NisrUNITED STATES

DEPARTMENT OF COMMERCE

NATIONAL INSTITUTE OF STANDARDS

AND TECHNOLOGY

NATL INST. OF STAND i TECH R.I.C.

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PUBLICATIONS NIST Technical Note 1338
NATIONAL INSTITUTE OF STANDARDS

TECHNOLOGY

Research Information Center

Gaithersburg, MD 20899

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Dielectric Characterization

and Reference Materials

Richard G. Geyer

Electromagnetic Fields Division

Center for Electronics and Electrical Engineering

National Engineering Laboratory

National Institute of Standards and Technology

Boulder, Colorado 80303-3328

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U.S. DEPARTMENT OF COMMERCE, Robert A. Mosbacher, Secretary

NATIONAL INSTITUTE OF STANDARDS AND TECHNOLOGY, John W. Lyons, Director

Issued April 1990
National Institute of Standards and Technology Technical Note 1338

Natl. Inst. Stand. Technol., Tech. Note 1338, 124 pages (Apr. 1990)

CODEN:NTNOEF

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1990

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, DC 20402-9325
CONTENTS

Page

ABSTRACT 1

1. INTRODUCTION 2

2. NATIONAL NEED FOR ENHANCED DIELECTRIC METROLOGY AND

REFERENCE MATERIALS 3

3. DESIRABLE PROPERTIES OF REFERENCE MATERIALS .... 7

4. ELECTROMAGNETIC CHARACTERISTICS OF MATERIALS 11

4.1 Physical Concepts Governing Electromagnetic Behavior 11

4.1.1 Anisotropy 12

4.1.2 Class A Dielectrics 13

4.1.3 Polar Versus Nonpolar Materials 14

4.1.4 Complex Material Constituent Properties 16

4.1.5 Distinction Between Ohmic Conductivity and

Dielectric Loss Factor or Between Faradaic

Diffusion Transport and In-phase Polarization

Phenomena 17

4.1.6 Quality Factor of Dielectrics 18

4.2 Polarization Mechanisms Intrinsic to Materials 19

4.3 Dispersion and Relaxation Processes in Materials 22

4.3.1 Debye Relaxation . 24

4.3.2 Generalized Relaxation Distributions 25

4.3.3 Universal Dielectric Response 27

4.3.4 Relationships Between Real Effective Permittivity

and Loss Tangent 28

4.3.4.1 Materials With Loss Factors That Are

Constant With Frequency 2! 4.3.4.2 Absorbent Materials Having Single

Relaxation Times 30

111
Page

4. ELECTROMAGNETIC CHARACTERISTICS OF MATERIALS (Cont.)

4.3.4.3 Generalized Relationship for Any Dielectric

Material Having an Arbitrary Number of

Relaxation Times 33

4.3.4.3.1 Example of Hilbert Transform

Relationships in Prediction

of Dielectric Properties for

Absorbent (Dispersive)

Materials 39

4.3.5 Effect of Temperature Changes 44

4.4 Other Sample Characteristics Important to the Search for

Reference Materials 51

4.4.1 Sample Homogeneity 52

4.4.1.1 Inhomogeneous Sample in Field of Arbitrary

Dielectric Measurement Fixture 54

4.4.1.2 Coupling of Electromagnetic Field Components ... 58

4.4.2 Isotropy 66

4.4.2.1 Isomorphism 68

4.4.2.2 Polymorphism 75

4.4.3 Hardness 78

4.4.4 Tenacity 82

4.4.5 Wettability 83

4.4.6 Piezoelectric Versus Pyroelectric 84

5. SUITABLE DIELECTRIC REFERENCE MATERIALS 85

6. CONCLUSIONS 95

7. REFERENCES 108

8. APPENDIX 110

IV
ABSTRACT

Dielectric reference materials are analyzed with respect to

fundamental requirements of linearity, homogeneity and isotropy.

Generalized frequency- and temperature -dependent dispersion

relations are presented which allow the prediction of broadband

dielectric behavior from limited measurement data, determination

of valid modal field structure in cavity or waveguide fixtures,

and identification of discrepancies and errors in measurement

data. An approach for examining the influence of deviations of

sample homogeneity on a precisely specified electromagnetic field

structure is outlined, and sufficient conditions for isotropic,

uniaxial, or biaxial anisotropic dielectric behavior are reviewed

in terms of a material's chemical lattice physics. These characteristics direct the choices of suitable reference materials

useful for confirming or improving the accuracy of dielectric

measurements

Key words: anistropy; Debye material; dielectric; dispersion;

homogeneity; microwave complex permittivity; reference materials;

relaxation.
1 . INTRODUCTION

There is a need to know the dielectric properties of many different

materials in order to design microwave and millimeter wave devices. There are

additional needs for the validation and error analyses of dielectric measurement techniques and for the distribution of standard reference materials.

Standard reference materials permit the confirmation and improvement of the

accuracy of measuring procedures.

Materials, whether in the solid, liquid or gaseous states, may be

electrically nonlinear, anisotropic, inhomogeneous , and dispersive both with

respect to frequency and temperature. Because of these intrinsic complicating

factors, it becomes difficult to ascertain the accuracy and precision with

which dielectric measurements are made until reference materials are developed

whose properties are sufficiently well-known so that they can be used as

measurement standards.

The organization of this report is as follows. Section 2 contains a

general overview of the national need for dielectric metrology and reference

materials. Desired properties of ideal dielectric reference materials are

described in section 3. Fundamental electrodynamic behavior of materials is

reviewed in section 4.

Section 4 is critically important to the understanding of dielectric

measurements and the physical qualification of suitable reference standards.

Materials are described in terms of their complex constituent properties in an

electric or magnetic field. Frequency- dependent polarization mechanisms are

discussed, and generalized relaxation relations are derived that are applicable to the rf and microwave regions. These relations allow the predictive

broadband characterization of any material, provided suitably sampled
dielectric property measurements are made as a function of frequency. For

most materials the dielectric loss measurement error is much greater than the

error in determination of real effective permittivity. Hilbert transform

relations are derived for determination of the dielectric loss factor from

discretely sampled real effective permittivity data. These relations, which

are not limited to any portion of the frequency spectrum, are applied to

frequency -sampled permittivity and dielectric loss factor data for an

absorbent material having a single relaxation time.

The effect of temperature changes on the electrical properties of

materials is next analyzed through basic concepts from statistical thermodynamics. Lastly, the dependence of important electrical properties of

isotropy and uniaxial or biaxial anisotropy on fundamental molecular lattice

symmetries is reviewed. Polymorphous phase changes can occur with temperature

that alter the isotropic nature of materials, and it is important to recognize

multi -phase lattice structure changes as well as coefficients of thermal

expansion in the choice and use of dielectric reference or transfer standards.

Suitable low- loss dielectric reference materials that exhibit low to high

polarizability are given in section 5 on the basis of measured data taken over

a broad range in both frequency and temperature. The fundamental electromagnetic characteristics discussed in sections 3 and 4 are used as guidelines

in this selection. Finally, section 6 summarizes the results of this study

and makes recommendations for future work.

2. NATIONAL NEED FOR ENHANCED DIELECTRIC METROLOGY AND REFERENCE MATERIALS

It is appropriate to review the national need and necessity for improved

dielectric materials characterization. In parallel with dielectric
characterization will evolve the use of reference materials whose properties

are well-known and quantified parametrically with temperature, frequency,

mechanical and chemical stress, aging, etc. that they serve as basis points

for application and for measurement standards.

Components fabricated with dielectics are critical to the performance

of all electronic equipment used in communications, antennas and antenna

housings, navigation, power generation and distribution systems, guidance and

instrumentation control systems, radars, computers, sonars, frequency standards, and a large variety of rf, microwave and optical sensing devices. The

continued migration to higher frequencies and the miniaturization of electronic equipment has meant that the normal operating temperature range over

which dielectric component behavior must be known and perform satisfactorily

has generally increased. There is a need both to know and to predict degradation and stability of dielectric materials over this range. Degradation of

component dielectric materials leads to drastic losses in equipment reliability. In order to have increased reliability, all components must have more

accurate ratings, improved design, and better quality control that stem from

the development and more intelligent use of better dielectric materials.

These goals can only be attained if the metrology for characterizing

dielectric behavior concomitantly becomes more precise, with quantitative

specification of procedure accuracies for the method(s) used.

The requirement of reliability for dielectric component devices

necessitates a knowledge of measured performance under a wide range of

qualifying conditions. Some of these are:
Frequency and Strength of Applied Field

Change in dielectric constant and absorption with frequency;

linearity as a function of applied field strength.

Temperature

Change in dielectric characteristics due to thermal relaxation,

volatilization, phase changes, and possible breakdown. Increasing

miniaturization generally means new developments for dielectric

components. It also necessitates more precise and enhanced dielectric

metrology capabilities. How might dielectric components be designed

and characterized that withstand higher temperatures due to increased

numbers of dissipative elements in component electronics or more

severe environments?

Relative Hvimidity from to 100 Percent

Critical components must have high insulation resistance for high

voltage and special circuit applications; they must have nonwetting

surfaces and be arc resistant.

