound. It was much used by Lister on gauze dressings, the formula
of which is given elsewhere.
Glycerin.—It is said to have certain antiseptic power, but is used
principally as a staple solvent of carbolic and boric acid. Soluble in
all proportions in water and alcohol.
Hydrargyrum Bichloratum Corrosivum (v. Bergman, Schede,
Buchholz, Billroth, R. Koch).—The most valuable and effective,
although the most toxic of all antiseptics. It appears as a white
crystalline powder. A 1-50,000 watery solution is efficacious as a
germicide (Koch; anthrax bacilli killed by 1-20,000 solution).
Albumen decomposes the bichlorid, forming a white insoluble
precipitate, albuminate of mercury. The same effect takes place in
aqueous solutions allowed to stand for a time—the resultant being
either calomel or metallic mercury. The addition of sodium or
ammonium chlorid or a weak acid, such as tartaric, prevents this. As
much sodium as of the sublimate, weight for weight, should be used
(Koch). When tartaric acid is used for this purpose, five times the
weight of the sublimate is employed.
For all surgical purposes, except in irrigation, solutions of 1-500
and 1-1,000 are used. For the sterilization of wounds and during
operations a 1-3,000 is employed.
 For the ready preparation of such solutions sublimate tablets can
be obtained, properly mixed with one of the above-named salts. The
dyed tablets are to be preferred, to prevent error on the part of the
user. Tablets containing 1 gm. sublimate, 1 gm. sodium chlorid, and
colored with eosin, are advocated by Angerer.
As metallic substances immediately decompose the bichlorid in
solution, instruments cannot be placed in it, nor may it be kept in
metallic vessels, glass being preferred.
Alcoholic solutions of sublimate are used to cover catgut, silk, and
rubber drainage tubes.
Since sublimate is extremely toxic, great care must be used to
prevent its absorption or retention in wounds. A strong solution must
immediately be followed by a weaker one.
Toxic symptoms resemble arsenic poisoning very much, and are
ushered in by an acute irritation of the wound, especially if moist
sublimated gauze has been used, vertigo, and vomiting. The mucous
membrane of the mouth becomes affected, followed by salivation
and bleeding from the gums. There may be intestinal hemorrhage
and an inflammation of the entire intestinal tract and kidneys,
increasing in severity and resulting in death.
The early symptoms must be at once met by removal of the cause.
Albumen and milk should be given internally, with stimulants as
needed. The mouth is to be rinsed out at frequent intervals with a
saturated solution of chlorate of potash.
Hydrogen Peroxid (Love).—A powerful nontoxic antiseptic. It is
used in five- to fifty-per-cent aqueous solutions, and is most
efficacious in suppurating wounds, in which it destroys the
microörganisms of pus. It foams actively when brought in contact
with the latter, and is said to render a wound aseptic by one or two
applications. A standard preparation of known strength must be
obtained, however, to get good results.
Iodin.—A very powerful nonirritating antiseptic. Used especially
for washing wounds. The proper solution is made by mixing two
drams of the tincture (℥j iodin to ℥Oj alcohol) with one pint of warm
water (Bryant). The one-per-cent solution of the trichlorid is equal in
its effectiveness to a four-per-cent carbolic solution (Langenbuch).
Lysol.—Very similar to creolin, both in composition and effect. Is
nontoxic, and employed in two-per-cent aqueous solution. Appears
as a soapy liquid, and forms a clear solution with water.
Potassium Permanganate.—An active disinfectant, quickly
destroying the odor of decomposition, and for that reason is splendid
for the washing out of foul wounds. It is nonpoisonous, and has
moderate antiseptic power—the five-per-cent solution killing resting
spores. Its effect is limited to a short time only, as the secretions from
a wound decompose and precipitate it into an inactive form. It is
employed in aqueous solution, differing in color from light ruby to
dark brown; that is, 1-1,000 to 1-100. The solution, known as
Condy’s Fluid, has a strength of 1-1,000.
Salicylic Acid.—A derivative of carbolic acid, and an effective
nonirritating antiseptic. It is only slightly soluble in cold water, 1-300.
When combined with boric acid, it becomes more soluble. This
antiseptic cannot be used for instruments, however, as it corrodes
them. Its other objections are that it evaporates quickly from
dressings and that it is expensive.
Sodium Chlorid.—Is a common agent used for the irrigation of
putrid wounds in two-per-cent solution. For irrigation during aseptic
operation and for covering sterilized sponges it is used in eight-per-
cent solution (v. Esmarch). This corresponding to the normal salt
solution. Its use in connection with corrosive-sublimate solutions
(Maas) has been referred to.
Thymol (Rancke, Bouillon, Paquel).—The aromatic principle of
thyme. Efficient as an antiseptic in 1-1,000 aqueous solution. It has a
pleasant odor, and is nonirritant and nontoxic. Exhibited in colorless
crystals. An excellent solution is prepared as follows:

