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Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental Monitoring,
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 ENVIRONMENTAL REMEDIATION TECHNOLOGIES,
REGULATIONS AND SAFETY

HUMIDITY SENSORS:
TYPES, NANOMATERIALS
AND ENVIRONMENTAL
MONITORING
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

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Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
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Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 ENVIRONMENTAL REMEDIATION TECHNOLOGIES,
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HUMIDITY SENSORS:
TYPES, NANOMATERIALS
AND ENVIRONMENTAL
MONITORING
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

CHRISTOPHER T. OKADA
EDITOR

Nova Science Publishers, Inc.

New York

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 Copyright © 2011 by Nova Science Publishers, Inc.

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LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA

Humidity sensors : types, nanomaterials, and environmental monitoring /
edited by Christopher T. Okada.
p. cm.
Includes bibliographical references and index.
ISBN:  (eBook)
1. Hygrometers. I. Okada, Christopher T.
QC916.H86 2011
551.57'10287--dc22
2010047633

Published by Nova Science Publishers, Inc. † New York

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 CONTENTS

Preface vii
Chapter 1 Water Vapour Sorption and Humidity – A Survey on
Measuring Methods and Standards 1
Erich Robens, Katrin Rübner, Peter Klobes
and Devrim Balköse
Chapter 2 Environmental and Bio-Medical Applications Using
Quartz Crystal Microbalance (QCM) Humidity
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Sensors Modified with Nano-Assembled Thin Films 93

Serhiy Korposh, Roman Selyanchyn
and Seung-Woo Lee
Chapter 3 Holographic Humidity Sensors 117
I. Naydenova, J. Raghavendra, S. Martin and V. Toal
Chapter 4 Surface Modified Electrospun Nanofibrous
Membranes for Humidity Detection Based on Quartz
Crystal Microbalance Technique 143
Xianfeng Wang, Bin Ding, Jianyong Yu
and Gang Sun
Chapter 5 Monitoring Relative Humidity Using Zno Based
Film Bulk Acoustic-Wave Resonator 161
Xiaotun Qiu and Hongyu Yu
Index 177

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 PREFACE

There is a substantial interest in the development of relative humidity

sensors for applications in monitoring moisture levels at home, in clean rooms,
cryogenic processes, medical and food science. This new book presents
current research in the study of humidity sensors, including measuring
methods and standards of water vapor sorption and humidity; environmental
and bio-medical applications using quartz crystal microbalance humidity
sensors and surface modified electrospun nanofibrous membranes for humidity
detection.
Chapter 1 - Under environmental conditions water exists in all three
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

classical states of matter: solid, liquid and gas. The water molecule is non-
linear and therefore polar. In comparison with other liquids water has
anomalous features; about 63 exceptional properties are recorded. This article
starts with reviewing properties of water, typical occurrences and definitions
such as relative and absolute humidity and moisture content.
Water is present everywhere in nature and engineering; it may be helpful
or harmful. The survey concerns both: atmospheric hygrometry and usual
measuring methods of the moisture content of solids and liquids as well as
water sorption. The determination of the atmospheric humidity is among the
more difficult problems in metrology. In contrast, humidity determination of
materials is simple; however the definition of the dry state is difficult. Because
water is bound at and in solids and liquids in many different ways it turns out
that the humidity content of materials is difficult to define and to measure
accurately. We provide a survey on the measuring methods, describe the most
important ones and discuss advantages and accuracy.
In the search for extraterrestrial water special remote measuring methods
have been developed analysing the spectrum of electromagnetic radiation

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 viii Preface

either of natural sources or produced by a probe and reflected. Spacious

deposits have been detected photographically. In situ investigations are made
using conventional methods.
With regard to the problems of measurements, standardisation of
measuring methods and procedures is required. There exist many institutions,
which are engaged in investigating the use of water and standardising
measuring methods. In tabular form, we give a survey on existing standards.
Chapter 2 - Nano-assembled thin films prepared by a layer-by-layer
approach on QCM resonators were used as sensitive elements for monitoring
relative humidity. Different types of films, polymer-based (PDDA/PSS )n film
and porphyrin-based (PDDA/TSPP )n and (PDDA/MnTSPP )n films (where
n=5, 10, and 15), showed linear responses to relative humidity changes in the
range of 4%–94%. An increase of the number of bilayers deposited on the
QCM electrode enhanced the sensitivity to relative humidity. The porphyrin-
based films showed ca. 4.5 times higher sensitivity towards relative humidity
than the polymer-based films, owing to the presence of the higher number of
free sulfonic acid groups. Incorporation of the metal ion into the porphyrin
pyrrole ring was not significant in sensitivity. However, all films showed a
good reversibility to the stepwise changes of relative humidity and the
response and recovery times (t90) were very fast, within 15 sec.
Additional examples of the QCM humidity sensors for environmental and
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

medical sensing are presented. In particular, a respiratory monitoring system

based on QCM frequency oscillations was designed and investigated. The
developed system, in which the sensor response reflects lung movements, was
able to track human breathing parameters such as respiratory rate, tidal
volume, and inspiratory/expiratory flow, which were tested on healthy
volunteers.
Chapter 3 - This chapter presents holographic devices for sensing the
relative humidity in the environment. The principle of operation of two main
types of holographic sensors based on transmission and reflection holograms is
described and their properties are theoretically modelled. The effect of
different factors such as change of the overall refractive index, change of the
hologram‘s thickness due to swelling/shrinkage of the layer and change in the
refractive index modulation due to absorption/desorption of moisture are
considered. In the experimental studies emphasis is given to reflection
holographic humidity sensors which can provide a visual indication of the
relative humidity observed as a change of the colour of the reflected light. The
work presented focuses on holograms recorded in acrylamide based
photopolymers. The results from studies of their sensitivity, reversibility,

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 Preface ix

relative humidity range of operation and response time are summarised. The
operational temperature range is also studied.
The potential use of the humidity sensors as user-verifiable security
holograms is described as well as applications in packaging and environmental
sensing.
Chapter 4 - Electrospinning exhibits the unique ability to produce diverse
forms of fibrous assemblies with remarkable specific surface area and high
porosity, making electrospun nanomaterials highly attractive to ultra-sensitive
sensors and other nanotechnological applications. In this chapter, electrospun
fibrous chitosan (CS) membranes modified with polyelectrolytes (polyacrylic
acid (PAA) and polyethyleneimine (PEI)) were used as sensing materials
coated on quartz crystal microbalance (QCM) for humidity detection. A series
of nanofibrous membranes containing polyelectrolytes are fabricated on QCM
and characterized regarding their morphology, sensitivity and hysteresis.
Sensing experiments are carried out by measuring the resonance frequency
shifts of QCM due to the additional mass loading. The results indicated that
the response of the sensors increased by three to four orders of magnitude with
increasing the relative humidity (RH) from 8 to 95% at room temperature,
exhibiting high sensitivity and that, in the range of 20-95% RH, the Log (f )
showed a good linearity. Additionally, the prepared sensors exhibited
remarkably enhanced sensitivity with increasing the coating loads of
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

polyelectrolytes on QCM. Furthermore, the dynamic Langmuir adsorption

model was used to determine the kinetic parameters such as adsorption rates
and Gibbs free energy for various RH between 70 and 95%.
Chapter 5 - Humidity is a dynamic parameter that is essential for various
fields of industry as well as human lives. There is a substantial interest in the
development of relative humidity (RH) sensors for applications in monitoring
moisture level at home, in clean rooms, cryogenic processes, medical and food
science, and so on. Humidity sensors based on changes in the capacitance or
resistance of the sensing element from absorption of water vapor have been
investigated extensively. Alternatively, surface acoustic wave (SAW) resonant
sensors have also been developed with polymer films deposited on top of a
SAW resonator as the sensing layer. In this chapter, a novel RH sensing device
using ZnO based film bulk acoustic-wave resonator (FBAR) was described.
The resonant frequency of the FBAR decreased in a two-stage manner as RH
increased in the environment. For low RH (RH < 50%), a frequency downshift
of 2.2 kHz per 1% RH change was observed. This effect was attributed to
water molecules replacing the adsorbed oxygen on the ZnO surface, thus
increasing the density of the film, resulting in a frequency drop. For high RH

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 x Preface

(RH > 50%), a frequency downshift of 8.5 kHz per 1% RH change was
obtained, which was due to the mass loading effect of the water layers formed
on the ZnO surface. It was demonstrated that the two-stage response of the
FBAR can be interpreted using the power law theory for semiconductor gas
sensors and the mass loading effect of the resonator. UV light was applied to
monitor its effects on the humidity sensing performance of the FBAR. UV can
enhance the sensitivity at low RH (frequency downshift increased to 3.4 kHz
per 1% RH change), while degrading the sensitivity at high RH (frequency
downshift decreased to 5.7 kHz per 1% RH change). The mechanism of the
influence of the UV illumination was interpreted.
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 In: Humidity Sensors ISBN 978-1-61209-246-1
Editor: Christopher T. Okada © 2011 Nova Science Publishers, Inc.

Chapter 1

WATER VAPOUR SORPTION AND HUMIDITY –

A SURVEY ON MEASURING METHODS
AND STANDARDS

Erich Robens1, Katrin Rübner2, Peter Klobes3

and Devrim Balköse4
1
Institut für Anorganische Chemie und Analytische Chemie der Johannes
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Gutenberg-Universität, Duesbergweg 10-14, D-55099 Mainz, Germany,

2
BAM - Federal Institute for Materials Research and Testing, Unter den
Eichen 87, D-12205 Berlin, Germany,
3
BAM - Federal Institute for Materials Research and Testing , Richard-
Willstätter-Str. 11, D-12489 Berlin, Germany
4
Izmir Institute of Technology Faculty of Engineering Department of
Chemical Engineering, Gulbahçeköyü Urla İzmir Turkey

ABSTRACT
Under environmental conditions water exists in all three classical
states of matter: solid, liquid and gas. The water molecule is non-linear

1 [email protected]
2 [email protected].
3 [email protected]
4 [email protected]

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 2 Erich Robens, Katrin Rübner, Peter Klobes et al.

and therefore polar. In comparison with other liquids water has

anomalous features; about 63 exceptional properties are recorded. This
article starts with reviewing properties of water, typical occurrences and
definitions such as relative and absolute humidity and moisture content.
Water is present everywhere in nature and engineering; it may be
helpful or harmful. The survey concerns both: atmospheric hygrometry
and usual measuring methods of the moisture content of solids and
liquids as well as water sorption. The determination of the atmospheric
humidity is among the more difficult problems in metrology. In contrast,
humidity determination of materials is simple; however the definition of
the dry state is difficult. Because water is bound at and in solids and
liquids in many different ways it turns out that the humidity content of
materials is difficult to define and to measure accurately. We provide a
survey on the measuring methods, describe the most important ones and
discuss advantages and accuracy.
In the search for extraterrestrial water special remote measuring
methods have been developed analysing the spectrum of electromagnetic
radiation either of natural sources or produced by a probe and reflected.
Spacious deposits have been detected photographically. In situ
investigations are made using conventional methods.
With regard to the problems of measurements, standardisation of
measuring methods and procedures is required. There exist many
institutions, which are engaged in investigating the use of water and
standardising measuring methods. In tabular form, we give a survey on
existing standards.
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

1. INTRODUCTION
Water is present everywhere in nature; this could be advantageous or
disadvantageous. Handling of a variety of materials includes often the use of
water, as solvent or dispersant medium, adsorptive, reacting agent, cleaning
agent and lubricant. For handling, storage and quality assurance of foods,
pharmaceuticals, textiles, plastics, paper, wood and building materials the
water content must be known. Many processes, such as corrosion protection,
refrigeration, air conditioning in museums, greenhouses, saunas, laboratories
and climate chambers as well as humidors for manufacturing of pure materials,
require the control of the air humidity. An extreme control of humidity is
required for insulating gases, such as those in transformers and power plants,
as well as protecting and other pure bulk gases. Natural gas transport requires
control of humidity down to a measuring range of ppm in presence of high

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 Water Vapour Sorption and Humidity 3

contents of solid and liquid contaminants as well as corrosives in varying

concentrations. In general, insulating liquids must be free from traces of water.
Very different applications of humidity measurements are made under
very different circumstances within a wide measuring range from nearly zero
up to saturation and sometimes with high sensitivity. Thus, a great variety of
measuring methods is applied [1-4]. Because the term "humidity" is not well
defined and because the different measuring methods deliver not always
comparable results standardisation of measuring methods and procedures is
required.
A humidity measurement covers two groups of measuring problems: the
atmospheric humidity and the material moisture. In both groups, the
phenomena and its mathematical description are very different and so are the
methods and instrumentation for measurement and control. The two groups are
of high importance for life and techniques and thus, a large variety of
measuring instruments is available on the market.