Resistance to Shock and Vibration

Fracturing of dielectric materials due to vibration can cause total

loss of power generation for communication links, radar systems and

sonar devices. Embrittlement of dielectrics as a result of exposure

to corrosive environments leads to fracture followed by electrical

failure. How can the sensitivity to shock and vibration be predicted

or measured? Plasticized resins comprising some dielectric components

volatilize as a result of heat and moisture. What dielectric
materials can be substituted that have similar electrical properties

but that do not volatilize? How can these substitutes be measured and

with what accuracy?

• Resistance to Surface Contamination

Failures occur on insulating surfaces, printed circuit boards, and

thin film dielectric components. How can these components be improved

by glazing or surface treatments? What is the effect of various

contaminants on the electrical behavior of dielectric surfaces and how

might these effects best be measured so as to control degradational

environmental factors?

• Service Life

Ultra- low loss ceramic materials are often used in critical highfrequency circuits. What is the load life of ceramic capacitive

elements? At what point does dielectric breakdown occur, particularly

at microwave frequencies? What are the chemical and physical factors

and mechanisms which control degradation of a dielectric under

prolonged exposure to voltage stress and high temperature?

Resistance to Atomic Radiation

How does exposure to atomic radiation affect the properties of

dielectric components? To what extent does radiation affect the

impedance characteristics of field measurement probes?

This discussion is only a brief review of design requirements that of and

by themselves justify an important need for standards in the form of dielectric reference materials and measurement methods. Many other requirements
could be made when specific applications are considered. For example,

conductive elastomers are used for draining off electrostatic charge that

collects on insulating surfaces (antennas, radomes) . It is important to know

what changes occur in the dielectric properties of these materials due to

heat, aging, and weather exposure. In addition, dielectrics must retain

stable and dependable properties when subjected to various processing and

fabrication activities. Therefore research and development addressed to

dielectric nondestructive evaluation are important and practical issues,

particularly with regard to quality control.

It is often stated that specifications for thermal stability, exceptional

dielectric strength, low dielectric loss, and high resistance to environmental

conditions are unnecessarily stringent. However, these specifications are

justified not only by safety factors, but also by a history of a dielectric

materials failure in service. Specifications should become more conservative

and with this increase in material specifications will come a corresponding

need for more precise dielectric measurements together with reference

materials that are suited for both application and test procedures

3. DESIRABLE PROPERTIES OF REFERENCE MATERIALS

Ideal reference materials usually have several characteristics; some are

of primary importance and others of lesser or secondary value. The characteristics of an "ideal" dielectric reference material are given in table 1.
Table 1. Characteristics of an Ideal Dielectric Reference Material

Primary Electrical Attributes

• Linearity

• Homogeneity

• Isotropy

Secondary Nonelectrical Attributes

Thermal Expansion

Softening Point

Moisture Absorption

Hardness (Machinability)

Chemical and Mechanical Stability

Availability

Cost

The principal requirements for a dielectric reference material are that

it behave linearly in an applied electric field, be homogeneous and isotropic

over the frequency range of interest, and be insensitive to the environment in

terms of temperature, chemical changes, or aging. A candidate reference

material must then be understood well enough to avoid any problems with

respect to these requirements. It is essential therefore that measurement

techniques be analyzed in sufficient detail that bounds on measurement errors

can be specified. In this way deviations from homogeneity, say, of a

candidate material can be distinguished from measurement inaccuracies.

Several dielectric constant ranges are describable in terms of material

application in the microwave region. A reference material for each of these

ranges would be useful in metrology efforts. The general ranges are:
Low Dielectric Constant, Low Loss (Cp < 4, tan5 < 0.001)

This type of material is used to reduce distributed capacitance effects

in all interconnecting, mounting, or packaging media. A dielectric

reference material of this type would be very useful for calibrating

measurement systems that are concerned with the dielectric characterization of radomes or antenna housings, substrates for millimeter-wave

antenna systems, and packaging media used for enclosing solid explosives

or propellants. Generally, it would be useful to have a low e^, tanS

reference material that is moldable or extrudable, that is stable over a

wide range in temperature, and that has good working strength. For

temperatures up to 250°C an organic reference material may be used; for

applications above 250°C an inorganic material such as a low-density

ceramic holds promise.

High Dielectric Constant, Low Loss (e^ > 10, tanS < 0.001)

A reference material of this type is useful as a calibration standard for

miniature capacitive elements or for substrate materials used in high

frequency microstrip transmission lines. For these applications thermal

stability and low temperature coefficient of €p are highly desirable.

Materials for these uses must be capable of fabrication into thin

flexible films on substrates. When dielectrics of this type are used for

microstrip transmission lines, they should also have minimal surface

defects, since the surface roughness of microstrip transmission lines at

frequencies of 1 GHz and above strongly affects the attenuation of the

line.
Very High Dielectric Constant, Ultra-Low Loss (Cr > 100, tan5 < 0.0002)

A reference material having this dielectric property would be useful in

the characterization of capacitive elements in critical high-frequency

circuit applications, where materials of high dielectric constant and

ultra- low loss are needed. These materials typically must have Cp > 100

and have loss tangents < 0.0005 at 1 MHz and above, over a temperature

range from -40° to 100° C. They also must have volume resistivities on

the order of 10^^ fl-m from -40° to 200°C and possess high dielectric

strengths over the same temperature range.

Reference materials for the dielectric ranges above could be de Jure

standards for application. In all three cases, low-loss to ultra-low loss

is important over a broad range in frequency. Depending on the temperature

range of application, reference materials may or may not be organic (plastics)

compos itionally. The materials are generally of Cole -Cole type over the

frequency range of interest, with negligible relaxation; such relaxation

behavior is discussed on section 4.

Although the characteristics of an ideal dielectric reference material

are divided into primary electrical versus secondary nonelectrical attributes,

this distinction is artificial. In fact, all properties except availability

and cost depend on the molecular (chemical) lattice physics of the material.

Understanding the characteristics of ideal dielectric reference materials

necessitates a general discussion of electromagnetic characteristics of all

materials, polarization mechanisms intrinsic to materials, and temperatureand frequency -dependent relaxation processes. In addition, it is necessary to

consider fundamental lattice structures in searching for reference materials

10
that have preferred isotropic behavior, that are nonpolymorphic , and that have

suitable hardness, tenacity, and wettability features.

4. ELECTROMAGNETIC CHARACTERISTICS OF MATERIALS

4.1 Physical Concepts Governing Electromagnetic Behavior

Any material is electromagnetically characterized by its permittivity £

(F/m) , magnetic permeability /x (H/m) , and electrical conductivity o (S/m)

Maxwell's equations, together with the constitutive equations relating field

quantities in terms of material properties, completely govern electromagnetic

wave propagation and behavior in that medium.

The constitutive equations for a linear, homogeneous and isotropic medium

may be expressed in the frequency domain as

B = /x H , J = a E , (1)

and D = e E ,

where the magnetic induction B (Wb/m^) is related to the magnetic field

—>• -V H (A/m) by the magnetic permeability; the current density J (A/m ) is

related to the electric field E (V/m) by the conductivity; and the dielectric

displacement field D (C/m^) is related to the electric field by the permittivity. Any deviation from linearity is usually included by making e, /x, or a

field dependent. For anisotropic media, €, /x, or a is a second rank tensor as

opposed to just a scalar function of frequency or simply a constant. For

inhomogeneous media €, /x, or a is a function of spatial coordinates.

11
4.1.1 Anisotropy

When a dielectric is placed in an electric field E , the material becomes

polarized, and the dielectric displacement field is often written

D = e^ E + P , (2)

where P is defined as the electric polarization of the material (dipole

moment per unit volume) , or

P = e, X E ; (3)

X, the proportionality constant, is called the electric susceptibility, and

the factor e^ (free space permittivity equal to 8.854 x 10"^^ F/m) is included

in eq (3) to make x dimensionless . Then eq (2) becomes

D = e^ (1 + X) E (4) or

D = e^ e* E , (5)

where €* = 1 + x is called the dielectric coefficient or complex permittivity

of the medium relative to a vacuum . The presence of a dielectric always

affects the ratio of D to E by a factor of Cp . For linear materials the

dipole moment induced in a dielectric by an external field E is directly

proportional to E . As long as the electrical properties of the dielectric

-* -* are independent of direction, it is Isotropic; that is, P and E are

collinear. For an anisotropic material, however, the polarization (or charge

separation) obtained when an electric field is applied along one coordinate

axis will be different than that produced by the same field applied along a

different coordinate axis. Quantitatively, this can be expressed by writing

12
P = e^ X

• E , (6)

where X = [x^ ii + Xy jj + X^ kk] and Xx- Xy, X^ are the principal

components of anisotropy of the electric susceptibility tensor expressed in

dyadic form. For isotropic materials Xx = Xy = X^, and eq (6) reduces to

eq (3). Equation (6) shows that P and E are not collinear when Xx ^ Xy = X^

or when Xv = Xw ^ X:, or when Xv ^ X„ =^ X, (for two- or three-dimensional

anisotropy), so that the electric susceptibility tensor may, in general, be

viewed as an operation which takes a vector E and converts it into a new

vector P which is not collinear with E

4.1.2 Class A Dielectric Materials

If the nonpermeable dielectric material is not only linear and isotropic,

but also spatially uniform (or homogeneous) , we categorize it as a Class A

dielectric. Spatial uniformity means simply that all spatial derivatives of

the susceptibility tensor are zero. Class A dielectrics, whether in solid,

liquid, or gaseous phases, make suitable primary reference materials provided

the material characteristics possess long time stability (as a function of

ambient conditions). However, material dielectrics that are linear,

isotropic, and homogeneous when placed in an electric field at one frequency

may not be isotropic or homogeneous at another frequency or under different

temperature or pressure conditions. Similarly, dielectrics that behave

linearly when placed in electric fields of low strength may not be linear in

high strength fields (or at high temperature). Consequently, Class A

dielectrics should be qualified as to their electrical characteristics with

respect to frequency, polarization, and magnitude of applied field strength,

as well as temperature and pressure.