℞ Thymol 20 parts
Alcohol 10 ”
Glycerin 20 ”
 Aquæ 1,000 ”

It is used especially in washing out cavities where carbolic acid

cannot be employed, and for cleansing mucous membranes
preparatory to operation.
Zinc Chlorid (Morgan, Bardeleben, Billroth).—Extensively used
as an antiseptic, especially in the oral cavity, where, by sealing the
lymph spaces with a plastic exudate, it hinders the absorption of
septic matter. It is only slightly antiseptic, however, in ten-per-cent
aqueous solution. Zinc chlorid represents the active agent in
Burnett’s fluid. May be effectively employed in the proportions of
from twenty to forty grains to the ounce of water. Care must be
exercised to prevent its retention in alveolar tissue, since it may
occasion serious sloughing. As a cleansing agent for infected
wounds it is of great value, although the sulphocarbolate of zinc may
be preferred, as it is less irritating and less toxic.
Peroxoles.—Beck has introduced a group of preparations, known
as peroxoles; liquid antiseptics containing a solution of hydrogen
peroxid in combination with other disinfectants. The preparations are
composed of from thirty-three to thirty-eight per cent alcohol, about
three per cent of hydrogen peroxid, and one per cent of thymol,
menthol, or camphor, the name given them being according to the
last ingredient—thymosol, menthosol, or camphorosol. The
association with these disinfectants greatly increases the antiseptic
power of hydrogen peroxid. Aqueous solutions containing ten per
cent of the peroxoles are usually employed. These correspond to a
one-per-cent solution of mercuric chlorid, and possess a more
energetic action than five per cent carbolic acid.

ANTISEPTIC POWDERS
Aristol (Dithymol Di-iodid) (Eichhoff).—Reddish-brown powder
containing forty per cent iodin. Soluble in ether, chloroform, and fatty
oils, sparingly in alcohol. Must be kept in dark glass bottles. Is
incompatible with corrosive solutions. Used externally as iodoform.
 Dermatol (Bismuth Subgallate).—An odorless yellow insoluble
powder, containing fifty-three per cent Bi₂O₃.
Iodol (Tetraido Pyrol) (Kalle).—A light grayish-brown powder,
containing eighty-nine per cent iodid. Slightly soluble in water,
soluble in alcohol and chloroform. Its action is very similar to
iodoform, and has taken its place to a great extent, first, because it is
odorless, and secondly, because any quantity used exerts no toxic
effect (Wolfenden). It is dusted upon the wound. Its action is due to
the liberation of iodin, which acts upon the albuminous elements,
and the ozone set free oxidizes the products of decomposition. It has
a slight escharotic effect, forming a thin crust over the surface to
which it is applied, thus effectually remaining in constant contact with
it. That it is quickly absorbed is shown by its presence in the saliva
and the urine.
Orthoform (Methyl Ester of Meta-Amido-Para-Oxybenzoic Acid).
—Nonpoisonous, white, odorless powder of moderate antiseptic
power, and well suited for wounds involving mucous membranes. It
has a decided anesthetic effect, lasting for several hours upon
painful wound surfaces.
Iodoform (Formyl Iodid, Féréol).—A lemon-yellow crystalline
powder of penetrating, saffronlike odor. Contains ninety-seven per
cent iodin. Insoluble in water, but forms solution with alcohol, ether,
chloroform, and the fixed volatile oils. Has a decided stimulating
effect on wounds by preventing putrefaction and deodorization
(Mikulicz). Its antiseptic value has been much discussed, but
practically it has found favor with the majority of surgeons. According
to research, iodoform is a powerful antiseptic, from the fact that the
product of its decomposition in the presence of germ life renders the
ptomains in a wound inert, thus preventing suppuration, or at least
checking the absorption of such, which is often a serious matter in
infected wounds. It is not sterile, and may contain ptomains which in
themselves would produce pus, but as associated with the iodoform
do not occasion it.
 CHAPTER V
WOUND DRESSINGS