2. WATER STRUCTURES
Under global environmental conditions water exists in all three classical
states of matter: solid, liquid and gas. The water molecule is non-linear (Figure
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

1) and therefore polar. In comparison with other liquids it has anomalous

features; about 63 exceptional properties are recorded [5].

Water in the Gaseous Phase

In gaseous phase water is present as a dimeric complex along with single

molecules [6] (Figure 2). Air contains always water vapour in a concentration
from near zero up to the saturation value determined by temperature. In
addition, liquid or solid agglomerates may be present and visible as clouds,
droplets, snow or hailstones. Contaminations should be taken into account,
thus, little droplets of ionic solutions are formed with salt from sea water, and
dust provides nuclei for condensation.

Water in Liquids

Liquid water consists mostly of aggregates of several molecules (Figure

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 4 Erich Robens, Katrin Rübner, Peter Klobes et al.

3). In addition, water can form mixtures and solutions in liquids. Due to its
high polarity, dissociation and ionization of substances can occur.

Figure 1. Schematic structure of a water molecule.

Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Figure 2. Structure of dimeric water molecule in vapour.

Water Near Solid Surfaces

At ambient temperatures up to about 35 °C, free bulk water consists of

unstable and quickly varying aggregates of several molecules (Figure 3);

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 Water Vapour Sorption and Humidity 5

single molecules are seldom. As shown in Table 1, water is bound at a solid

differently.
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Figure 3. Possible structures of water molecules.

Interpacked water filling larger pores and spaces between grains has the
same structure as free bulk water. Likewise, capillary water fills capillaries
(macropores) and nanopores (mesopores). Due to water uptake, the structure
of some materials can store large amounts of water and/or can undergo
swelling. A solid surface exposed to the atmosphere is more or less covered
with physisorbed water molecules attracted by van der Waals forces (London
dispersion forces). These are induced, fluctuating dipoles. Whilst their
temporary mean value is zero, the binding energy per atom is of the order of
0.5 eV. Down to temperatures of -50 °C, liquid water layers have been
observed in fissures of permafrost structures. About two layers of physisorbed
water molecules at a solid surface or at the surface of ice behave in a quasi-
liquid state down to a temperature of 33 K. Such quasi-liquid layers behave
like free water; however, the surface influences the structures within about
eight layers. Thus, bound water has properties different from those of free

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 6 Erich Robens, Katrin Rübner, Peter Klobes et al.

water [6]. Physisorption is reversible because the electron orbital structure is

not influenced and only weak deformation of the molecular grid occurs. Parts
of the adsorbate vaporise with decreasing vapour pressure or increasing
temperature and a new equilibrium responds to the new ambient state.
Nevertheless, to remove physisorbed water completely in a reasonable time,
warming up is often required in addition to vacuum.
Binding forces at polar surfaces and induced electrostatic dipoles at
metallic surfaces are much stronger; they are of the order of 0.1 kJ mol-1.
Though there is still no chemical bond, and thus, such bindings should be
classified as physisorption.
Chemisorption is a dissociative stoichiometric bonding at surface
molecules of the solid. Binding enthalpies range between 100 and 500 kJ mol-1
Chemisorption is irreversible. Energy is required to release molecules,
whereby hydroxyl groups may recombine to form water molecules.
Absorptive binding of water is associated with diffusion of water
molecules, which are first physisorbed at the surface, into free molecular sites
in the interior of a material.
The formation of a hydrate and binding as water of crystallisation are
chemical reactions.

Table 1. Water near solid surfaces

Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Type of water Formation process

Free bulk water Filling of volumes

- volume water Filling of macropores and interspaces between
- interpacked water particles

Water bound physically at the solid Adsorption (physisorption) at the outer surface and
surface at pore walls and micropore filling
- physisorbed water layers Adsorption (physisorption) and condensation in
-capillary water in mesopores mesopores (capillary condensation)

Water bound chemically at the surface Adsorption and chemisorption at the outer surface
- chemisorbed water and at pore walls

Water bound in the solid bulk material Adsorption and diffusion → absorption
- absorbed water

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 Water Vapour Sorption and Humidity 7

Binding enthalpies are stronger than those of physisorption. Nevertheless

such reactions may be completely reversible and may take place even at low
temperatures.
Natural and technical surfaces are always contaminated. Impurities at the
surface are hardly avoidable. Water may emulsify or dissolve such species by
forming an ionic salt solution e.g.
A typical effect accompanying water sorption is swelling. By expanding
the matrix of dry material, additional volume is available for water molecules.
For example, the small specific surface area of dry clay minerals increases by
water uptake to values between 10 and 2200 m2 g-1 as determined by the BET
method.

3. AIR AND GAS HUMIDITY

The following chapter is concerned with the water content of air and
process gases [7]. The earliest and still widely employed application of
detection of air humidity is in weather forecast because humidity is one
important parameter. Weather forecast has been made most probably since the
beginning of mankind. Animals and plants are equipped with humidity sensors
as well, and it is believed that some animals can forecast weather.
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Although living in highly developed countries and mostly in protected

environments, weather is still governing our life and it influences also
industrial processes. Water vapour in air causes atmospheric phenomena such
as rain, snow or frost and affects solids by corrosion of metals, caking of
powders and deterioration of delicate technical devices. Humidity sensors with
linear, quick and reversible responses have been developed for measuring
water vapour concentration in air [8].

Historical

The first record of a water vapour adsorption experiment is found in the

Bible. In the Book of Judges [9] we read,

"And Gideon said to God: If you want me to save Israel by my hand, as

you said, behold, I put fresh sheared wool on the floor and if the dew falls
only on the wool, and it will be dry at all the earth beside, than shall I know
that you want to save Israel by my hand, as you have said. And it was so:

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 8 Erich Robens, Katrin Rübner, Peter Klobes et al.

When he got there in the early morning and wrung out the wool, he could
press out the dew from the wool, a bowl full of water. After that Gideon said
to God: Your anger should not flare out against me, if I speak again: Only
once more I will try it with the wool: Only the wool shall be kept dry, and
dew shall be upon all the ground. And God did so in the following night: The
wool remained dry and the dew was on all the ground."

Already Luther remarked that the description of the experiment is unclear.

Nevertheless, there are plausible explanations for the inconsistent results [10-
11].
A strange volumetric device, which was in use until recently, should be
mentioned: "The doctor of Cairo" (Figure 4). These artistic bowls served for
dew sampling during cool nights. The condensed water was used for medical
purposes.
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Figure 4. ―The Doctor of Cairo‖ (dew sampler).

The aim of the first gravimetric adsorption measurements was to forecast

weather by determination of atmospheric humidity. The very first to describe
such an instrument [12], was the German cardinal Nicolaus Cusanus (1401-
1463). In his book "Idiota de Staticis Experimentis", which was published in
1450, that means "The layman about experiments with a balance" (Figure 5)
[13], he let this ignorant person, probably his mechanic, suppose,

"If anyone hangs on one side of a big balance with dry wool and loads of
stone on the other side until equilibrium is established, at a place and in air of
moderate temperature he could observe that with increasing humidity the
weight of the wool increases and with increasing dryness of the air it

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 Water Vapour Sorption and Humidity 9

decreases. By these differences it is possible to weigh the air and it is likely

that one might perform weather forecasting."
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Figure 5. Nicolaus Cusanus (1401-1463). "Idiota de Staticis Experimentis" 1450.

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 10 Erich Robens, Katrin Rübner, Peter Klobes et al.
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Figure 6. Sketches of gravimetric hygrometers/barometers of Leanardo da Vinci.

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 Water Vapour Sorption and Humidity 11

About 20 years later the Italian architect and painter Leo Battista Alberti
(1404-1472) described a similar device,

"We know, that a sponge becomes wet from atmospheric humidity and
by this fact we make a balance with which we weigh the weight of the air and
the dryness of the winds." [14].

From Leonardo da Vinci (1452-1519) we have three designs of inclination

balances loaded with a sponge or with cotton (Figure 6) [15-17]. With
reflected face he added to the sketches,

"To recognize the quality and density of the air and to forecast rain."
and

"Means to detect, when the weather will break-up."

In the following decades a large variety of hygrometers had been

developed [1-4].

Definitions
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Air humidity is the amount of water vapour in the air disregarding the
possible presence of liquid or solid aggregates like raindrops, fog, snow or
hailstones. The parameter "air humidity―, which is a function of temperature,
is governed only by the availability of water and the thermal energy available
for evaporation. Air humidity can be expressed in several ways [18]:

 Absolute humidity AHair is defined as the mass of water vapour mw

presented in unit mass mair or unit volume Vair of dry air.

mw
AH air  g kg 1 (1a)
mair

or
mw
AH air  g m -3 (1b)
Vair

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 12 Erich Robens, Katrin Rübner, Peter Klobes et al.

 Relative humidity RHair is the ratio of the amount of water vapour in

the air mw at a specific temperature to the maximum mass that the air
could hold at this temperature mw,max usually expressed as a
percentage.

mw
RH air   100 % (2a)
m w,max

 Another definition is the ratio of the partial pressure of water vapour p

in a gaseous mixture of air to the saturation vapour pressure p0 at a
specific temperature. The values differ slightly near the saturation
point.

p
RH air   100 % (2b)
p0

 Relative humidity is the most frequently encountered measurement of

humidity because it is regularly used in weather forecasts.
 Specific humidity SHair is the ratio of water vapour to air (dry air plus
water vapour) in a particular volume of air. Specific humidity ratio is
expressed as a ratio of kilograms of water vapour, mw, per kilogram of
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

air, mair + mw.

mw
SH air  (3)
m air  m w

 The dew point is associated with the relative humidity. This is the
temperature at which water vapour saturates from gas into liquid or
solid usually forming rain, snow, frost, or dew. At this temperature the
relative humidity is 100 %. From the dew point temperature, the
relative humidity can be derived by means of tables.

Measuring Methods of Air Humidity

The peculiar characteristic of the water molecule facilitates its

identification and allows the application of very different methods to
determine humidity. The methods are standardised in all industrial states [19].

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 Water Vapour Sorption and Humidity 13

Water vapour is as a primary contaminant in process gases at very low-levels

of particular interest to the semiconductor industry. Therefore, efforts are
directed toward developing water vapour measurements and standards at the
part per billion level and below for characterisation of moisture concentration.
Measuring instruments and standards are normally used in industrial
applications for contamination control in process gases.