13
4.1.3 Polar Versus Nonpolar Materials

Dielectric materials may also be divided into one of two categories:

polar and nonpolar. A nonpolar material (such as inert or rare gases) is

simply one that contains no (equivalent) dipoles (or separation of charge)

when the material is not in an electric field. A polar material, on the other

hand, possesses permanent polarization, even in the absence of an electric

field, due to its molecular structure. Polar materials have permanent dipole

moments at the microscopic or molecular level. A common polar material is the

water molecule, which has the structure illustrated in figure la.

H,0

(a) (b)

Figure 1. The structure of the water molecule (a) and

its equivalent dipolar representation (b)

14
Hydrogen has one valence electron and oxygen has six, so that there is a

tendency for electrons to form a closed shell having effectively eight

electrons around the oxygen. This results in covalent bonds similar to those

in the hydrogen molecule. In addition, the atoms become charged because of

this electron transferral, and two dipoles are established as portrayed in

figure lb. The permanent moment of the HjO molecule is the vector indicated

^y ^H o ^^ figure lb. The HjO molecule may be contrasted with the COj molecule

shown in figure 2. The individual moments of each CO pair cancel, yielding a

zero permanent moment. In general, any distribution of charge may be

described in terms of its multipole moments [1].

^co Pco © © ^

C Pco2=0

(a) (b)

Figure 2. Structure of the COj molecule (a). Net dipole moment is zero (b) .

The relevance of this discussion to dielectric material properties is

that the existence of permanent dipole moments on the molecular level gives

rise to a type of polarization mechanism when an electric field is applied

which is frequency dependent. Without an applied electric field in the case

of the water molecule, the individual molecular dipole moments point in random

directions, so that macroscopically their vector sum vanishes. In the

presence of the applied electric field, E, though, there is a pronounced

15
tendency of the dlpoles to line up in the direction of E , creating an

orlentational polarization whose magnitude can be computed [2].

4.1.4 Complex Material Constituent Properties

The solution of Maxwell's equations yields all of the quantities that

describe the propagation of electromagnetic waves in terms of the propagation

constant jk where

k^ = w/i (we - ja) (7)

for expC+jwt) time dependence for angular frequency w and time t.

In general, the constituent electrical properties may be written as

complex quantities; that is, for exp(+ja;t) time dependence,

e = e' - je" = [e^ - je^] e^ = e^e^ ,

a = a' + ja" , (8)

and n = n' - j/i" = [/x^ - j/i'^] n^ = /i*/ig .

(Note that for anisotropic materials each component of the e, o, or /i tensor

matrix is, in general, a complex quantity, depending on the nature of

anisotropy.) The imaginary part of the propagation constant contains all

necessary information about energy loss in a material medium during wave

propagation. If magnetic properties are ignored, we may consider only the

complex forms of e and o in eq (7)

we - ja = w (e' - je") - j (a' + ja") = (a" + we') - j (a' + we") . (9)

16
Here (we' + o") may be considered an effective permittivity and (a' + we") as

an effective conductivity. The term (a' + jcr") physically represents carrier

transport due to ohmic and Faradaic diffusion mechanisms, respectively,

whereas (e' - je") represents dielectric relaxation mechanisms. From eq (9),

the loss tangent is simply defined as

tanS ^- (* ^ !> ^ f^r^ff- <^°>

where ^ is the phase between E and J. If there are no dielectric losses,

e" -» 0. Similarly, if there are no Faradaic losses, a" -* 0; hence,

tanS = -^ , (11) Wc

which describes losses physically due to ohmic conductivity.

4.1.5 Distinction Between Ohmic Conductivity (a') and Dielectric Loss Factor

(e") or Between Faradaic Diffusion Transport (a") and In- Phase

Polarization Phenomena (e')

It is often stated that it is artificial to make distinctions between

ohmic carrier transport phenomena and dielectric loss characteristic of a

material when that material is placed in a time-varying electric field.

Actual dielectric measurements are indifferent to the underlying physical

processes. To the extent, however, that physical and chemical processes are

understood, distinctions can be made and materials designed to have certain

electromagnetic characteristics.

The lack of distinction between two loss mechanisms from only measurement

data can be seen by inspection of eq (10) . Another way to see the relation

between conductivity and the imaginary part of the permittivity is to write

Ampere's law,

17
V X H = J + 1^ . (12)

at

where J is the conduction current in a material medium due to an applied

electric field. For sinusoidal fields, eq (12) can be rewritten as

VxH = a E + e -^

at

= j'^ [e;, - j(e-^ + 4r^i^oE . (13)

Hence, without other physical information it is evident that a conductivity a

is equivalent to an imaginary part of 6 given by

^R = 7^ ' (1^)

we_

'

so an equivalent form of eq (10) is

tan5 = -^ = loss current ^5^

e ' charging current

4.1.6 Quality Factor of Dielectrics

The quality factor Q at a given frequency f of a dielectric is defined as

the inverse of the loss tangent,

1 e' we' E.^

s_

tan5 e" we" K'

27rf ;

^ \

18
^ average energy stored per half cycle

energy dissipated per half cycle

VA

W

(16)

The quality factor Q can be used as a descriptive characteristic of any

dielectric material.

4.2. Polarization Mechanisms Intrinsic to Materials

The previous discussion shows that the relative permittivity of a

material is the permittivity of the material normalized with respect to

the permittivity of a vacuum. We can describe the electrical constituent

properties of a material medium by the complex dielectric constant which, for

isotropic material, may be written as €*(x,y,z) = e'(x,y,z) -j e"(x,y,z),

where e' is the effective permittivity and £" contains all of the information

about energy loss (that due to both dielectric losses and ohmic conductivity)

in the material during wave propagation.

As an aside, we recall that a pulse or "signal" of any specified initial

form can be constructed by superposition of harmonic wave trains of infinite

length and duration. The velocities with which the constant-phase surfaces of

these component waves are propagated depend on the propagation constant, or on

the parameters 6, /i, and a. If the medium is nonconducting and the quantities

e and \i are independent of the frequency of the applied field, the phase

velocity is constant and the signal is propagated without distortion. The

presence of a loss mechanism, however, yields a functional relation between

the frequency and phase velocity, as well as between frequency and attenuation. Hence in a lossy or absorptive medium the harmonic components suffer

19
relative displacements in phase in the direction of propagation, and the

signal arrives at a distant point in a modified form. The signal is dispersed

and attenuated, and a mediiom in which the phase velocity is a function of

frequency f (or in which the complex dielectric constant e* is a function of

frequency) is said to be electrically dispersive.

The quantity e'(f;x,y,z) is a measure of the amount of polarization of

the material. There can be a number of different polarizing mechanisms

present, each having a characteristic relaxation frequency and dielectric

dispersion centered around this relaxation frequency. At the relaxation

frequency there is maximal absorption. Figure 3 illustrates the dispersions

of e' (and a) that may be observed in materials in the frequency range 10^ to

10^^ Hz. At the highest frequencies, the polarizing species in a material are

the electrons. Electronic polarization occurs when an applied electric field

causes a net displacement of the electron cloud of an atom with respect to its

nucleus. At frequencies below about 10^' Hz, there is also a contribution

from atomic polarization. Atomic polarization occurs in structures

(molecules, solutions, etc.) in which atoms do not share electrons equally and

electric fields displace the electron clouds preferentially towards the

stronger binding atoms. It also occurs when charged atoms are displaced with

respect to each other. Dipolar polarization, that is, the orientation of

polar molecules (molecules with asymmetric charge distributions) , occurs at

frequencies below about 10^° Hz.

20
< ^

CO •>. o

1—

(

) o =)

C ) Q

CXI \—

o

O

o

UJ

1 en

LU (J

Q

Maxwell-Wagner (Interfacial)

Polarization

Dipolar (Orientational)/'^

/

Atomic (Ionic)

Polarization « Electronic

Polarization ^ ^Conductivity

I 10^ 10' 12 10" 10

FREQUENCY (Hz)

10 15

Figure 3. Dielectric dispersion for various types of polarization.

At frequencies below about 10^ Hz, there are various types of charge

polarization which may be collectively referred to as Maxwell -Wagner

mechanisms [3,4]. One of these, interfacial (space-charge) polarization,

occurs when migrating charge carriers are trapped or impeded in their motion

by local chemical or electric potentials, causing local accumulations of

charge and a macroscopic field distortion. Another low- frequency mechanism

that can occur is due to mixtures of materials having differing electrical

properties (such as conducting spheres imbedded in a dielectric) . Several

different equations are available to describe the resultant properties [5,6]

for various geometries of the imbedded conductor: conducting spheres or rods

in a dielectric, alternating layers of dielectrics and conductors, etc. The

common cause of these effects is the distributions of charge that occur at

21
conductor-dielectric boundaries and the resultant action under applied

electric fields which can yield very large low- frequency dielectric constants.