The dressing or treatment of wounds, considered herein,

embodies particularly that practiced by the surgeon in the
performance of plastic operations.
The elasticity of the skin is especially serviceable in bringing about
desirable restorative results, but, owing to its extreme vascularity
and the infrequent supply of venous valves, as in the face, there is
considerable danger of infection, with rapidly spreading septic
inflammation.
Sutured Wounds.—Before the wound is closed all hemorrhage
must be arrested, either by catgut ligature, in exceptional cases, and
by torsion or pressure, as generally practiced. Gauze sponges
dipped into hot sterilized solution are most suitable for the latter
purpose.
The edges of the wound must be coapted perfectly by cutaneous
sutures of sterilized silk of suitable thickness. Formaldehyd catgut is
often used because of its limited absorption. Ordinary catgut should
not be employed, as its early absorption interferes with obtaining the
proper union, and by becoming softened invites sepsis.
The wound, if small, may be powdered over with any of the
antiseptic powders, such as aristol or iodol. It must be remembered
that such powders form a hard crust with the serous oozing of
wounds, which, by reason of pressure from the dressing applied over
it, is very liable to separate the edges of the wound, thus increasing
the width of the scar, a very important factor in facial surgery.
Where perfect apposition has been made, the dusting powders
may be used and a covering of Lister’s protective silk plaster placed
over it. The edge of the strips of plaster must be incised at distances
of about ⅛ inch, so as to snugly take on the curvature of the parts
and at the same time thoroughly seal over the area to prevent
subsequent contamination.
The plaster is made of taffeta silk, preferably of flesh color, coated
on one side with copal varnish and a mixture prepared as follows:

℞ Dextrin ʒj;
Starch ʒij;
Carbolic acid ℥ij.

When applied, it should be moistened with an antiseptic solution

only. This can be applied only to dry surfaces, however, and should
be rarely used, since subsequent hemorrhage or oozing will raise the
plasters, inviting sepsis.
It is better, however, in all cases to employ several layers of an
antiseptic gauze, such as fifteen-per-cent iodoform or boric-acid
gauze to cover the wound, and back it with absorbent cotton, over
which a bandage or the silk protective is applied to retain it. The
gauze absorbs the secretions, at the same time rendering them
harmless.
At no time should cotton be placed next to the wound, as it forms a
hard mass with the secretions, the removal of which requires enough
force to injure or hazard the union of a new wound. Nor should a
plaster dressing be pulled off without thoroughly moistening it first,
withdrawing the various layers one by one. The gauze, when
moistened, readily leaves the wound without injurious traction. An
excellent dressing for small, dry wounds, and one that causes little
tension, is collodium, or, better, iodoform-collodium painted over the
surface. The latter may be prepared as follows;

℞ Iodoformum 5j;
Collodium 5x.
[Küster.]