Table 2. Methods for the Measurement of Air and Gas Humidity

Method Principle of measurement

Measuring method
Hygrometer Measurement of parameters, like change of length,
mass, electric resistance, electric capacity, sorption,
dew point, that depends on humidity
Psychrometer Measurement of evaporation coldness by temperature
difference
Dew point meter Observation of condensation at a surface (chilled
mirror) in dependence of temperature
Gravimetric train Elaborate absorption system maintained as the primary
standard for humidity measurements
Humidity sensor
Dielectric measurement Capacitive measurement with a condenser taking the
advantage of the high dielectric constant of water
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Electric conductivity Electrochemical measurement of conductivity

measurements
Microwave and infrared Measurement of absorption of radiation
spectroscopy
Nuclear magnetic resonance Measurement of resonance between a high-frequency
spectroscopy electromagnetic field and 1H nucleus of water of a
sample, which is arranged into a strong homogeneous
magnetic field
Activation analysis Measurement of absorption of fast neutrons or -rays
Moisture indicator Qualitative test observing colour change

Hygrometry

The earliest hygrometers made in the 15th century were balances loaded on
one side with textile [17, 20]. Today the gravimetric method is applied as a
primary standard for humidity measurements. The NIST gravimetric
hygrometer has an uncertainty of 0.1 % mass fraction. Furthermore, a suitable

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 14 Erich Robens, Katrin Rübner, Peter Klobes et al.

mass sensor is the quartz crystal balance whose surface is covered by a

hygroscopic film or by a microporous substance [21-22]. As the mass of the
crystal changes due to adsorption of water vapour, the frequency of the
oscillator changes. Ultrathin Linde Type A (LTA- type) molecular sieves
grown on a quartz crystal microbalance have high sensitivity, good
reversibility and long life at low humidity ranges [23].
The simplest and still widely used mechanical hygrometer is the hair
hygrometer of Horace Bénédict de Saussure [24] (Figure 7). It measures the
elongation of hair with increasing humidity due to swelling of the hair cells.
Hairs from humans, sheep or horses are used; today also plastic strips or fibres
are used. Whereas the mass adsorbed is somewhat proportional to relative air
humidity the elongation of the hair or fibre (up to ~ 2.5 %) is not linear and the
scale is spread in the middle of the measuring range. The traditional folk art
device known as a "weather house" works on this principle with a sensor being
catgut or hair.
More accurate measurements and electronic recording of results are
achieved with a coulometric hygrometer. It measures the change in the
electrical impedance or resistance of a thin layer of a hygroscopic material,
lithium chloride or phosphorus pentoxide e.g. (Figure 8).
Other hygrometers sense changes in electric capacity (with an electret
e.g.), volume, or the transparency of various substances that respond to
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relative humidity. The oxide sensor is made up of an inert substrate material

and two dielectric layers, one of them is sensitive to humidity. The moisture
molecules pass through the pores of the surface and cause a change to a
physical property of the layer beneath it. An aluminium oxide or silicon oxide
sensor has two metal layers that form the electrodes of a capacitor. The
number of water molecules adsorbed will cause a change capacity of this
condenser due to the high dielectric constant of water.
The measurement of the electrical resistance of thin hygroscopic films or
of semiconductors can be used in hygrometry and, likewise, as sensors in head
space analysis in order to determine material humidity. Typical substances
include lithium chloride, stearic acid and zinc stearate [25]. The relation
between conductivity and relative humidity is in general not linear and may be
applied only within a restricted measuring range. Highly sensitive humidity
sensors based on single SnO2 nanowires have linear response in conductivity
to humid air [26]. Cells with MnO2 clay solid electrolytes have good linearity
and fast response in galvanic potential to changes in humidity [27].

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 Water Vapour Sorption and Humidity 15
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Figure 7. Hair hygrometer of Horace Bénédict de Saussure (1783). Figure 7a: Large
hygrometer. The hair is stretched between a and b. Figure7b: Hand hygrometer. The
hair is stretched between y and z.

Thick film and disc humidity sensors based on semiconducting hubnerite

(SnWO4) compositions show a maximum sensitivity factor when doped with
Li+ andW6+ sites in hubnerite material that contributes to hubnerite sensing
mechanism [28].

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 16 Erich Robens, Katrin Rübner, Peter Klobes et al.

Figure 8. Coulometric hygrometer: Keidel cell (1950): platinum electrodes on a

substrate covered with a thin film of P2O5.

A silicon oxide sensor can be an optical device that changes its refractive
index when water is absorbed into the sensitive layer. A wavelength shift can
also be detected on the output, which can be precisely correlated to the
moisture concentration.
Optical methods include the observation of colour transition of chemical
compounds when reacting with water molecules. They are widely used to
control the activity of drying agents and as breakthrough indicators [29]. Test
methods of qualitative water indication include redden of blue cobalt(II)
chloride [26, 30]. Usually, blue cobalt(II) chloride is dispersed in silica gel.
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Sensors, which consist of such salts, are dispersed on different substrates, such
as cellulose, cellulose acetate, polyvinyl pyrollidon, wool, calcium sulphate,
silica gel, zeolites and alumina. Wool impregnated with cobalt chloride is blue
in dry state and converts to yellow by moisture adsorption [31]. Humidity
indicating gels, which are light blue in dry state and dark blue in moist state,
are obtained by dispersing copper sulphate in silica gel. Yellow lead iodide is
obtained from a mixture of potassium iodide and lead nitrate by moisture
adsorption. Polymer dye systems changing colour with air humidity can also
be used as humidity sensors. A high sensitive optical humidity probe has been
developed by use of violet Nafion crystal violet films. At a wavelength of 650
nm, a reversible change in the absorbance of the films with relative humidity is
linear in the range of zero to 1 % of moisture [32]. For rough control of air
humidity in closed rooms, cheap colour indicators on plates are offered.
The colour indicator tube (Dräger Tube or Stain Tube) is used for a quick
and rough measurement of moisture in natural gas pipelines. Each tube
contains a chemical that changes its colour when the gas passes through. For

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 Water Vapour Sorption and Humidity 17

use, the tube is inserted into a gas pump, used once and discarded. The error
can be as high as 25 percent.
In absorption spectroscopy, light passes through a gaseous sample and the
amount of light absorbed at a specific wavelength is measured. A tunable laser
provides a source of narrow, variable wavelength light that can be used to
analyze the small spectral features. According to the Lambert-Beer law, the
amount of light absorbed by the gas is proportional to the amount of gas
present in the light‘s path; therefore, this technique is a direct measurement of
moisture.
Lyman-alpha hygrometer [33] is a hygrometer based on the absorption of
radiation by water vapour at the Lyman-alpha line, which is an emission line
of atomic hydrogen at 121.567 nm. Lyman-alpha radiation can be generated
by a glow discharge in hydrogen, and a nitric oxide ion chamber normally
accomplishes detection. Two magnesium fluoride windows both at the
radiation source and at the detector bound the absorption path. Lyman-alpha
hygrometers are used on aircraft and on meteorological towers for high-
frequency humidity measurements. Inconveniences of the method, like drift of
the source intensity or contamination of the windows, are overcome by special
calibration techniques or by baselining the high-frequency output to the
humidity values provided by a slower, but stable, hygrometer.
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Psychrometry

In 1825 August constructed the first psychrometer (Figure 9) on a

proposal of Leslie [34-35]. Richard Assmann (1845-1918) added a ventilator,
and this aspiration psychrometer [36] is regarded as a standard instrument for
air humidity measurements (Figure 10). It consists of two thermometers; the
bulb of one of it is kept wet usually by means of a humidified cotton envelope.
Evaporation from the wet bulb lowers the temperature, so that the wet-bulb
themometer shows a lower temperature Twet than those of the dry-bulb
thermometer Tdry. Evaporation is supported by an air stream, which is
generated either by a ventilator or by whirling the thermometer in the air by
hand (sling psychrometer). From the temperature difference, the partial
pressure of water vapour in the air pH20 can be determined using Sprung‘s
formula [37].

pH2 0  p0  C psy (Tdry  Twet )

(4)

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 18 Erich Robens, Katrin Rübner, Peter Klobes et al.

where p0 stands for the saturation pressure at the temperature of the wet bulb
Twet and the psychrometric constant Cpsy = 0,67 hPa K-1 stands for a height up
to 500 m and Twet > 0 °C. The relative humidity can be derived by means of
graphical tables.
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Figure 9. August psychrometer (1825). Figure 10. Friedrich Aßmann‘s aspiration

1 dry thermometer, 2 wet thermometer, psychrometer (1887). H cotton envelope,
3 cotton strip, 4 water reservoir. G air channel, Th thermometer,
W ventilator, U motor.

Dew Point Hygrometry

In 1820, John Frederic Daniell invented a dew point hygrometer, which

came into widespread use. The Lambrecht dew point hygrometer is a metal
mirror with good thermal conductivity, such as silver or copper. The mirror is
properly plated with an inert metal, such as iridium, nickel or gold, to prevent
tarnishing and oxidation and is polished. It is cooled by evaporation of ether
until moisture just begins to condense onto it (chilled mirror, CMH) (Figure
11). The decrease of light intensity due to scattering is observed optically. The

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 Water Vapour Sorption and Humidity 19

temperature at the beginning of opaqueness of the metal is the dew point

temperature.

Figure 11. Lambrecht dew point hygrometer (1881). 1 thermometer, 2 metal mirror, 3
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gap, 4 reference mirror, 5 container filled with ether, 6 air supply, 7 air pump.

Today the mirror is cooled using a Peltier cooler. The temperature of the
mirror is controlled by electronic feedback to maintain a dynamic equilibrium
between evaporation and condensation on the mirror, thus, to measure the dew
point temperature closely. A beam of light, typically from a solid-state LED, is
aimed at the mirror surface and a photodetector monitors the reflected light. A
platinum resistance thermometer (PRT), which is properly embedded in the
mirror, monitors the mirror temperature at the established dew point. Knowing
the atmospheric temperature and the dew-point temperature, the relative
humidity can be determined by means of a table. Among the various
hygrometric techniques, the dew point method is considered as the most
accurate (relative accuracy is about 1 % above 5% RH). Only the gravimetric
train, which is used as a primary standard, exceeds it.
In order to increase the accuracy of this type of hygrometer, surface
acoustic wave (SAW) devices are very useful because of their dual ability to
detect the dew deposition and to measure the temperature with great accuracy
[38]. Rayleigh wave properties were investigated in order to study the

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 20 Erich Robens, Katrin Rübner, Peter Klobes et al.

influence of dew deposition. The experimental device is cooled by means of a

Peltier element until dew deposition. Because of polarization of the Rayleigh
wave, the dew position induces a substantial attenuation of the wave amplitude
and a shift in the wave velocity (mass-loading effect). In order to combine the
influence of the temperature and the dew deposition, a thermocouple is
deposited on an LST-cut quartz plate. The frequency versus temperature
response is used for the dew point detection.
The application of paint and other coatings is very sensitive to humidity
and dew point. Condensed water can disturb the operation and can even
damage the electronic and micromechanical devices of camcorders and similar
apparatus e.g., which are therefore equipped with a dew warning (dew check).
Usually, this is an electric sensor whose resistance increases when moisture is
present.
Quartz crystal resonator (QCM) dew/frost point sensors operating in the
range -90 °C to 15 °C have a fast response time, high sensitivity and accuracy.
It was possible to distinguish between supercooled dew and frost from a single
scan of quartz crystal resonator [39-40].