Still another dispersion mechanism for dielectric behavior at low

frequencies, which is often distinguished from Maxwell -Wagner effects, is that

which occurs in colloidal suspensions [6] . Maxwell -Wagner effects occur when

the charge around conducting particles in a dielectric medium is a thin

coating which is much smaller than the particle dimensions [7]; the charge

responds to an applied electric field independently of the charge on nearby

particles. In colloidal suspensions, on the other hand, the charge layer is

on the same order of thickness or larger than the particle dimensions; hence

it is affected by the charge distributions of adjacent particles. The theory

of dispersion phenomena in colloidal suspensions is presently a fertile area

of research. Dukhin [7] has shown that colloidal responses result in far

higher low- frequency dielectric constants than those resulting from typical

Maxwell -Wagner mechanisms, with dielectric constants on the order of 10^ not

uncommon.

4.3 Dispersion and Relaxation Processes in Materials

Polarization processes occurring in material media as a result of

electromagnetic wave propagation are physically damped by either resonance or

relaxation. We recall that resonance is the state of a harmonic oscillator

when being driven at its preferred frequency. Relaxation, on the other hand,

is the state of a critically damped or overdamped oscillator. The effects on

£', e" of these two differing types of dispersion and absorption processes,

which occur in dielectric materials, are shown in figure 4.

22
log f log f

(a) Relaxation (b) Resonance

Figure 4. Two differing types of dispersion and absorption processes

occurring in dielectrics as a function of frequency.

At microwave frequencies, we are principally dealing with dipolar

or orientation polarization phenomena. In this case, the frequency is

sufficiently low so that the rotation of polar molecules has time to take

place. At a frequency of w = 1/T , €' decreases because the individual dipoles

can no longer keep in step with the applied field. The relaxation time T

represents the time required for the dipoles to revert to a random distribution. This is a diffusion process which is represented by figure 4(a).

Atomic and electronic polarization processes, on the other hand, take place in

the infrared and optical portion of the spectrum (1 THz and above) and lead to

the resonance- type dispersion and absorption phenomenon represented by

figure 4(b). A given medium may display any or all of these four

characteristic polarization phenomena, depending on its composition and

molecular or atomic structure.

23
Relaxation processes are those observed in dielectric materials at

microwave frequencies and below. Thus, it would be useful to consider some

relaxation models. The relaxation models discussed here are based on the

general equation of charge motion,

q + ifia)-' q + (/xe)"^ q = , (17)

where q is the charge and • represents differentiation with respect to time.

All derivatives are with respect to time. Another relaxation model is based

on the diffusion of charged ions whose concentration is spatially variable.

In this case,

^' Q (t;x,y,z) + ^

Q (t;x,y,z) + ^Q (t;x,y,z)

5^2 - V ' -' ' 5y2 - ^ ' -' ' Q^2

= I

-^ Q (t;x,y,z) + | Q (t;x,y,z) . (18)

where Q, the concentration of charged ions, is a function of geometry and

time. K(t) is the diffusion coefficient and r; is a constant. For the latter

case, spatial derivatives must be taken in determining diffusion relaxation

which, in terms of electrical circuit analogues, lead to generalized

distributed impedances (as opposed to lumped impedances) and nonlinear

behavior [8]

.

4.3.1 Debye Relaxation

Materials having single relaxation time constants are called Debye

materials. The complex permittivity in a Debye material is given by [9,10]

24
e' - je" =

^oo 1 + JWT + 1

=

^cx, 1 + oj't'

-^ 1

(19)

where e^ is the measured dielectric constant at zero frequency

(€j J, = GgCp) , and 6^ is the relative dielectric permittivity at infinite

frequency (e^^^^^^^g = £ 6^) . The derivation of the complex permittivity as

a function of frequency in any dielectric material having only one relaxation

time is given in the Appendix. In general, single relaxations are seldom

observed. Multiple relaxations or distributions of relaxations are instead

found, as we would expect from our discussion on polarization mechanisms.

4.3.2 Generalized Relaxation Distributions

Wyllie [11] has given an expression for material media in which multiple

relaxations are found. In this case, the complex permittivity may be written

oo D(T)(1 - JWT)

e' . je" = e^ + (e, - e^) f "^'^^" ' -^"'

dr , (20) °°' I 1 + U)' 7'

where D (T) is the time constant distribution function normalized such that

ooJ D(r) dT = 1 . o

One of the most commonly observed simple relaxation distributions in

lossy media at microwave frequencies and below is the Cole-Cole distribution

[10]. In the Cole-Cole distribution, eq (20) reduces to

e' - je" = e^ + —^^—^^^—- , (21)

1 + (jWT)

25
where < m < 1. The loss tangent for the Cole-Cole distribution is

tanS = -^ =

€'

eiury-"" sin[(l-in)f]

1 + ^ + (2 + e)(uTy-"' COS [(l-m)f ] + (wT)2<'-'"'

(22)

where 9 = (€ - e )/e . The ra = case corresponds to a Debye material (single

relaxation) . The m = 1 case corresponds to an infinitely broad continuous

distribution (one having no relaxation). In the latter case the imaginary

part of the complex permittivity disappears, and the real part becomes

frequency independent.

The Cole-Cole distribution corresponds to a symmetric distribution of

relaxation times of width m, VThereas a Debye material yields a plot of e"(e')

that is a semicircle whose center lies on the e" = axis, a Cole-Cole €"(£')

plot is a semicircle whose center lies below the horizontal e" = axis, on a

line drawn from (€' = e^, €" = 0) that makes an angle of mW/2 with the

horizontal axis. This is shown in figure 5.

i

i

Debye Cole-Cole

Figure 5. e" versus €' plots for Debye and Cole-Cole materials

26
In practice it is often difficult to access the actual form of the

distribution function from dielectric data; however, its width, principal

relaxation time T , and symmetry can be determined. Furthermore, the actual

power- law frequency dependence of the complex permittivity can be found by

suitably sampling the e" (£') function in frequency. A corollary to this

statement is that a number of differing metrological techniques would be

necessary to characterize completely an arbitrary dielectric material.

Finally, fairly simple relations describing the functional relation of e* with

frequency arise from relatively complex distribution functions. For example,

the relaxation time distribution function for a Cole-Cole material is

D(r) = — "^"'"^

(23)

T [27r cosh [(1-m) In t/t^] - cos mn]

4.3.3 Universal Dielectric Response

In addition to the Cole-Cole expression, there are three other empirical

relations commonly used to describe a non-Debye response. These are the

Cole-Davidson [13], the combined Cole-Cole, and the Williams -Watkins [14]

expressions. A characteristic feature of all the above empirical relations,

besides being based on eq (17) , is that at frequencies away from the relaxation frequency they reduce to expressions showing a power- law dependence on

frequency for both e' and e". This common characteristic led Jonscher [15,16]

to define this power-law dependence as the "universal dielectric response";

that is,

€' = Kw'^ , (24)

where K and c are constants (c > 0) that depend on the material.

27
4.3.4 Relationships Between Real Effective Permittivity and Loss Tangent

4.3.4.1 Materials With Loss Factors That Are Constant With Frequency

The generalized relaxation given by eq (20) can be used to derive a

relation between values of loss tangent and real effective permittivity.

Equation (20) can be written

00 17/ \

and e"(a;) = J /^^^f, dr . (26)

o 1 + (JJ T^

The essential model posed by eq (25) and eq (26) is that a dielectric

consists of dipoles which have a range or continuum of relaxation times. Over

a restricted frequency range, measured values of the loss factor e" for some

dielectrics are nearly constant, or approximately independent of frequency.

One of the simplest relaxation distributions which can lead to this result is

a simple inverse power law of the distribution function F(T) with relaxation,

that is

,

F(T) = F/T, r # , (27)

where F^ is constant.

Then

and

00 e'(w) - € = F„ r — (28)

T')

oo

O

J. > U/ I

28
The integrals in eqs (28) and (29) are in standard form [17] and can be

reduced to

and

^'('^) - ^oo = y ^^ ^

e" = F„ tan-^wr I = F^ I

(30)

(31)

For two values of e ' , measured at w = w^ and w = Wj, eq (30) gives

e; (w,) - e',(uj,) = ^ in\ - in^

w: w' or

Ae'(w) = e;(a;,) - e'^(oj^) -^ £n 4 2 w?

(32)

From eq (15) and eq (31)

so that

or

-^ = •?-£' tan5

IT IT

Ae'(a;) = - e' tan5 £n

^

-—7- = — tan6 m —^ . e' TT w.

(33)

(34)

(35)

This result gives the change in real effective permittivity between two

frequencies w^ and Wj and relates that change in real effective permittivity

to the loss tangent of the dielectric material. Garton [18] first presented

this result, although it does not seem to be well known and some published

measurements are not consistent with it.

29
Equation (35) may be used in three ways:

(1) Check measured, complex permittivity values for discrepancies

(or predict one measurement from the other)

.

(2) Indicate where peak absorption frequencies occur.