To this may be added oil of turpentine or castor oil, which permits of

greater flexibility. Boric lint, applied wet, is also good. It must be
moistened thoroughly before removal. Larger wounds should be
dusted over with one of the powders mentioned and covered with
folds of gauze and absorbent cotton, held in place with gauze
bandages.
Such dressings are allowed to remain until the sutures are taken
out, unless there is sign of soiling. As these secretions readily
decompose, it is best to remove the cotton and upper layers of
gauze and renew them every day, or as often as is necessary. The
wound, in this way, is not disturbed whatever, and the antiseptic
properties of the lower fold of gauze is sufficient to keep the wound
surface clean.
In most superficial wounds it is best to remove the sutures at the
end of forty-eight hours, unless there are reasons for retaining them
longer, as the coapted surfaces are then sufficiently united to permit
of other dressings, such as aseptic plaster, now extensively used.
Before these are applied the skin is washed with alcohol or ether to
assure a dry surface to facilitate adhesion.
Sutures drawn as stated leave no possibility of stitch scars and
reduce the occurrence of possible stitch abscess to a minimum. As
there is always slight oozing following their removal, aristol or iodol
may be powdered over them before applying the plasters. This
brings us to the rather late question of sutureless coaptation of
superficial incisions.
Sutureless Coaptation.—This method, first practically
demonstrated by Bretz, may be used with considerable advantage in
wounds about the face, and overcomes the strain of individual
sutures, besides avoiding the possibilities of stitch infection.
 Fig. 21. Fig. 22.
Plaster Sutures.

The method involves the proper placing of strips of plaster at

either or opposite ends of the wound. The distance between the
incision and the edge of the plaster must not be less than ¼ inch or
more, according to the length of the wound and its position. In place
of the strips of rubber adhesive plaster, the aseptic Z. O. plaster
should be substituted to overcome the objections of the infections
therefrom.
 Fig. 23. Fig. 24.
Angular Plaster Sutures.

The inner edges of the plasters are raised slightly, and interrupted
sutures are inserted through them instead of the skin (see Fig. 21).
They are then tied as shown in Fig. 22. In angular incisions the
plasters are cut as desired to insure perfect coaptation, as in Figs.
23 and 24. The advantages of this method, besides those already
mentioned, are that the wound is always open for inspection and
permits of free drainage. If thought best, a small strip of iodoform
gauze may be placed over the threads or even under them, if there
is little tension.
Since the introduction of the aseptic Z. O. (Lilienthal) strips, the
above method may be discarded as unnecessary and requiring too
much time for their application. Strips of the antiseptic plaster are
placed across the wound at right angles, or, if the surface be a
curved one, obliquely to the wound. The plasters are furnished in
strips of the width desired, packed in two germ-proof envelopes.
They are extremely adhesive to dry surfaces. Besides being aseptic,
they are slightly antiseptic and nonirritating. The strips are placed in
position, leaving an open space between them while the assistant
brings the edges of the wound into position.
Where there is tension of the parts this method is not to be
employed. The wound may be dusted as when sutured and dressed
in the same manner. The plasters are removed about the sixth day
by drawing the ends of the strips toward the wound. Their second
application is unnecessary, regular dressings being substituted.
From the above it must not be inferred that all plastic wounds are
amenable to the above methods, because many require specific
treatment, as later described.
Granulation.—Wounds left open for granulation should be dusted
over with some stimulating antiseptic powder, such as aristol or boric
acid, and then covered with iodoform or borated gauze. The
granulating surface must be gently washed with a mild solution of
peroxid.
Prolific hypertrophic granulations, that jut out over the surface, are
touched with a lunar caustic point, avoiding the epithelial edge of the
wound, where it causes considerable pain. Pale and loose granular
points should be scraped away with the sharp spoon curette to
hasten better growth.
If the skin edges are thickened and curled upon themselves, it
may be best to curette or to reduce them by cauterization, so
stimulating epitheliar spreading. Sterile gauze is then loosely laid
upon the surface, backed with a highly absorbing material, such at
charpie cotton (Burns), wood wool, and poplar sawdust, retained in
gauze bags (Porter). The absorbing layer should be light and
pervious to the air, to facilitate not only free absorption, but ready
evaporation of the secretions.
Changing Dressings.—All dressings must be absolutely sterile
and all precautions, as primarily carried out, must be followed in
changing them.
It is rather infrequent to use permanent dressings in plastic
surgery, but where the wound appears aseptic, with a dry serous
crust over the line of healing, it should not be disturbed except for