Radiometry and LIDAR Hygrometry

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LIDAR (light detection and ranging) is an optical remote sensing

technology that measures properties of scattered light to find information of a
distant target [41-42]. By means of laser pulses and by measuring the time
delay between transmission of a pulse and detection of the reflected signal, the
distance to an object can be determined. Whereas radar uses radio waves,
LIDAR uses much shorter wavelengths of the electromagnetic spectrum,
typically, in the ultraviolet, visible, or near infrared region. In general, it is
possible to image a feature or object only about the same size as or larger than
the wavelength. Thus, LIDAR is highly sensitive to aerosols and cloud
particles. An object has to produce a dielectric discontinuity in order to reflect
the transmitted wave. Different types of scattering are used for different
LIDAR applications, most common are Rayleigh scattering, Mie scattering
and Raman scattering as well as fluorescence. The wavelengths are ideal for
measurements of smoke and other airborne particles (aerosols), clouds, and air
molecules. Since the deployment of the GPS (Global Positioning System) in
the 1980s precision positioning has become possible. Airborne LIDAR
systems monitor glaciers and have the ability to detect subtle amounts or
growth or decline. In atmospheric physics, LIDAR is used as a remote

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 Water Vapour Sorption and Humidity 21

detection instrument to measure densities and movement of certain

constituents of the middle and upper atmosphere, such as clouds. Inelastic
scattering is observed with Raman spectroscopy. Since the energy change in
this case is quantified, the spectrum is characteristic for the target molecule.
Water molecules scatter predominantly green light, Nd:YAG laser light with a
wavelength of 532 nm is reflected with 660 nm wavelength. This process is
applied to determine the relation of a water vapour mixture in the atmosphere.
Radiometers operating in the millimetre or submilimetre range of
wavelength have an enhanced sensitivity to low water vapour and liquid
contents in comparison to conventional microwave radiometers operating
below 30 GZ (1 cm). The temperature and humidity profile up to 5 km above
ground is determined in the arctic by using ground-based millimetre wave
radiometry and variational retrieval technique [43].

4. HUMIDITY OF LIQUIDS
In liquids, traces of water often deteriorate electrically insulating
properties or cause corrosion. Humidity can be determined by means of some
types of hygrometers described above. For example, an electrical resistance
hygrometer with aluminium an aluminium oxide moisture sensor can express
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the absolute humidity of gases and liquids in dew point temperature, parts per
million by volume (PPMv) or parts per million by mass (PPMw). Any gas
hygrometer can be used in head space gas analysis or after thermal
evaporation. Likewise, some moisture measuring methods designed for solid
materials can be applied, in particular thermogravimetry.

5. MOISTURE OF SOLID MATERIALS

Historical

The earliest report on a dehydration process is found in Vitruvius ( about

70 to 10 BC) "Books on Architecture" [44-45]. He describes conscientiously
the process of calcination of limestone,

"The reason why lime makes a solid structure on being combined with
water and sand seems to be this: Those rocks, like all other bodies, are
composed of the four elements. Those which contain a larger proportion of

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 22 Erich Robens, Katrin Rübner, Peter Klobes et al.

air, are soft; of water, are tough from the moisture; earth, hard; and of fire,
more brittle. Therefore, if limestone, without being burned, is merely
pounded up small and then mixed with sand and so put into the work, the
mass does not solidify nor can it hold together. But if the stone is first thrown
into the kiln, it loses its former property of solidity by exposure to the great
heat of the fire, and so with its strength burned out and set free, and only a
residuum of heat being left lying in it, if the stone is then immersed in water,
the moisture, before the water can feel the influence of the fire, makes its
ways into the open pores; then the stone begins to get hot, and finally, after it
cools off, the heat is rejected from the body of the lime.
Consequently, limestone when taken out of the kiln cannot be as heavy
as when it was thrown in, but on being weighed, though its bulk remains the
same as before, it is found to have lost about a third of its weight owing to the
boiling out of the water. Therefore, its pores being thus opened and its texture
rendered loose, it mixes readily with sand, and hence the two materials
cohere as they dry, unite with the rubble, and make a solid structure."

Thermogravimetry begun with Talabot, who equipped a laboratory with

39 balances for humidity control of silk, which was imported from China by
ship, at Lyon in 1833 (Figure 12) [46-47]. The whole equipment including the
lovely enamel-work, which shields the ovens, seems to be lost. In 1915 Honda
appears to be the very first to use the expression "thermobalance" for his
instrument (Figure 13) [48-49]. Soon afterwards such instruments were used to
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investigate the metabolism of plants (Figure 14).

In 1877 Hannay [50] described a gravimetric method to determine
dehydration isotherms of salts. He conveyed water vapour, which was released
from a heated sample into a cylinder that was filled with an ad- or absorbent,
by means of a carrier gas.

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 Water Vapour Sorption and Humidity 23

Figure 12. Désiccateurs Talabot 1833. Conditioning apparatus at Lyon for the
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

measurement of the humidity of silk.

Figure 13. Honda‘s thermobalance.

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 24 Erich Robens, Katrin Rübner, Peter Klobes et al.

Figure 14. Gravimetric instruments for the investigation of the metabolism of plants.

The cylinder was weighed periodically. Warming up samples in a heating

chamber and sequential measurements of the decreasing sample mass in order
to determine the desorption isotherm is still widely used [2-3].
In 1886 Warburg und Ihmori [51] built a beam microbalance for
adsorption measurements. The first vacuum microbalances with
electromagnetic compensation were made by Emich [52-53] and Urbain
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[54] in 1912. Today a variety of electrodynamic compensating vacuum

microbalances is available on the market [55-56]. Several apparatus equipped
with such balances for automatic measurement of adsorption isotherms are
offered also. The first one has been built in 1962 [57] (Figure 15). Many of
those microbalances were used first to measure water adsorption from the
atmosphere. Today the measurement of humidity is facilitated by so called
drying or moisture balances, which are laboratory scales equipped with an
infrared or microwave heater (Figure 16) [7].

Material Moisture Measuring Methods

There are indeed two types of humidity: Air humidity, which is

independent from the other components of the air, and the humidity of
materials, which is influenced or even dependent on the material in question
that may be a solid, a liquid or a gas.

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 Water Vapour Sorption and Humidity 25

Figure 15. Sartorius Sorptomat of Sandstede and Robens. Apparatus for the automatic
measurement of adsorption isotherms. On the left a Gast vacuum microbalance sticks.
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Figure 16. Drying or moisture balance Sartorius, with halogen infrared heater.

The common term humidity also comprises liquid contents other than
water, solvents e.g. [58]. In the following, we restrict ourselves to the content
of water (moisture) generally expressed as the amount of water in relation to
unit mass or unit volume of the sample.

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 26 Erich Robens, Katrin Rübner, Peter Klobes et al.

Table 3. Methods for the measurement of moisture content

Method Principle of measurement

Oven-drying Thermal activation of the sample and gravimetric
Moisture balance measurement of mass loss
Thermogravimetry Mass loss under controlled temperature programme
Sorption measurement Variation of (partial) water vapour pressure and measurement
Desiccator method of mass change
Standard contact Contact with standard of defined humidity, measurement of
porometry mass change
Dielectric Capacitive measurement with a condenser taking the
measurement advantage of the high dielectric constant of water
Electric conductivity Electrochemical measurement of conductivity
measurements
Microwave and Measurement of absorption of radiation
infrared spectroscopy
Nuclear magnetic Measurement of resonance between a high-frequency
resonance electromagnetic field and 1H nucleus of water of a sample,
spectroscopy which is arranged into a strong homogeneous magnetic field
Activation analysis Measurement of absorption of fast neutrons or -rays
Calorimetric method Measurement of heat capacity and conversion heat
Karl Fischer Titration using Karl Fischer reagent
Phosphorus pentoxide Thermal activation of the sample, absorption of water
Moisture indicator Qualitative test observing colour change
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The peculiar characteristic of the water molecule and its anomalous

features facilitates its identification and allows the application of very different
methods to determine water content and humidity depending on the ambient
conditions. However, only a few methods provide reliable values [59] of the
water content of solids and enable to distinguish between free bulk water,
adsorbed vicinal water, absorbed and chemisorbed water. Furthermore, just the
gravimetric methods measure the sum of volatile substances within a solid,
whereas, in general, the task is to determine the water content only. Mostly
applied methods used as routine tests are summarised in Table 3.

Drying Methods

The classic laboratory method of a moisture measurement of solids is the

determination of the loss on drying (LOD). On the other hand, drying of the
sample is necessary in order to adjust definite starting conditions for
adsorption experiments. In both cases careful methods, which avoid damage of

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 Water Vapour Sorption and Humidity 27

the sample, should be applied. The following methods have proved to be

useful.

Drying at Elevated Temperature

A temperature as high as possible at which the sample is not damaged is

determined by pilot tests using thermogravimetry. The drying process can be
controlled thermogravimetrically as well.

Vacuum Drying

Vacuum is applied at a pressure below saturation pressure of water at

ambient or elevated temperature. The degree of dryness may be assessed by
observing the pressure increase after locking of the connection valve to the
vacuum pump.

Drying by Means of Desiccants

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The sample is placed in a desiccator equipped with a desiccant, usually

silica gel with moisture indicator, phosphorous pentoxide (p-drying),
magnesium perchlorate or concentrated sulphuric acid.

Cold Trap Drying

At ambient temperature, the sample vessel is connected to a cold trap,

which is cooled by means of a mixture of dry ice with alcohol (d-drying) or a
refrigerator. In addition a vacuum pump may be connected to the cold trap.

Gas Flow Drying

An inert gas is passed above the sample usually at elevated temperature.

The procedure is time consuming.

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 28 Erich Robens, Katrin Rübner, Peter Klobes et al.

Freeze Drying, Lyophilization

Usually, the material is placed in a freeze-drying flask that rotates in a

bath called a shell freezer, which is cooled below the triple point of water by
mechanical refrigeration, a dry ice and methanol mixture (193 K) or liquid
nitrogen (77 K). Then the frozen water in the material sublimes directly from
the solid phase to the gas phase by reducing the surrounding pressure with a
vacuum pump and adding enough heat. To avoid recrystallisation, sensible
materials are frozen very fast.

Solvent Exchange

The water included in the material is replaced stepwise by other solvents,

methanol, ethanol, isopropanol, alcohol solutions in increasing concentrations
30 %, 50 %, 60 %, 70 %, 80 %, 90 % 96 % DMSO or diethlyether e.g. The
final solvent is vaporised at elevated temperature. The last solvent should be
volatile and should have a low surface tension. This complicated and slow
method avoids damage by crystallization particularly of biological materials.
Supercritical drying is a process to remove liquid in a precisely controlled
and gentle way. It is useful for the production of aerogels and for the
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preparation of biological materials. When a substance crosses the boundary

from liquid to gas the substance volatilises and so the volume of the liquid
decreases. Sensible structures like cell walls collapse because of the surface
tension at the solid-liquid interface. To avoid this, the sample can be brought
from the liquid phase to the gas phase without crossing the liquid-gas
boundary on the phase diagram by passing through the supercritical region at
high temperature and pressure above the critical point. Densities of the liquid
phase and vapour phase become equal at the critical point of drying. Fluids
suitable for supercritical drying include carbon dioxide (critical point 304.25 K
at 7.39 MPa) and freon (about 300 K at 3.5-4 MPa). Nitrous oxide has a
similar physical behaviour to carbon dioxide, but is a powerful oxidizer in its
supercritical state. Supercritical water is also a powerful oxidizer partly
because its critical point occurs at a very high temperature and pressure (647 K
and 22.064 MPa).