(3) Determine which modal roots are valid in cavity or waveguide

measurement fixtures

.

4.3.4.2 Absorbent Materials Having Single Relaxation Times

Carton's work [18] may be extended for the Debye model of a dielectric,

where tan5 is not constant with frequency. From eq (19) the charging and loss

terms of a Debye dielectric may be written

e' = e^ + ^

" °°

, (36)

1 + u't'

1 + uj't^

'

so that if we consider two measurement frequencies, w, = w^^ - Aw and

^2 = 0;^ + Aw, where oj^ is the arithmetic mean of w, and u}^' ^^ ^^^ write

Ae' = e;(a;,) - e;(u}^)

[1 + w^T^d +^y] - [I + u^ithi -^y]

= ^'^ " '-^

^^ 7^— • [1 + uya +^y] [1 + o^ithi - ^y]

(37)

30
If Aa> << ^

(1 + AW)2 ~ 1 + 2-A^

'^0 ^o

and (1 Aw \2 w

1 - 2 Ao; w„

so that Ae', = ^(^s - ^cq) ^"^^ Aw

(1 + w^rO 2-.2n,2 W^

(38)

or Ae' =

4 e" w„To' Aw

1 + O^lT^ ^0 ' (39)

where

e"

(e - € ) w T ^ S 00^ 1 + w^r^

(40)

may be considered as the approximate mean value of the loss term between

measurement frequencies w^ and Wj. In this case,

1

= 2 Aw

w_

(41)

Therefore

2 e" uT w, Ae' = :Ar in -^

1 + u}ir w. (42)

or

2 e' w„T f,

Ae' = 2_ tan5 £n -^ , 1 + w! T^ f

' (43)

so that

Ae' ~ 2 WpT £nlO ~

e' 1 + w!t2

tan5 log,o

-^

J- 1 (44)

31
Lynch [19] has extended Carton's work for the Debye single relaxation model

and has shown that

4f' = a tan5 log.^ -f- (45)

t r,

where 1.0 < a < 2.3 for 1 < w^^T < 4. The point is that eq (34) and/or

eq (35) is generally valid, within a factor of 1.5, for a wide range of

frequencies on both sides of a Debye absorption curve. Problems in applying

either of the relations given by eq (35) or eq (45) arise because:

(1) The assumption that the loss tangent of a dielectric is either

constant or varies in a Debye fashion over a range in frequency is

only approximately true

.

(2) Changes in measured real effective permittivity as a function of

frequency are not often reported with sufficient precision to allow

strict testing of the relations.

Despite the problems in applying real effective permittivity and loss

tangent relations, Lynch [19] has compared reported measured values of loss

tangent to calculated values of the loss tangent for several materials up to

K-band. This comparison is given in table 2.

The validity of relations between real effective permittivity and loss

tangent is worthy of further research, particularly for non- Debye relaxation

mechanisms. Such relations might help identify discrepancies and errors in

reported permittivity measurements.

32
Table 2. Comparison of Reported With Predicted Value of Loss Tangent

(after reference [19])

Relative

Permittivity Loss Tangent

Material Frequency (Geometric Mean) Reported Predicted

Polystyrene 50 Hz 2.55 0.001 < 0.003

9 GHz 2.55 0.004

Polytetrafluoroethylene 50 GHz 2.12 0.000 05

(Teflon) 0.000 7 24 GHz 2.10 0.000 25

Phenol - Formaldehyde 100 MHz 5.00 0.0068

Resin, containing 0.078

5.8% water 1 GHz 4.05 0.084

Water at 0°C 3 GHz 79.8 0.31 0.76

9.3 GHz 45.4 0.91 1.76

24 GHz 16.3 1.70

Water at 75°C 3 GHz 61.9 0.055 0.033

9.3 GHz 60.4 0.17 0.25

24 GHz 51.7 0.43 0.43

4.3.4.3 Generalized Relationship for Any Dielectric Material Having

an Arbitrary Number of Relaxation Times

A generalized relationship may be derived between real effective

permittivity e' and loss factor e" for dielectric materials possessing an

arbitrary number of relaxation times. In general, the permittivity can be

regarded as a system function characterizing the electrical properties of a

material with the applied electric field as input and the displacement field

as output. In the time domain the material permittivity is simply the

transient system response. Consider the (real) permittivity e(t) of any

material that is impulsively excited at time t = with an electric field.

33
The permittivity e(t) can always be decomposed into the sum of an even

function € (t) and an odd function e^(t) ; that is,

e(t) = CgCt) + e^(t) (46)

where e^Ct) = [e(t) + e(-t)]/2 (47)

and e^(t) = [£(t) - €(-t)]/2 . (48)

The decomposition process is shown schematically in figure 6 for a transient

system response that contains no singularities at the origin.

Also,

^eCt) = e^(t), t > (49)

and eg(t) = - ejt), t < , (50)

so that

e^(t) = ejt) sgn(t) (51)

and eg(t) = e^(t) sgn(t) , (52)

1, t > where sgn(t) =

\ (53)

1, t < .

(See figure 7.)

34
(a)

(b)

i .o(t)

A/2

-A/2

^t

(c)

Figure 6. Decomposition of permittivity e(t) into even CgCt)

and odd e.Ct) parts.

35
k

sgn(t)

1

-1

Figure 7. The function sgn(t) .

The importance of eq (51) and eq (52) is that the even and odd

decomposition functions of any material's permittivity in the time domain can

be written as the product of two time functions. Taking the temporal Fourier

transform F of the material permittivity function yields,

F {e(t)) = e'iu)) - j€"(a;) , (54)

where

and

F (ejt)) = €'(u;)

F (eo(t)} = - je"(w) ,

(55)

(56)

and where the Fourier transform F(u;) of an arbitrary function f(t) is given

by F(a;) = / f(t) e"'^'^ dt . The Fourier transform of the product of two t ime

functions equals the convolution of their respective transforms divided by Iw

.

Since

F {sgn(t)) 2 (57)

36
we may straightforwardly substitute eqs (55), (56), and (57) into (51) and

(52) to obtain

e"(a;) = i e'(w) * -

and e'(u) = - i e"(w) * ^

where * denotes convolution, or

oo e"(w) = i f

_1!_(h) du (58) w ' w-u -(X)

and e'(oj) = - ± j- _l_i^ du . (59)

TT .^ W-U

Equations (58) and (59) are valid when no singularities in e(t) exist at

t = 0. The -j- sign denotes Cauchy principal value. In other words, eqs (58)

and (59) are exact expressions for obtaining the loss factor 6" or real

effective permittivity €' from the real effective permittivity or loss factor,

respectively, for any material provided e(t) contains no impulses at the

origin. The restriction that e(t) contains no impulses at the origin means

that e (w) ^ as w ^ oo . In fact, there is always an optical polarization

that defines an optical dielectric constant £ , as given in eq (A-5):

e = n' = 1 +

_2o

, (60) oo F

where n is the refractive index of the material under the influence of the

electric field E. Therefore,

lim e (w) = lim e' (u) = e^ , (61)

a; -> oo (jj -^ oo

37
so that an impulse exists at the origin for e(t) . This means that an even

term € 5(t) (Dirac delta function weighted by 6^) is present in e(t) and

£g(t), but not in €^(t) . In other words, eq (58) is still valid, but e^ 6(t)

is lost in eq (59). We can then conclude that €"(w) is given by eq (58), but

only the quantity e'(w) - 6^ is recovered from eq (59) (e'(a;) can be

determined from measurements of e"(a;) only within the real optical limit e ).

Hence eq (58) and (59) should be written

oo e"(a;) = ^ i -^-^ du (62)

TT •' W-U -oo

and e'(u}) = e_ - - i ^^ du . (63)

The integral expressions on the right of eqs (62) and (63) are the

Hilbert transforms of the permittivity and loss factor, respectively, and

provide a means for computing the loss (or real effective permittivity) from

observed real effective permittivity (or loss) measurements that are made over

a range in frequency. The integration variable u in eqs (62) and (63) is just

a dummy variable, not necessarily the same as the angular frequency u) for

which e" or e ' is desired. Also, the relations given by eqs (62) and (63) are

true for rf, microwave, mm, and IR frequency ranges. In other words, there

are no frequency ranges restricting the validity of eqs (62) and (63) . The

only suppositions implicit in the derivation of these relations are

(1) Dielectric material behaves linearly in presence of electric field.

(2) Constitution of dielectric material does not change within analysis

time.

38
(3) Dielectric is causal (does not polarize before stimulus of electric

field)

These relations are quite useful for two reasons,

(1) Uncertainty in loss measurements for both low-loss standard

reference materials and absorbent materials is usually much greater

than the uncertainty in real effective permittivity measurements;

that is

Ae" ^^ Ae'

e"

Therefore precise measurements of real effective permittivity over a

range in frequency can be used to determine the loss factor.

(2) Prediction of absorbent dielectric characteristics can be made from

out-of-band measurements.