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 Water Vapour Sorption and Humidity 29

Gravimetric Measurement of Material Moisture

Gravimetric measurements to determine the humidity or dry mass of a

solid material are based on the removal of water by reducing the partial
pressure of water vapour of the gaseous phase above the sample. This may be
done with a vacuum pump, by a condensation process within a desiccator or
by means of a dry gas flow. Controlled heating of the sample shortens the
measuring time. In addition to physisorbed water, chemically bound water
may also be removed. The mass decrease of the solid sample is measured
gravimetrically or the water mass removed is weighed.
Gravitational balances measure not the mass but the sum of mass plus
buoyancy of the sample. The buoyancy of the adsorbate must also be taken
into account in case water is predominant in spongy structures in comparison
to the skeleton. Measurements are disturbed by convection and, at low
pressures, by thermal gas flow. During the drying of large samples shrinkage
of porous materials or agglomeration of fine materials result in encrustation.
This obstructs evaporation from interior and distorts the drying process.
Oven-drying is a widely used method. Here the sample is dried at a
constant temperature. Humidity is removed by circulating air. The sample is
weighed after reaching mass constancy. Such measurements give reliable
"true" results of the moisture content only in case of well known drying
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

characteristics of the material. Weighing at intermediate times and deriving a

kinetic curve may obtain more information. However, very different results
may also be obtained by this method due to the different binding types of
water (Figure 17).
Because the manual laboratory method is relatively slow, automated
moisture analysers that can reduce the time necessary for a test from a couple
hours to just a few minutes have been developed. Electronic moisture balances
are equipped with an infrared or microwave heater and a device to remove the
moistened air. The moisture balance (Figure 16) is a simplified model of a
thermogravimetric apparatus, also known as conditioning apparatus.
A thermogravimetric apparatus (Figure 18) consists of a balance and a
heating unit to adjust the sample temperature at a constant value or to control
the defined temperature increase [60]. Measurements are made either in air, an
inert gas flow or vacuum [61].

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 30 Erich Robens, Katrin Rübner, Peter Klobes et al.

Figure 17. Infrared drying of candies at ---- 90°C, --- 95°C,  100°C, --- 110°C,
and water content measured using the Karl Fischer method ────, © Isengard.
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Figure 18. Diagrammatic view of a thermogravimetric apparatus with vacuum

thermobalance (MOM Derivatograph). 1 balance beam, 2 sample, 3 counterweight, 4
oven, 5 vacuum pump, 6 temperature sensor, 7 recorder, 8 temperature program
control. The records for thermogravimetric analysis (TGA): DTA differential thermal
analysis, DTG differential thermogravimetry, TG thermogravimetry, DDT differential
thermal dilatometry, thermal dilatometry.

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 Water Vapour Sorption and Humidity 31

Figure 19. Quasi-isothermal water desorption from activated carbon (Merck) according
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

to Staszczuk. Mass loss (Q-TGA) and its time derivative (Q-DTG) are plotted. ©
Stasczuck.

To investigate the water content, measurements are performed at low

temperatures. Physisorbed water and condensed pore water vaporise mainly up
to 100 °C. Chemisorbed components and crystal water are liberated at higher
temperatures. Quasi isothermal thermograms (QTGA) are measured at slow
temperature increase whereby the sample is held under saturation vapour
pressure using special sample containers (Figure 19). QTGA can be evaluated
for binding parameters and for pore size distribution.

Measurement of Water Sorption Isotherms

To measure adsorption isotherms of water vapour, the mass adsorbed is

usually determined gravimetrically as a function of stepwise varied pressure at
constant temperature [62]. Alternatively, the mass adsorbed may be
determined from volume, pressure and temperature in the sample vessel using

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 32 Erich Robens, Katrin Rübner, Peter Klobes et al.

the equation of state. Adsorption measurements are started from a dry sample
state in vacuum or dry atmosphere as well as from a defined humidity.
Desorption is started from a defined humidity, from saturation pressure if
possible.
Sorption isotherms may be measured simply by placing the samples in a
desiccator at constant temperature. Different humidities are adjusted by means
of salt solutions [63]. One sample is exposed to a defined single humidity by
the integral sorption method whereas the humidity around one sample is
stepwise varied by the interval method. Intermediate evacuation or movement
of the gas atmosphere can speed up measurements.
An apparatus of gravimetric water sorption consists of a microbalance and
a thermostat. Water vapour pressure is adjusted and varied by means of a
carrier gas flow loaded with water vapour (Figure 20a). Alternatively, using a
vacuum balance, either portions of water vapour are added or the pressure is
adjusted by means of a thermostated water reservoir (Figure 20b).
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

Figure 20. Apparatus of gravimetric water sorption consisting of a microbalance and a

thermostat. 1 vacuum balance, 2 sample, 3 thermostated case, 4 water, 5 vacuum
pump, 6 valve, 7 flow control, 8 humidifyer. 9 gas inlet, 10 gas outlet.

Figure 20a. Water vapour pressure is Figure 20b. Alternatively, using a vacuum
adjusted and varied by means of a balance, either portions of water vapour are
carrier gas flow loaded with water added or pressure is adjusted by means of a
vapour. thermostated water reservoir.

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
 Water Vapour Sorption and Humidity 33

Figure 21. Conditioning equipment for Standard Contact Porometry according to

Volfkovich, Bagotzky, Sosenkin and Shkolnikov. 1 sample layer, 2 standard layer, 3
diaphragm, 4 vessel, 5 screw flange, 6 centring tube, 7, 12 vapour inlet, 8, 9 O-rings,
Copyright © 2011. Nova Science Publishers, Incorporated. All rights reserved.

10 thermostat, 11 bellows.

Modified volumetric apparatus as widely used for the measurement of

adsorption of permanent gases may also be applied for the measurement of
water sorption isotherms. Here, condensation in the manifold must be avoided.
Drying processes can be easily observed by stepwise pumping of the water
vapour, which is developed from a sample, in a calibrated volume.
The standard contact porometry was developed by Volfkovich, Bagotzky,
Sosenkin and Shkolnikov [64]. Here, the sample is brought into contact with a
porous standard sample with defined water content (Figure 21). In
thermodynamic equilibrium, the liquid into the whole pore system has an
identical chemical potential. The humidity of the sample can be derived from
the equilibrium water mass in the standard. A set of standards allows the
determination of an isotherm even near saturation pressure.
In water adsorption isotherms, the specific adsorbed amount na is plotted
as a function of the relative vapour pressure p/p0.

Humidity Sensors: Types, Nanomaterials and Environmental Monitoring : Types, Nanomaterials and Environmental
Other documents randomly have
different content
 The animal being in its stall,
then apply the lotion, composed
of tincture of arnica, two
ounces; water, one quart. Use
this by means of a sponge and
saucer. Pour some of the liquor
into the receptacle. Saturate the
sponge and squeeze the fluid
upon the leg, but above the
injured knee. Do this after the
manner which is illustrated as
the proper mode of washing the
THE MANNER IN
wounded part.
WHICH LOTION
SHOULD BE Continue with the arnica
APPLIED TO AN lotion, night and day, for half a
OPEN JOINT.
week. No periods can be named
for applying the sponge, as
inflammations, and therefore the drying powers, vary in different
individuals; but the knee should be always wet. This should be
attended to for the first three days and a half, during which the
halter should be tied to the rack. At the end of that time turn the
horse very gently round. Remember the condition of the limb, and
allow time for the performance of an action which is always an effort
to the most agile of the equine species, as few stalls are a single
inch too wide.
The animal being with its face to the gangway, and fastened by
the pillar-reins, place the slings before it. Leave the creature to
contemplate the apparatus for half an hour. Then take the cloth and
hold it up to the inspection of the quadruped. Afterward place it
between the fore and hind legs—pausing and speaking kindly should
alarm be displayed. Thus by degrees fix it to the pulleys and bring it
near to the abdomen, which, however, should by no means be
touched. Then caress the creature's head, and present some of its
favorite food: eating generally tranquilizes the mind of an animal. So
much being done, proceed to fix the straps upon the chest and
withers. Then fondle the sufferer again, and it will permit the hind
tackle to be arranged.
When all is fixed, leave a pail of water suspended from one pillar,
and put an elevated trough, charged with favorite provender, in front
of the horse. Let it be watched till a week from the date of the injury
has expired, and never left during that period even for an instant. If
any restlessness is exhibited, the attendant should approach and
caress the creature. Quadrupeds—though none comprehend the
precise meaning of the language—love to be praised. The hand,
fondly applied to the skin, and the human voice, modulated by
kindness, seem to convey a purport to animals which they will suffer
pain to deserve. The writer lately had a favorite dog, whose aversion
was dry bread. It would hold the detested morsel in its mouth for
hours, looking most uncomfortable, but making no attempt at
mastication. Yet, upon praise being lavished, the eye would brighten,
and, rather than prove unworthy of so much commendation, the
hardest and stalest crust would be chewed and swallowed.
Watching is necessary, because many horses when thus
imprisoned, being left alone, grow terrified and injure themselves by
struggling their bodies out of the slings. The presence of any human
being assures the timidity and checks the active imagination of a
solitary animal. The author well knows that the learning of the
present time denies imagination to animals. Shying, is only the
creature imagining something which is not actually before it. What
are dreams but positive evidences of imagination? All people have
heard the suppressed bark and seen the excited limbs of the dog as
it slept upon the hearth rug. How many grooms have been
surprised, upon their earliest visit, to see the stable knocked to
pieces and the horse prostrated amid the ruin it has created! How is
this to be explained if imagination be not present in the animal? This
is the author's interpretation of the mystery. Dreams are active, in
proportion to the immaturity of the reason. Children often wake up
in tears, and continue screaming in terror for long periods if
unattended to. The horse starts out of a fearful vision; darkness is
about it; the fear augments; the
animal begins kicking; the
sound made by its own feet
increases the creature's alarm;
it lashes out frequently until it
has pounded part of its dwelling
into atoms and disabled itself to
that degree which makes the
highest punishment the
greatest mercy.
A high trough is required to
guard against the effects of that
itching which attends the
healing process, and provokes
the animal to strike its knees. A HORSE IN SLINGS FOR OPEN
This it would do against the JOINT.
manger were its head in the
customary position. Were a wall
before it, the knees might still be laid open; but with a high trough
nothing is within the reach of its injured joint. Even supposing one of
the slender supports, by the cunning of excitement, to be struck, the
substance should be too light to offer any dangerous resistance, the
blow being far more likely to overturn the machine than to lacerate
the limb.
When the quadruped has remained sufficient time in the slings to
have become familiar with them, pull up the cloth so that it may
slightly touch but not press against the belly. Then well secure it,
and leave the animal to rest its wearied limbs, or not, as it pleases.
Its suffering joints will soon teach the horse to bear the entire
weight upon such a support, and to sleep comfortably in the
contrivance. With a few, and only a few examples, living in slings
has induced such confirmed constipation as necessitated a daily
resort to bran mashes. Most horses, however, speedily accept and
grow fat, enjoying the relief thus afforded. Only one caution need be
given—look well to the tackle. The horse is very heavy, and should a
single fastening prove insecure, the result might convert a healing
wound into a hopeless injury.
With the employment of
slings, change the lotion for one
composed of chloride of zinc,
one scruple; water, one pint;
this need be applied only during
the day. It is too weak to
occasion pain, and should be
used with the saucer and
THE sponge, after the manner of
ALBUMINOUS washing a broken knee or open
BALL, WHICH joint, which has been previously
FORMS IN SHAPE illustrated. The strength,
OF AN OPEN nevertheless, is sufficient to
JOINT WHEN
TREATED WITH A coagulate the albumen of the
SOLUTION OF synovia. Thus it forms a species
CHLORIDE OF of natural bandage which
ZINC. excludes the air, while at the
same time it stimulates the
flesh and causes that to heal under the protection of its own
albuminous secretion.
The coagulated albumen frequently accumulates in front of the
knee. The author has seen it attached to the part quite of the size
and very near to the form of the largest apple. It must on no
account be touched, however large it may grow or however insecure
it may appear. Respect it, and it will fall off when its service is
accomplished. The cure is nearly completed when the white ball
falls. Shortly after the wounds being closed, and pressure made with
the fingers—not with the thumb—can be endured, the slings may be
removed; though the healing should be further confirmed before the
horse is allowed to stand opposite to any substance against which it
may strike what recently has been a fearful open joint.
 WOUNDS.

To this species of injury the horse is much exposed from the

recklessness or incompetence of those who assume to hold the reins
of authority. Occurrences which are politely termed "accidents,"
generally entail suffering upon the blameless animal. The common
provocatives of such accidents are either the drunkenness of man or
his utter ignorance of the mental attributes of the quadruped he has
possession of. The first cause shall be passed over in disgust; the
second merits some consideration, being rather a universal than an
individual fault.
When a horse pauses, always endeavor to ascertain the motive;
the reason may be groundless. By gentleness, convince the creature
that its fears are without foundation, and you earn a supremacy as
well as win a gratitude which will always be cheerfully
acknowledged. Never employ the whip to correct "the obstinacy of
the brute." The horse is naturally very fearful; were it not so, man
would never have obtained that mastery which is imperative for
domestication. Elderly gentlemen should never thrust their heads out
of carriage windows and shout to the driver to "go on." Such implied
chiding may urge the coachman to display severity, and the horse is
dangerous when alarmed. So long as the animal continues calm, the
superiority of man is submitted to; but once excite the terror of the
quadruped, and all earthly restraint is powerless. Dread assumes the
form of the wildest fury, and the horse tears onward, insensible to
mortal punishment and blind to every danger.
It is in this manner the most terrible wounds are produced. Such
injuries, in surgical language, are defined to be "solutions of
continuity," or "separations of the skin and soft parts underneath."
Neither of these definitions, however, includes a bruise or a contused
wound. Therefore, for the present purpose, a wound will be
interpreted an injury inflicted by external violence.
 A lacerated wound may be too trivial to attract the surgeon's
notice, as a scratch. It may also be a very serious affair, as when a
cart-wheel runs against a horse's thigh, tearing the flesh asunder.
Laceration is generally accompanied by contusion, though contusion
forms no necessary part of a lacerated wound. When such injuries
are inflicted, they are mostly followed by little hemorrhage; yet it is
far from unusual for an animal thus hurt to perish. Shock to the
system is the most serious of the primary effects. Beyond that the
immediate consequence appears to be insignificant. Little blood is
lost, for the vessels are stimulated by the violence which rends these
tubes and the soft structures asunder. Stimulation causes the torn
mouths of the arteries and veins to close or to retract. The ragged
coats of the vessels, the loose fibers of the flesh, and the jagged
cellular tissue likewise fall over the orifices, and help to stay the flow
of the vital current.
The dangers attending lacerated wounds
spring, in the first instance, from collapse.
This possibility being overcome, the
immediate peril has been surmounted; all
injuries of this nature are commonly
attended, however, with more or less
contusion. The force necessary to tear open
a portion of the body will, of necessity,
bruise or kill some part of the flesh. Any
DIAGRAM OF A SEVERE animal substance, when deprived of vitality,
LACERATED WOUND. must be cast off by a living body; a slough
must follow. Now that process is attended
with hazard in proportion as it is tardily accomplished. The period of
its occurrence is always one of anxiety; for when this process takes
place, the stimulation that originally caused the vessels to retract no
longer exists. All mechanical opposition to hemorrhage is, with the
loss of the dead matter, generally removed. Everything, therefore,
depends upon the fibrinous deposit—a sort of glutinous material
secreted by the body, which is commonly largely poured forth when
any slough by natural and speedy action is effected. Should the
frame be so far debilitated as to prevent all secretion of fibrin, the
most frightful bleeding must ensue.
The horse which has not recovered from the original injury will
then sink under the terrible depletion. Therefore, it is impossible to
form any opinion of the injurious effects or of the consequences
likely to follow a lacerated wound before some time has elapsed.
An incised wound implies a division, more or less deep, of the
soft parts. This form of injury produces less shock to the system,
and generally heals more quickly than any other. The principal
danger is encountered at the moment when the wound is inflicted;
vessels may be sundered, and they are cut in twain with the least
possible irritation to the parts within which they are situated. The
veins and arteries, therefore, do not generally retract any more than
do the soft structures. A gash into a fleshy substance always
produces a gaping wound, which is wide in proportion to the depth
and length of the injury. From that hurt the dark-colored venous
blood drains in a stream, while the bright scarlet or arterial blood is
propelled forth in jets, sometimes to a considerable distance. These
jets correspond with the pulsations of the heart; but as syncope or
fainting takes place, the emission ceases with the beating of the
circulatory center.
The danger consequent upon
an incised wound is ever
measured by the extent of the
hemorrhage. When large arteries
are divided, that fact is easily
told by the size and the force of
the jets sent forth. A strong
horse may, from that cause, be
dead in ten minutes. To enforce DIAGRAM OF AN INCISED WOUND.
the difference between a
lacerated and an incised wound,
the reader is reminded of those painful cases, frequently recorded in
the newspapers, where a limb is by machinery torn from a poor
man's body, and scarcely a drop of blood marks the deprivation; also
of death by severing a throat, when sensation ceases ere the stream
has flowed forth. The last is an incised, the first is a lacerated
wound.
An abraded wound, in its
mildest form, is simply a graze.
The reader will, however,
remember how acutely painful
such accidents always are. The
horse's sufferings are not highly
estimated by the generality of
people; nevertheless, an injury
of this description is not to be
despised, even when witnessed
on the animal. A broken knee, DIAGRAM OF AN ABRADED WOUND.
as it generally is exhibited, is
nothing more than an abrasion. An abraded wound may simply
mean that the insensible outer covering of the skin has been injured;
it may also imply that the soft structures beneath have been
sundered. Wounds of this kind are not free from danger when of
magnitude. Little blood may flow, but the cutis is the most sensitive
structure of the entire body. A needle's point cannot enter any part
of the skin without sensation warning the person of a puncture. In
human operations, division of the skin, or separation of the cutis, is
known to constitute the major portion of the patient's agony.
The suffering attendant on the latter class of injuries is increased
by almost every abrasion forcing grit or dirt into the substance of the
cutis. This, of course, is generally washed out. The torture
accompanying a large abraded surface is, therefore, very great; and
horses when suffering from accidents of such a nature sometimes
sink from the irritation consequent upon the injury. When the
animals survive, the roots of the hair too often have been destroyed,
and a perpetual blemish is the result.
 A punctured wound is
always dangerous; the hazard
in this, as in every species of
injury, is greatly increased when
inflicted on parts liable to any
vast amount of motion. Thus,
punctures occurring over the
stifle-joint too often set our
DIAGRAM OF A PUNCTURED best surgery at defiance. The
WOUND. muscles of the hind leg contract
The engraving with every movement of the
supposes the soft body. Added to that, the part
parts to have abounds with fascia.
been divided, in
order to show the The majority of these
ragged nature wounds heal by suppuration.
and large extent Fascia is a substance no pus
of the injury, with
the comparatively
can penetrate, and which is
small opening by more easily rent than
which this punctured. The exit of the
amount of harm secretion, therefore, is opposed
is characterized. in many directions, while the
ceaseless motion occasions the
matter to burrow. The sinuses thus produced are by the fascia
guided to the stifle-joint; and, when once the synovial cavity is
polluted by the intrusion of the unhealthy pus, all the best efforts of
science are useless.
When a punctured wound occurs, the skin, being elastic,
stretches before the instrument by which the wound is inflicted. The
soft parts beneath the skin, not being elastic to the same degree as
the integument, break down before the penetrating force. They are
torn or lacerated; for generally the muscles receive a larger injury
than would be calculated from the size of the instrument by which
the blow was inflicted. The rent flesh must be cast off by a slough—
corruption generally attends that process. Much of the pus secreted
cannot find an exit through the opening in the skin; a large portion
of it is confined within the puncture. There it decays, and, being
impelled by the motion of the limb, readily finds its way in all
directions save the upward one.
No judgment approaching to accuracy can be formed at the first
sight of a punctured wound. The probe may ascertain the depth of
the injury, but it cannot tell the extent of damage done to the
interior of the body. Therefore, whether the hoof is pierced by a nail,
or the muscles are lacerated by the shaft of a cart—be the
instrument large or small—the consequences likely to follow upon
the injury cannot be foretold.
A contusion, in its mildest form, is
simply a bruise. Injuries of this class,
when of magnitude, are very deceptive;
the surface is unstained by blood, and
there is no flesh exposed. For these
reasons the ignorant are apt to disregard
such accidents, and to express surprise DIAGRAM OF A CONTUSED
when they terminate otherwise than WOUND.
kindly. When a bruise happens, blood is
effused in smaller or larger quantities according to the extent of the
injury. A small quantity of effused blood, sufficient to discolor the
human skin, may be absorbed; but when the amount is large, the
powers of nature are defied. The blood thrown out, not being taken
up again, congeals, and ultimately corrupts. Then an abscess or a
slough is necessitated; both are attended with danger: the first may
be deep seated or superficial; either form is attended by much
weakness. That generates considerable irritation, and may even be
the cause of fatal hemorrhage; or it may lead to sinuses, the
direction, the number, or extent of which, when they do occur, is not
to be predicated. A bruise is, consequently, not to be judged of
hastily. The amount of pain which it provokes is even unworthy
dependence, as the injury may have hurt the bone or the tendon;
and then, though the accident is rendered very serious, in the first
instance no sign of agony announces the extent of the evil.
 With regard to treatment, when a lacerated wound occurs, the
first attention should be paid to the system, which has always been
much shaken. Give, therefore, the drink composed of one ounce
each of laudanum and sulphuric ether, with half a pint of water;
repeat it every quarter of an hour till the shivering natural to the
horse on these occasions has disappeared, and the pulse has
recovered its healthy tone.
Avoid all poultices of the ordinary kind; one composed of one-
fourth yeast and three-fourths of any coarse grain, excepting bran,
may be applied. So also may a lotion thus composed:—
Lotion for Lacerated Wounds.
Tincture of cantharides One ounce.
Chloride of zinc Two drachms.
Water Three pints.
Mix. Keep a rag constantly wet over the part.
Either will stimulate the parts, and probably prevent any
tendency to unhealthy action. The yeast poultice produces this effect
by giving off carbonic acid; the lotion accomplishes this intention by
both its active ingredients. Each is stimulating, also disinfectant, and
will counteract any filthy odor which may attend the sloughing
process; but the lotion is perhaps to be preferred, as it is more easily
applied. When the slough has taken place, should hemorrhage
ensue, dash upon the part jug after jug of the coldest water; or,
should no very cold water be at hand, drive upon the mouths of the
vessels a current of wind from the nozzle of the bellows. Continue to
do this till the bleeding ceases, or until a surgeon can be obtained to
take up the arteries.
The after-treatment is simple: apply frequently the solution of
chloride of zinc, one grain to an ounce of water; that lotion will
cleanse the wound and prevent unpleasant smells.
As respects feeding, this must be regulated by the character of
the pulse. Should the beat of the artery be quick and feeble, no hay
should be given; good, thick gruel should constitute the only drink
excepting in extreme cases, when two pots of porter may be allowed
each day. Good oats and old beans, both crushed and scalded,
should then constitute the food, and the utmost gentleness should
be exercised toward the animal.
Should the pulse be natural, allow three feeds of oats each day,
as, in every kind of injury to the horse, more danger is to be
apprehended from debility than from any excess of energy.
Incised wounds.—When these happen, always dash the part
with plenty of cold water or blow upon them with the bellows. Place
the horse in the nearest shed; motion promotes hemorrhage,
therefore a walk is not to be hazarded. The bleeding being arrested
—for, in severe accidents of this kind, there is no time to send for
assistance—let the animal remain perfectly quiet until the exposed
surface has become almost dry, but on being touched by the finger
feels sticky. Then draw the edges together, and keep them in that
position by means of sutures.
The best means of inserting
these sutures is with a curved
needle fixed into a handle. The
handle is wanted to obtain the
necessary power, and the
needle's point should be sharp
to penetrate the hide of the
horse, which in places is of
considerable thickness. The
FIXED SUTURE needle is thrust through the
NEEDLE: VERY
integument about one inch and
USEFUL
FOR INCISED a half from one margin of the
WOUNDS OF NO incision; it is brought out about
GREAT DEPTH. the same distance within the
divided soft parts. It enters the
opposite side of the sundered flesh even with the place whence it
came forth, and afterward it appears through the skin about equally
distant from the opposite edge of the wound. There is a hole near
the point of the needle; through this opening a piece of strong twine
or narrow tape is threaded; when, the instrument being withdrawn,
the twine or tape is pulled into the puncture which has been made.
The needle is then released, the suture being left in.