4.3.4.3.1 Example of Hilbert Transform Relationships in Prediction of

Dielectric Properties for Absorbent (Dispersive) Materials

An example of the use of eq (62) for predicting the loss factor e" from

discrete permittivity values €' is shown in figures 8 and 9. The dielectric

material shown in figure 8 has only a single relaxation time with e^ = 6 and

e^ = 2 . The predicted loss for this material is given in figure 9 and

compares with the exact (discrete) loss shown in figure 10 by no more than 2%

error over two decades in frequency. Similarly, the use of eq (63) for

predicting the real effective permittivity £' from discrete loss factor

values, e" shown in figure 10, is presented in figure 11. The predicted real

effective permittivity values in figure 11 can be seen to agree with actual

permittivity values in figure 8 within 1.9%.

39
4Jao

•ao

to

cd Hi

cdU bJ O 3 - o

VD

CO - •!-! >^ JJ

4J

O

.r^

C > 3

•i-l iw V CO awcfl

Cfl (U 'i-l > u

Cd cd r-l S

(Uuow o

r-l .r-l Q -O

00u

•I-l

AO
•HU (1) iJ >

•!-l

r-l

r-l •H 1) tS )-l u (1) (3 u O (1) X> M

)-l o

(/I CQ •r-l -^ T3

XI

0)

d

iJ IM

cfl (4-1 r-l Tt w 2 1) C s 4J CO fl (Tl W w H 4J

nS 3 W

1—

V-l

)-( nj 0)

f.) hO

<JM

H. • r-l «

V-.

M

soe 3

VU CO iw • r-l • > Wu c CO o u

I-l •r-l ^

OJy > c /->

•f-l lb >, o (j-i V

cfl •H

r-l cfl >

0) •r-l M w iJ

CO 4J T3 •r-l Q) r-l B

iJ nJ

u

•H Q)

>F-| l-l

a

T) (D Nw^

(U

V

t-l CO »o;

Pm S vj

o>

•r-l

Al
c

0) jaun

fi

(0 •d

a> u

(d • r-l t- 3 ;^ S

.H iw

CQ

ctf c

Vj •r-l U

U^• 3

eo:i4^ W

ffl

•k CQ

w

U cd H iH

cfl a> •<-l > v^ •H 0) iJ 4J

(d

a

iH e

0)M

<H

0)

k

iJ 4J U U u 0) u r-l n 0)

•1-1

H

Q t3

•r-l

42
a)

0)uu

V CO O

10

r-j Cfl W r-l - «^

c4

U

U - iw 3 * iw

a

'=>= o E

vo o C M-i - o w OC w 3 >

p-l

iJ

u « tC tu

ll ^ >

a)

a ni

•1-1 /-s

JJ

w

u o

0) I—

•do

•l-l

>( .r^ sa:

0^ T3

W

43
4.3.5 Effect of Temperature Changes

Polarization processes occurring in materials are generally strong

functions of both angular frequency w and temperature T. For this reason the

complex permittivity tensor may be generally written as

€* (x,y,z; w.T) = x*(x,y,z; w.T) + I , (64)

where €*, x* are the complex frequency- and temperature -dependent permittivity

and electrical susceptibility tensors, respectively, and I is the identity

matrix. In order to gain insight into temperature -dependent variations of the

complex dielectric permittivity over the frequency range where dipolar or

orientation phenomena occur, it is useful to consider concepts borrowed from

statistical thermodynamics. The results will then be compared to those

derived in the appendix for relaxation in dielectrics possessing one

relaxation time.

If the polarizability of a material can be related to the known

activation energy U of that material at a given temperature and under the

influence of a time -varying electric field, then a means for predicting the

dielectric behavior of that material as a function of temperature could be

grasped. Of course, such predictive capability will be constrained by the

assumptions implicit in the physical model and will need to be validated by

measurements of the dielectric constant as a function of both frequency and

temperature. Clearly, these types of measurements, combined with theoretical

physical models, will not only enhance the means for predicting the dielectric

constant, but can also aid in manufacturing (by inferring temperature fields

through variable frequency dielectric metrology)

.

44
Consider a bistable model of an elementary dipole within a dielectric

whose molecular groupings can be characterized by well-defined, permanent

dipole moments. In this type of model, we assume that a charge q may be in

one of two states that are separated by a distance d. These states are

defined as minima of the potential energy U and are portrayed in figure 12.

POTENTIAL ENERGY

y2qdE \-/

Figure 12. The potential energy of a bistable model as a function of

distance has two minima, depicted by states 1 and 2. The

depth of these minima are modified by an applied electric

field, and charged particles can occupy either state [20]

In this model, an electric field acting on the dielectric causes movement of

charge from the minimum of state 1 to the minimum of state 2. This charge

movement is equivalent to a 180° rotation of a dipole of moment

qd . (65)

45
The potential difference due to the applied electric field E is simply

0^-02 = 2p • E = qdE cos^ , (66)

where B is the angle between the direction of the electric field and the

dipole moment.

The interaction between individual dipoles within our dielectric can be

neglected by assuming that the total number N of bistable dipoles per unit

volume is small. For dipoles we may also generally assume that ^ = and that

equal potential energy exists for states 1 and 2 in the absence of an electric

field. The visualization can be made in this microscopic assembly that the

bistable dipoles are in a heat reservoir which consists of spontaneously

active particles that exchange energy through thermal fluctuations with each

other and the dipoles. Therefore the directions of the dipoles fluctuate.

Occasionally thermal fluctuations allow a charge in the minimum of state 1 to

acquire sufficient energy to go "over" the potential hill U and drop into the

minimum of state 2. In state 2 the energy of the charge is returned to the

heat reservoir and stays in state 2 until it acquires enough energy from the

reservoir to return to state 1.

The probability of a jump by a charge in a double potential well (state)

is derived and well known in classical statistical thermodynamics. Here it is

sufficient to state that the number of dipoles jumping per unit of time from

state 1 to state 2 is given in terms of the difference of potential energy

between the two wells as

u,, = Ae-(^*P^^/^T . (67)

46
where U is the activation energy, k is Boltzmann's constant (1.37 x 10"^^ ^/K)

and T is absolute temperature (K) . The constant A may or may not depend on

temperature. Generally, for ionic solids it does not, whereas for organic

polymers (plastics), A is inversely proportional to T. The ± signs within the

exponential of eq (67) dictate whether the minimum in state 2 is lower or

higher than that of state 1. Generally, U >> kT.

For dipoles in normal dielectrics, p is of the order 10"^^ C-m, whereas E

for fields below breakdown strength is always less than 10^ V/m. Therefore,

in general,

H « 1 . (68)

Note that pE/kT is dimensionless and that, as T -» <» , thermal fluctuations

dominate polarization, whereas when T -»^

, polarization (pE) dominates.

Equation (67) may be approximately written

U12 ^ ^ ^^ - ll^ ' ^^^^

where

u = Ae-^/^"^ (70)

is the frequency of jumps in the absence of an applied electric field.

Similarly, the frequency of jumps from state 2 to state 1 can be written

in linear form as

u,, ^ u (1 + ||) . (71)

Provided the number of charges N^ jumping per unit of time from state 1 to

state 2 is the same as that going from state 2 to state 1, Nj, the average

47
population of charges in the wells of states 1 and 2 will not change with

time. In other words at equilibrium

N, u,2 = Nj Uj, . (72)

The total number of bistable dipoles is constant or

N, + N2 = N . (73)

Equations (72) and (73) enable the calculation of N, and N2 in equilibrivun.

Since the polarization per unit volume P is defined as that number of dipoles

in one direction which is not compensated by dipoles in the opposite

direction, or

P = P3 = (N, - Nj) p , (74)

we have a basis from statistical thermodynamics to determine the variation of

polarization with temperature when the dielectric material is in equilibrium;

that is, from eq (72),

N^u a - §) = N,u (1 + ||)

or

N, - N, = (N, + N,)£| = n|| . (75)

Hence eq (74) may be written

kT

Pg = N -^ . (76)

We are now in a position to derive the frequency dependent properties of the

model by noting that the change in number of dipoles in state 1 is equal to

the outflow to state 2 less the inflow from state 2 or

48
dN

' - - N, u,2 + N2 U2, . (77)

dt

Since the total number of bistable dipoles is constant,

dN, _ dN

or

dt dt

^ <" - "'> .2^. (78) dt dt ' ^ '

so that eq (77) becomes

dN, _ 1 d(N,-N,) . . PE)

dt 2 dt ' kT

pE

+ N^ u (1 + ^) . (79)

Equation (79) can be simplified to read

or

1 d[N^_jy^ ^ . , (N, . N,) f u (N. + N,) £| (80)

1 dKN,_iypl __ _(,, .,^, ,,,,^. (31)

We now have a differential equation for the dipolar polarization of a

dielectric medium as a function of temperature; that is,

J_ dP ^ p ^ Np^,

(82) 2u dt kT

Note the similarity between eq (82) and eq (A- 7) in our derivation of

relaxation in dielectrics with a single relaxation time; in other words,

eq (82) is a relaxation equation with a relaxation time

49
r=^.Ae-/".

We may generalize eq (82) to

dt

7- -3^ + Pd = ^D E . (84)

where Pq is the dipolar polarization and a^ is the dipolar polarizability of

the dielectric material. Using simple Fourier transform methods we obtain

e* (w.T) - e^ (T) = —-^, (85)

or

and

e' (w.T) = e_ (T) + ^ , (86) °° 1 + wh^

e" (a;,T) =

"'"^^ (87)

(1 + W^T^)

and tan S (w.T) = ^^^ . (88)

«D + e^(T) (1 + <^'r')

The permittivity and loss tangent are directly proportional in this model to

the dipolar polarizability of the material, which is inversely proportional to

temperature.