THE MANNER OF USING THE FIXED SETON NEEDLE.

A second person pushes the wound
together, and, when the point of the
needle appears, threads it with a
piece of zinc wire or soft string. The
needle is then retracted, and
released from the wire or string,
whereby a suture is left in the
wound.

So many sutures as may be necessary are thus inserted—in small

wounds, these being about two inches asunder, but in larger injuries,
three inches apart. All are duly placed before any are tied; the whole
being ready, the wound is forced together by an assistant, while the
strings are fastened—care being exercised not to bring any of them
actually tight, lest the motion of the body or the swelling of the part
should drag the sutures through the flesh and thereby tear them
out.
A wound thus united may
possibly heal by first intention,
or the divided parts, when
brought together, may join, and
give no further trouble to the
surgical attendant.
Union by first intention is,
however, somewhat rare in the DIAGRAM OF SUTURES WHEN TIED
horse; and should not that take AND
place, suppuration will be LEFT IN A WOUND.
established. So soon as the pus
flows freely forth, and the sutures appear to tighten or drag, cut
them out by snipping the twine; but allow the strings to loosen
before you attempt their withdrawal.
If this is not done, the sutures will speedily find an exit for
themselves by causing the flesh against which the tension acts to be
absorbed; thus the original injury will be rendered more complicated,
and the ultimate blemish must be altogether greater.
All that is required after the establishment of suppuration is to
bathe the part with the solution of chloride of zinc, one grain to the
ounce of water. This lotion will suppress any fetor, and gently
stimulate the healing process, as well as prevent the sprouting of
fungoid granulations; it is necessary also to attend strictly to the
directions laid down for feeding during the curing of wounds.
 TWO KINDS OF SUTURES RARELY EMPLOYED UPON THE HORSE.

No. 1. The continuous suture,

which is employed for sewing up
portions of bowel when the
intestines are injured and
exposed.
No. 2. The deep suture or the quill
suture. In the horse pieces of
wood are substituted for quills.
The wood is notched in the
center; and upon the indentations
the sutures are fixed, to prevent
the movements of the animal
from displacing them. It is
sometimes employed to bring the
sides of deep and gaping wounds
closer together.

The treatment of an abraded wound chiefly consists in

cleansing the surface with plenty of cold water, which should be
allowed by its own weight to wash off any loose particles of dirt. No
cloth or other aid should be employed to scrub the living flesh as
though it were an insensitive board. The matter which cannot be
removed by simply sluicing, had better remain to be expelled by the
secretion of pus. The horse, especially when terrified, endures pain
very badly; indeed, the animal is so timid and so delicately framed
that it is always good surgery to spare all unnecessary suffering.
Support the body with laudanum and ether drinks, one ounce of
each to the pint of water, as often as they may be needed. Let the
food be generous, unless fever should arise, when the directions
already given must be attended to.
Punctured wounds require only one kind of treatment,
whether a nail be driven into the flesh of the foot, or the shaft of a
cart be forced into the substance of the thigh. Here the knife must
be employed; and, unless the animal shows evident symptoms of
excessive weakness, it is better, perhaps, to operate while the parts
are partially numbed by the shock, than to wait until a morbid
sensibility is provoked. Always enlarge the opening; do this in the
foot by cutting away the horn of the sole around the small puncture
left by the nail. When the soft parts are penetrated, probe the
wound first; then, if possible, insert a knife to the bottom of the
puncture, and, with the edge downward, draw it forth. By this
means a wound resembling a subverted < will be instituted. It will
be narrowest toward the extremity, and widest at the mouth. A free
opening affords a ready egress for all sloughs and pus. It materially
aids the healing process, and effectually prevents the establishment
of sinuses; while the clean incision left by the knife is of small
import, when taken into consideration with the other consequences
of a punctured wound.
Support the animal if necessary, or regulate the food by the
symptoms.
A contused wound, when slight, may be rubbed with the iodide
of lead ointment, one drachm of the active agent to the ounce of
lard; when all enlargement will sometimes subside, and the effused
blood may be absorbed. However, the horse commonly receives
injuries of magnitude. In the last case, take a sharp knife and draw
it along the entire length of the swelling. Make a long gash, only
through the integument, at every eighth inch, and be careful to carry
the knife through the integument, or to the lowest portion of the
detached skin. Any sac that may be left is certain to retain
corruption, and may produce fearful after-consequences. The
attendant measures consist in bathing the contusion with a lotion
composed of chloride of zinc, one grain, water, one ounce, and
diminishing the food or supporting the body as nature demands such
treatment.
The after-treatment of all injuries consists in keeping any
external orifices open till all sloughs and pus have disappeared. In
surgery, a large and depending opening, by means of which the
interior may drain, is always to be preserved, and the knife, to this
end, may be employed so often as the healing process threatens to
prematurely close the wound.
Formerly it was the practice to bleed after every injury; this was
done to prevent fever. However, observation has shown that the vital
powers are more often weakened than increased by the shock
attendant on severe accidents. Whenever the contrary happens, it is
far better to lower the pulse by repeated doses of aconite, than to
abstract that which will subsequently be necessary to repair injury.
It was also once the custom to fill wounds with tents or lumps of
tow, and to bandage every injured part. These habits only served to
confine that which nature was striving to cast out. They
consequently did much harm, and are now happily discarded.
A piece of loose rag, saturated in the oil or the solution of tar,
should, during summer, be suspended over the mouth of every
wound, to keep off the flies. The only tent which the author
approves of is when an incised wound happens where assistance is
far away, and difficult to procure. Then, to arrest the hemorrhage,
let the horse rug, a man's coat, or anything else be violently thrust
into the gash, and forcibly held there until proper assistance can be
obtained.
 Such is the present method of treating wounds; this to the
reader may appear very cruel; but could he have walked through
and have inhaled the atmosphere of the wards in hospitals
appropriated to such injuries as they existed in former times, he
would thoroughly understand that apparent want of feeling is, in
reality, the height of charity.
To conclude this part, the
author lays before his readers
the following bandage, intended
to meet an inconvenience
hitherto experienced when a
horse has the walls of the
abdomen punctured. The
constant motion of the part
A BANDAGE renders ordinary sutures of no
DESIGNED FOR avail, and for that reason
WOUNDS ON THE bandages, unless so tight as to
TRUNK OF THE check circulation, are of little
HORSE. use. The annexed is made like a
broad belt, and is buckled
round the body. The bars are composed of vulcanized India-rubber;
they will yield to the movements of the abdomen, and yet serve as
sutures supporting any pendant flap, while at the same time they
will allow the wound to be dressed without disturbing the bandage.
They also offer the advantage of permitting the attendant to pull one
support aside without removing the whole.
Every part in the horse subjected to much motion when
wounded, should have an adhesive plaster placed over it, and
retained there until the suppurative action is confirmed. By this
means is excluded the atmosphere, which, when this precaution was
neglected, has entered the wound, penetrated between the muscles,
and by distending the body increased the suffering, as well as led to
the worst of consequences.
 Wounds in veterinary surgery rank among the most formidable
cases with which the practitioner has to contend. They are not so
because the flesh of the horse is slower to heal than that of the
human being. Indeed, the scale in this respect inclines toward the
animal; but they are rendered slow to heal and difficult to cure by
two causes. The horse is always impatient of restraint; any effort to
confine the creature is more likely to provoke dangerous resistance
than to induce the slightest symptom of amendment. The quadruped
naturally delights in motion. It was formed for activity. Even when in
its stall the body is never absolutely still; the position is being
changed; the legs are frequently stamped; the head, eyes, ears, and
tail are never quiet. This innate quality retards the union of sundered
flesh. It favors the gravitation of pus between the muscles, and thus
generates sinuses. These are the torments of veterinary surgery.
Could the sinus be anticipated, or in all cases eradicated, the
principal difficulty would be removed; but intelligent as the horse is,
it proves impossible to make the animal comprehend the necessity
for quietude. Hence any trivial accident may lead to injuries of so
extensive a character and so malignant a nature as will set the best
endeavors or the most consummate skill at defiance.
 CHAPTER XV.
OPERATIONS.
The veterinary art is by no means rendered more successful by
the cunning of its stratagems. Many of its objects are accomplished
after the rudest and the most primitive methods. Not one, perhaps,
is more coarse than the present method of casting or throwing an
animal previous to an operation. The reader has only to ask himself
what condition the body must be in when, with the sight blinded, it
is suddenly jerked to the earth; and how far it is fitly prepared by so
violent a practice to be submitted to the knife of an operator?
 THE PRESENT MANNER OF CASTING A HORSE FOR OPERATION.