Equations (85) , (86) , (87) , and (88) describe dispersive dielectric

behavior for a bistable dielectric as a function of temperature and frequency.

The temperature -dependent permittivity and loss tangent are given in terms of

the dipolar polarizability, activation energy, and high-frequency (optical)

permittivity at temperature T. The derivation is limited to dielectric

materials where interaction between individual dipoles can be neglected and

for conditions where pE << kT (nonsuperconducting states).

50
An important area of further research would be to examine the

temperature -dependent dispersive effects on dielectric behavior using the

bistable model described above. Another fertile research area would be to

examine equivalent dispersive effects in a dielectric material that result

from either increased temperature or frequency. Still another would be to

generalize the bistable model.

4.4 Other Sample Characteristics Important to the Search for Reference

Materials

In a previous section the general electromagnetic characteristics of

materials were discussed. The electrical properties were defined by constitutive equations in terms of fundamental physical processes occurring in a

material in the presence of an electromagnetic field. It was further seen

that a number of physical polarization mechanisms are responsible for the

actual frequency -dependent behavior of a dielectric material. Provided the

real and imaginary parts of the complex permittivity have been sufficiently

sampled in frequency so as to characterize the relaxation distribution

function, the dielectric behavior of an arbitrary material can be predicted,

even at frequencies where measurement data are not taken. Since the differential equations describing the functional dependence of dielectric relaxation

times with respect to temperature are similar to those describing dielectric

relaxation times with respect to the time variations of an applied electric

field, relations can be derived that allow the prediction of dielectric

properties as a function of temperature and frequency. In practical application these relations permit the determination of temperature of a dielectric

by measurement of its permittivity. Or, by changing the temperature of a

51
dielectric, we might control and predict its complex permittivity; this can be

extremely useful in microstrip applications.

In other words, the same material dielectric value could be expected for

different combinations of temperature and frequency. Provided the material

has been adequately characterized with frequency, the dielectric behavior can

be predicted for any temperature or excitation frequency (when the same

physical relaxation processes occur) . This would allow the prediction of

dielectric properties at very high frequency from measured properties at lower

frequencies and temperatures; this is a fundamental metrology problem. The

applicability of temperature or frequency dispersion relations to any

dielectric is a subject for further research. Measurement precision will

undoubtedly need to be greater than that of many reported results

.

This prologue is necessary for the understanding of dielectric sample

measurements and the implications on physical processes occurring in the

material under the influence of an applied electric field. These physical

processes, which control the constituent properties, direct the choices of

suitable reference materials. As we shall see later, they are also important

in choosing the optimal metrology technique for any given physical dielectric.

4.4.1 Sample Homogeneity

In section 3, where desired properties of dielectric reference materials

were discussed, it was stated that measurement techniques must be analyzed in

sufficient detail that bounds on measurement errors can be specified.

Measurement errors are both systematic and random and result from departures

of the measurement system from assumptions used in an idealized theoretical

model. Common fixtures used in dielectric metrology include sections of

52
transmission line (coax or rectangular waveguide), open or closed cavities,

and various bridge circuits. In the first two cases, the modal structure of

the applied electric field to the sample under test is very precisely

specified so that corrections may be made to measurement data that are due to

departures of the actual fixture from the idealized theoretical model of that

fixture

It is beyond the scope of this Technical Note to characterize any

particular dielectric measurement fixture that can lead to inaccuracies in

property determinations. However, it is within the scope of a standard

reference material search to consider inhomogeneity within the actual sample.

In this way deviations from homogeneity, say, of a candidate material can be

distinguished from measurement inaccuracies. The influence of deviations from

homogeneity on a very precisely specified electromagnetic field structure

needs to be determined in order to quantify the homogeneity of a reference

sample

In the past, homogeneity of any reference sample was treated in a very

practical, if not expedient, manner. Measurements were made on many samples

of the same material produced by the same manufacturing process with fixture

error bounds specified. These measurements were then compared, either

nationally or internationally, with other laboratory measurements made with

different fixtures.

While an inhomogeneous sample affects or even can destroy the expected

modal field behavior within a precision fixture, the quantitative determination of when and how much a sample's inhomogeneity affects field structure

remain undetermined. How precisely dielectric measurements can define

inhomogeneities within a sample also remains unknown and is probably fixture

53
dependent. In order to address the effects of sample dielectric inhomogeneity

on the impressed electromagnetic field structure of a measurement fixture, it

is necessary to reapply Maxwell's equations. The same analysis approach

outlined below can also be used to quantify measurement errors that result

from an eccentric waveguide or cavity fixture, nonuniform air gaps around a

dielectric sample in a loaded transmission line or cavity, or nonorthogonality

of endplates to the axis of a cylindrical cavity dielectric measurement

device. All of the above lead to degenerate mode structures whose magnitude

and ultimate effect on precision dielectric measurements can be ascertained.

4.4.1.1 Inhomogeneous Sample in Field of Arbitrary Dielectric Measurement

Fixture

In this section a brief formulation in the frequency domain is given for

examining the electromagnetic field interaction of any impressed source field

on a dielectric that is three-dimensional, of arbitrary shape, and that

possess any internal structure or loss characteristics. We start with

Maxwell's equations where exp(+ja;t) time dependence is assumed. Ampere's and

Faraday's laws may be written, respectively.

V X H = J + jwe E = (a + jwe) E + J^ (89)

and

V X E + jw/i H = . (90)

-

Here J is the total current density, and for convenience we use eq (14) to

distinguish the conductivity or loss factor from the permittivity of medium

described by 6 , /i and o. J^ is an impressed current density. For now we will

consider the physical situation of a sample dielectric and source contained in

54
freespace and a sample which may be Inhomogeneous in conductivity and

permittivity, but not in magnetic permeability.

The differential sample parameters may be defined as

'^s - '^d - ^0 = ^d

and

where a^, €^ axe the conductivity and permittivity of vacuum, respectively,

and a^, €^ are the conductivity and permittivity of the dielectric sample,

respectively. The differential sample parameters defined above are

responsible for scattering incident electromagnetic energy. The effect of the

sample is described by replacing the sample with an effective scattering

current.

Ampere's law for our scattering lossy dielectric sample then becomes

V X H - jwe^ E = J s + Jo • (91)

In the customary development of the Helmholtz vector wave equation,

VxVxE = vv-E- v^E = - jw/i V X H = u^ne^E - jw/x (Jg + J^)

or V X V X E - k^ E = - jw/i (J3 + J^) , (92)

where k^ = w^^q.

As an aside, we know that free charge is absent from a uniformly lossy

sample, so that V • E = — • E. Provided the permittivity of the sample

55
under test remains spatially invariant, V • E = 0, so the usual vector

Helmholtz equation may be written,

V^E + k^ E = + jWM (Js + Jq) • (93)

In the case posed, the two equations to be solved are

V X V X E(r .w) - k^ E(r .w) = - jw/x J(r ,w) (94)

and

V X V X H(r ,w) - k^ H(r ,a;) = v x J (r ,a;) , (95)

where

J(?,w) = J3(?,a;) + J^(r,a;) . (96)

From Gauss' law, V'B=V'/iH = 0, soV*H = provided /x is spatially

-* Invariant. Hence, since V • V x A = 0,

/xH = V X A . (97)

Similarly, since V x v^ = for any scalar potential function V which is

differentiable, we may write from eq (90),

E = - jw A - V0 . (98)

Substitution of eqs (97) and (98) into eq (89) yields

VxVxA = k^ A + n J ^

- fi (a + 2U}e)VrJ} or vv • A - v^ A = k^ A + A* Jq - /i (a + jci;e)vV' , (99)

where k^ = - ja;/i(a + jwe).

56
If the Lorentz gauge condition is imposed

V • A = - n (a + ja;e)V' , (100)

then eq (99) is reduced to a vector differential equation containing the

vector potential function A only; that is,

V^ A + k^ A = - |i J jj , (101)

which is the inhomogeneous vector Helmholtz equation. By taking the

divergence of eq (99) and using the continuity equation, ^ ' Jq = - J'^Pq' ^^'^

the gauge condition (eq (100)), we may obtain the differential equation for rp

v^V + k^V- = TT ^0 ' (102)

where p^ is the free charge density and eq (102) is the inhomogeneous scalar

wave equation. Solutions for eqs (101) and (102) that correspond to outgoing

waves from the source are given by

A(r) = fi Uj J(?,) G^(?;r^) dv (103)

and

V'(r) = -^ jjj p,(?„) G^(?;?,) dv , (104)

where

~ i k I r ~r I

47r I r - r ^ I

The function G^(r;r^) is the free -space Green's function pertaining to the

three-dimensional scalar wave equation, where r denotes the position vector

57
of a field observation point and r^ denotes the position vector of a source

point. From eqs (98) and (100) we can write

E(r;a;) = - jw [A(?;a;) + -5- VV • A(?;a;) ] (106)

k

and

H = i V X A . (107)

Hence, once we know the solution for A(r), the electromagnetic field vectors

->• -* E and H can be found.