There are few operations in veterinary surgery which a person of

moderate nerve and average intelligence might not himself perform.
The author has seen gentlemen with titles, and others holding high
rank in the army, indulge in the strange pleasure of singeing living
flesh with the heated iron. But he has never beheld horsemen
handling the knife. The latter would better become their hands than
the first severe and disfiguring instrument, which, however useful it
may have been found in certain cases met with in human surgery,
nevertheless would be well abolished from veterinary practice,
because of its indiscriminate abuse. Firing is employed for every and
for no reason. Now recourse is had to it because the joints are weak.
Then it is adopted because a gentleman is fond of seeing his horses
scored. Next, it is used to gain time, and thus prolong the treatment.
Generally it is brought forward because the practitioner does not
know what else to do. Lastly, it is esteemed the crowning measure
of routine practice.
The author, however, has never been necessitated to resort to so
violent an agent. It is a most unseemly ornament in unprofessional
hands; in this book, which is intended for the general public, the use
of the firing-iron is altogether omitted.
The knife, especially to the animal, is the most humane of
remedies. It often affords instant or immediate relief. The animal
seems to suffer more from the restraint imposed than from the
wounds inflicted. The chief sensation, with all forms of life, resides in
the skin; so that the integument be quickly and effectually divided,
the soft parts underneath have but little feeling. The interference
with these last rather produces faintness or sickness than acute
suffering; the knowledge of which fact will embolden many a
humane person, though the writer trusts it will not be credited by all
who are of an opposite character, since boldness, unrestrained by
humanity, only renders the individual a savage without the savage's
excuse.
Such operations as embriotomy, castration, and lithotomy are
intentionally omitted, from a conviction that no gentleman would
undertake them; and because, in every instance, they had better be
intrusted to a regular veterinary surgeon.
Before undertaking any operation, always reflect on what you are
about to do, and make up your mind how you design to do it.
Irresolution causes more suffering than the most perverted
determination can inflict. It is always well (however much in practice
the operator may consider himself) to first perform the intended
operation upon the dead subject. This is a custom which the writer
invariably adopted; and frequently it has supplied his memory with a
refresher which, in the hurry of practice, was found a most timely
warning.
Never use small knives. Such things look pretty. The sight of a
large blade may appear very ugly; but it does at one movement that
work which an instrument of notching smallness would not in twenty
hacks accomplish. Understand thoroughly that which you are about
to perform, and always choose the tool likely to get through the
business quickly. Periosteotomy cases were formerly sold by
veterinary instrument makers which contained a knife of moderate
doll's dimension. The writer, to accomplish the purpose which that
little knife was specially made for, was accustomed to employ a
bistoury larger than those in ordinary use among gentlemen of his
profession.
Where you anticipate much bleeding, always endeavor, if
possible, to divide the main artery with the first incision. This is by
far the most humane, and therefore the safest practice. The vessel,
being divided, can be taken up, and all further flow of blood thereby
checked. But if the artery be left to the last, it remains to fill the
smaller branches. These are of necessity frequently severed. Each,
as it is cut, bleeds more or less freely; thus the hemorrhage is far
greater, and the operation far more difficult, than if the main trunk
had been secured at the earliest possible period.
Always tie both ends of an artery; because, though the main
stream flows through that portion of the vessel nearest the heart,
yet the other half, being fed by the smaller trunks, and the current
having a tendency to regurgitate, a considerable quantity of the vital
fluid may flow out of the mouth, which, in general opinion, has no
medium of supply.
If, during an operation, you make an accidental incision into a
vessel, either take it up, (which is the better way,) or cut it short off
when there is a chance of its retracting and of the bleeding being
thus arrested. Vessels of large size may, when requisite, be excised
and tied; the vital current being afterward carried on by the
dilatation of the lesser ducts.
To tie an artery it is imperative to secure the end of the vessel;
this, if possible, should be accomplished with the forceps. When the
mouth of the vessel is much retracted, it may be necessary to
employ the knife; but that practice should be viewed only as the last
resort of the proficient surgeon.
The end of the artery being fixed and drawn forth, a piece of
strong silk, thrice twisted, (after the method represented in the
inferior circle of the annexed illustration,) is passed over the vessel.
The silk is then drawn tight, and will generally remain fixed.
However, sad accidents have occurred by operators trusting to so
doubtful a security; for that reason it is always advisable to make
another twist, (as shown in the smaller circle of the illustration,)
which will render the knot secure.
Even a vessel of the second
magnitude may be obliterated,
as the carotid artery or the
jugular vein, without life being
necessarily sacrificed. However,
it is always well to spare these
parts, or when either is lost to
arrange so that the absence of
THE LOUP BY them may entail the least
MEANS OF possible inconvenience upon
WHICH THE ENDS the animal. Thus, if the carotid
OF RTERIES ARE artery be lost, place the food
SECURED.
low down, and thereby aid the
flow of blood to the head. If the
jugular vein be destroyed, then put the fodder high up, that the
current from the head may be facilitated.
Never, on any account, remove any portion of skin which is not
involved in some fearful injury, or separated from its attachments by
the action of disease.
Skin is the part of the body which is never reproduced, and even
the place whence it is absent always heals slowly. However loose the
skin may appear, however disproportioned it may seem after some
tumor has been removed, respect every particle of it. Before the
wound can heal, inflammation must set in. That process ended, the
skin, under its action, will have contracted, and in the end there will
be only sufficient integument to cover the part; whereas, if the
slightest amount be excised, to such an extent there will for a long
time remain a gaping sore.
Never spare the knife. Think well before you touch that tool; but,
having it in hand, assure yourself its edge is sharp, and never do at
two cuts that which might have been accomplished in one.
Always slit up a sinus where such a proceeding is possible. When
the sinus is too long, supposing the pipe to take an internal
direction, as from the withers to the chest, insert a seton with the
guarded seton needle, a representation of which is given below.

THE GUARDED SETON NEEDLE.

The blade of this instrument is generally about two feet long.

Before using it, the cutting head is always retracted by pulling back
the nut at the extremity, and securing it in its place by means of the
screw situated on the middle of the handle. The blade then reposes
upon a blunt companion, and may with impunity be inserted down
any sinus or false canal. Having reached the bottom of the pipe, and
all important vessels being passed, the screw is loosened, and the
projecting end of the blade at the extremity of the handle is struck
forcibly, when the sharp point is driven forward, and this pierces the
flesh.

THE SETON NEEDLE PROTRUDED, AND SECURED WITHIN THE HANDLE

BY MEANS OF A SCREW.
 Behind the cutting head there is a free space. Through that
opening a long piece of tape is threaded, and the instrument is
withdrawn, pulling the tape into the sinus, in which it remains. A
knot is made at either end of the tape; thus a seton is with safety
placed in situations where the depth to be penetrated would defy
ordinary measures, and the vessels to be passed would render such
measures more than doubly hazardous.
The use of a seton is to act as a drain, or to stimulate an
unhealthy canal—to provoke a sinus to secrete healthy pus, instead
of a thin and often a foul discharge—and thus to cause the diseased
pipe to heal or to become obliterated.
When operating, always make your first incision through the skin
rather too large than in the least too small; remember, the division
from within outward occasions much less pain than the separation,
made after the ordinary fashion, from without inward.
Never spare hair; the substance is readily reproduced. It can be
wished to be spared only to conceal the fact of an operation having
been performed. Always refuse to become a party to dishonesty. Do
what is necessary for the proper performance of your office. The
removal of hair, which may otherwise interfere with your sight, is
essential: therefore cut it off, regardless of any wish to the contrary.
Instruct your assistants beforehand how to cast the horse; leave
that business to them: never meddle yourself. The writer has seen
veterinary surgeons, in their operating dresses, push and haul with
the utmost energy. Such silly people have doubtless thought
themselves exalted by this exhibition of violence. It would have been
more to their credit had they devoted half the energy to teaching
their people beforehand. But in what condition must their hands and
temper be after having taken a lead in a struggle with a horse for
mastery!
A surgeon should always be cool. His head should direct his
hand; his knife should be held lightly; his eye should be quick, and
his mind prepared to meet any accident. He should do his office
neatly, and, if possible, without soiling his person. The ripping cut
and the bloody hands alone distinguish the ignorant butcher from
the scientific operator.
During every operation enjoin the strictest silence upon the
spectators. The horse is never vicious, but it is always timid. Sounds
have a powerful effect upon animals which cannot understand
speech. Every word uttered, even in a whisper, should be of
assurance to the sufferer; for the horse is only to be feared in its
efforts to escape from some supposed peril. It becomes mad in its
alarm. It then puts forth its strength and exerts it without regard to
consequences. Man has everything to hope from the fortitude and
noble forbearance of the creature. It responds to kindness with
something more than submission; it answers sympathy by the most
entire confidence and utter dependence. The life, the feeling, the
natural powers are all subservient to the great love which is
embodied in a horse's attachment. There is not among created
beings one which has so large a sympathy; the horse must attach
itself to something; to love seems essential to its being. The stable
in which it is captive the patient prisoner learns to regard, as it were,
a palace. The pace is always more willing when returning to
captivity; freedom has no charm; the field has no allurement to the
horse which has lived any time in the most crimped, confined, and
uncomfortable of stalls. It will quit the spring grass to be fastened
once more in the place to which it has been accustomed and has
grown attached.
Then, however much removed from itself, it must pour the
richest of its affections on some animal, should man, in pride, refuse
to accept the offering. Creatures the most opposite have been the
horse's favorite. How often do we hear of the liking formed between
a goat, a dog, a cat, and the horse! Love has a strange freemasonry
of its own; how else can we account for the larger creature being
able to make its longing understood by the smaller life? There may,
however, be between animals some substitute for language; but we
can hardly suppose any recognized signs exist between birds and
the equine species. Yet a famous animal-painter had a pony which
formed a violent and lasting affection for a bantam cock. These two
used to march side by side up and down the field in which the larger
animal was confined; for so very expansive is the horse's love that it
will embrace not only its abode, but some life, however distant
apparently from its own.
The voice of the person who is accustomed to groom and feed
the animal, if he has been only ordinarily humane in the
performance of his office, will at all times reassure the beating heart
of a prostrated horse. But vast injustice to the animal's better
qualities is done by the mode of casting it. It is violently jerked off
its legs; by a sudden pull it is thrown "with a burster" upon its side.
There it struggles. If mastery sides with the animal, then let the men
be speedy in their flight. The quadruped, in its fear, designs no harm
to any person. It means only to escape from the terrible danger
which encompasses it. Still, it is regardless in its alarm, and may do
more injury than the most evil intention could accomplish. There is
an engraving of the method of casting horses commencing this
chapter. Let the capable reader imagine the effect produced upon
the timid quadruped when it is violently flung upon the earth with a
sound well denominated "a burster."
The horse is much better made to lie down gently, after the
method adopted by Mr. Rarey. Half, and far more than half, the
terror excited by an operation may thus be avoided. The confusion
and bustle, conjoined with violence, which naturally attend "casting,"
must make a lasting impression upon the retentive mind of the
animal, and, we may suppose, must aggravate the pain, thus
materially endangering the result of an operation. The hobbles may
be fixed quite as readily when the horse is down as when the animal
is standing. Nay, they may be fixed more readily, as the horse, when
down, has lost three-fourths of its power.
Mr. Rarey's method of throwing the most unruly animal is thus
described by that gentleman:—
"Everything that we want to teach the horse must be
commenced in some way to give him an idea of what you want him
to do, and then be repeated till he learns it perfectly. To make a
horse lie down, bend his left fore leg and slip a loop over it, so that
he cannot get it down. Then put a surcingle around his body, and
fasten one end of a long strap around the other fore leg just above
the hoof. Place the other end under the surcingle, so as to keep the
strap in the right direction; take a short hold of it with your right
hand; stand on the left side of the horse, grasp the bit in your left
hand, pull steadily on the strap with your right; bear against his
shoulder till you cause him to move. As soon as he lifts his weight,
your pulling will raise the other foot, and he will have to come on his
knees. Keep the strap tight in your hand, so that he cannot
straighten his leg if he rises up. Hold him in this position, and turn
his head toward you; bear against his side with your shoulder—not
hard, but with a steady, equal pressure—and in about ten minutes
he will lie down. As soon as he lies down he will be completely
conquered, and you can handle him as you please. Take off the
straps, and straighten out his legs; rub him lightly about the face
and neck with your hand the way the hair lies; handle all his legs;
and, after he has lain ten or twenty minutes, let him get up again.
After resting him a short time, make him lie down as before. Repeat
the operation three or four times, which will be sufficient for one
lesson. Give him two lessons a day; and when you have given him
four lessons, he will lie down by taking hold of one foot. As soon as
he is well broken to lie down in this way, tap him on the opposite leg
with a stick when you take hold of his foot, and in a few days he will
lie down from the mere motion of the stick."
What prevents the hobbles being buckled on? What prevents all
necessary arrangements being carried out? What, indeed, but the
stubbornness inseparable from ignorance! Veterinary surgeons, as a
rule, are not an educated class. In proportion as their information is
limited, so is their adherence to established custom likely to be
intractable.
There are, besides the hobbles, two other inventions designed to
limit the capability of resistance. One is the side line. A soft collar is
put over the horse's head and a hobble is fastened to the foot it is
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