4.4.1.2 Coupling of Electromagnetic Field Components

The method of potentials in an infinite domain has been used to solve

Maxwell's equations in terms of the free -space Green's function that is a

solution to the three-dimensional scalar wave equation. The free-space vector

Green's function for a source pointed in one coordinate direction may be

derived in terms of this scalar Green's function. Since an arbitrary source

field has components in all three coordinate directions, three vector Green's

functions are generally needed. These can be compactly designated as the

constituents of the free-space dyadic Green's function.

Consider an infinitesimal source located at r^ with a current moment

-l/(ja;/Li) pointed in the x-direction. That is,

J(?) = 4^- 5(r-?„) U^ , (108)

-*-* where S(r-r^) is the Dirac delta function and U^ is the unit vector pointed in

the x-direction. Hence

jji J(?^) dv = ^

U^ . (109)

58
Substitution of eq (108) into (103) gives

so that if we denote the electric field produced by this elementary source by

G^('^)(r;r^), then

G„('^)(?;r^) = (1 + J_vv) GJr;r„)U^ , (110)

which is a solution of the equation,

V X V X G^''^(r;rQ) - k=^ G^'^'^Ur ,r^) = - 5(r -r^) i\ . (Ill)

(Here we use the same notation as that of Tai [21].) It is straightforward

to show that the function G^ '(rir^) satisfies the radiation condition as

I r ]- oo, or

lim r [V X Gj^hr;r^) - jkr x G^^'^) (?; r^) ] = . (112)

I r I -> oo

Gq^ '(rir^) is designated in Tai's [21] notation as a free-space vector

Green's function with a source pointed in the x-direction. Since a vector

source can point in the y-direction or in the z-direction as well, we have two

more free-space vector Green's functions which we may denote by G^^^' (r iv i^)

and Gq^ '(rir^) which satisfy the following respective equations and whose

respective solutions are given by

V X V X G„(y)(?;?„) - k^ G„(y)(r;?3) = - 5(?-?„) Uy , (113)

V X V x G„(^)(r;?„) - k^ G^^^hr;r^) = - 5(?-r„) u^ , (114)

59
and

G^^y^?;?^) = (1 + -^ w.) G^Cr ;?q) u^ , (115)

G^^^^C?;?^) = (1 + -^ vv) Go(?;r„) u, . (116)

which also obey the same radiation condition as described in eq (112) . The

free -space dyadic Green's function is defined by

G„(?;?^) = G^(^)(?;?„)u^ + G ^^^hr ;r ^) u^ + G ^^^hr ;r ^) u^ . (117)

Summarizing eqs (111), (113), and (114) yields

V X V X G^(r;r„) - k^ G^,(r;r^) = - I 5(r-r^) , (118)

where I is the idem factor or unit dyad defined by I = u^U^ + ^sM^ + ^z^z

and A • I = I • A = A. Substitution of eqs (110), (115) and (116) into

eq (117) gives

G,(?;r^) = (1 +-^ w.) G,(?;?„)I

= (I + -1- vv) G,(?;?,) . (119)

Similarly, the three separate radiation conditions for the vector Green's

functions can be combined to give

lim r [V X G(r;rQ) - jkr x G^(r;rJ] = . (120)

r -* oo

60
Recall Green's vector theorem,

JSJ [W-VxVxQ-Q-VxVxW] dv

= JJ [QxVxW-WxVxQ]- ndS . (121)

-* -^ -*^ -* = -^ -* ^ Letting W = E(r), Q = G^ir •,t: ^) • a where a denotes a constant but arbitrary

vector, we obtain

Ijj [t{r) • V X V X G^(x;v^) a - [G^(?;?^) -a] • v x v x E(r)} dv

= - J/ {[V x E(r)] X [G^Crir^) • a] + E(r) x v x G^(r;?^) • a}- ndS

S

= - JJ {[n X V x E(?)] • G^(?;?o) a + [n X E (r ) ]

• V x G^(?;?^)- a) dS , (122)

-> where n is the outward unit vector normal to the surface S. Substitution of

eq (94) and eq (118) into eq (122) yields

^^^ {E(?) • k^ G^(?;?o) • ^ - E(r) • I 5(r-r^) • a

- G^(r;r^) • a k^ E(?) + G^(?;rJ • a • jw/x J (r ) ) dv

= - ^^ {[n X V X E(?)] • Gq(?;?o) • a + [n X E (?) ] s

• V X Gq(?;?o) • a} dS .

Since ^^^ E(r) • I 8{r-r^) • a dv = E(r^) a, eq (122) may be rewritten

(deleting • a since a is a constant vector) as the Schwinger integral

equation [22]

61
E(?) = jw/i Jjj J(?„) • G^(r^;r) dv

+ jj {jw/i [H(r^) X n] • G^(?o;r)

+ [n X E(r^)] • v^ x G^(r^;r)} dS , (123)

where V indicates differentiation with respect to the source point

coordinates. From the radiation condition for an electromagnetic field in

free -space we have

lim r

1C -* oo vx(|j - J^^^ (l) =

or lim r [-jw/i H(r) - jkn x E(r)] = .

(124)

(125)

If we consider the volume to be of infinite extent, so that the enclosing

surface S recedes to infinity, then eq (123) may be written in the following

form using eq (125),

E(r) = jw/z /// J(?„) • G^(r^;r) dv

+ JJ [n X E(?„)] • [v^ X G„(?o;?) - jkn x G^(r^;r)] dS .

S

->• 00

Because of the radiation condition described by eq (112) , the surface integral

above goes to zero so that

E(?;w) = jw/i jjj G„(r ;?o)

' J(rQ) dv

V

= j'^/^ /// G,(?;?,) • [J,(v^) 4- J^(r„)] dv . (126)

62
i

The physical situation at hand consists of a primary current source and

secondary source (s) In a homogeneous full space; because the surface boundary

Is at Infinity, the surface Integral In eq (123) vanishes. A further

simplification can be made in eq (126) by directly calculating the incident

field E (r) due to the source current in the absence of the sample under

test, so that

E(?;a;) = E'^^'ir) + jw/i /// G^(r;r^) J3(?^) dv . (127)

V

The induced secondary current density in eq (127) can be thought of as a

superposition of point electric current dipole distributions. That is, the

current density may be written as

J3(r) = Idl 5(x) 5(y) 6(z) ,

-

where Idl is a current dipole moment. The dyadic Green's function we need to

look for is a solution to eq (118) . In component form eq (118) becomes

[V X V X - k'j G'^"(r ir^) = - S(v-r^) 5"^"

. (128)

Thus a component of the Green's tensor, say G^^^, can be Interpreted as

the y- component of the electric field due to a unit point dipole in the

z-directlon. Equation (127) may be written more explicitly as

E(?;a;) = E^"^(?;a;) + jw/z J// [a^ + 2<^e^] G^(r;r^) • £(?„) dv , (129)

sample

vol ume

where the volume Integral is only over the sample volume since a^ and 6^ are

Identically zero outside the sample. Once the field is found in the interior

63
of the sample, the field at any exterior point can be found by using eq (129).

The magnetic field may be found by use of eq (90)

,

H(r ;a;) = H^"'=(?;a;) - ^

jjj [a^ + 3(^6^] F(?;?,) • E(?,) dv , (130)

J ^ sample

vol ume

where the tensor F(r;rg) - F""" whose elements are given by

px, . ^. ^ , (131)

ay az

?xz

tZX

?zz

py^

ac^^ acy^

ay az

ac" acy^

ay az

acy^ ac'^'^ ax ay

acy^ ac^^ ax ay

ac" ac'^'^ ax az

ac^^ ac"

pzy ^ _aG^ . ac^y ax ay

pyx ^ ac"^ . ac^^ ^ pyy ^ ac^y . ac^y az ax

az dx

The conductivity and permittivity may vary spatially within the target

volume. The procedure would first be to solve for the electric field within

the target so as to obtain the scattering current, after which the magnetic

field may be determined.

Equation (129) may be used in straightforward fashion only after the

field in the interior of the target has been calculated. A common technique

is to divide the target into a number of cells where the electric field is

constant in each. One then sets up a matrix equation of the form

M • E = E^"'^ so that E may be found by inverting M. However, the matrix M is

large and nonsparse so that inversion is not a trivial problem. Further, the

64
target must be divided into a relatively fine mesh for accurate field

calculations when the fields are taken to be constant within each cell. For a

three-dimensional problem in which the target is described by N points in each

direction one is faced with inverting a 3N^'^ x 3N^'^ matrix for each frequency,

since the three field components must be solved simultaneously due to the

coupling implied by the Green's tensor. Thus, for a sample under test which

is described by 100 points in each direction, the complex matrix to be

inverted would be 3000 x 3000. Another approach to the solution of eq (129)

is to allow E(rp) within the sample to be approximately E^"'^ (Born

approximation). This approach is valid for low- loss dielectric scatterers

where contrasts in the imaginary part of the complex permittivity are close to

zero such that very small phase changes are effected.

Equation (129) is an integral equation in the conductivity crs(xQ,yQ, z^^)

and permittivity ^s^^^o'^o' ^o-^ °-^ ^^ inhomogeneous lossy dielectric sample under

the influence of an applied electric field, E(x,y,z;a;), for an arbitrary

fixture. Iterative Born techniques may be used to solve for the complex

permittivity when losses are not low. It should also be noted that in modern

laboratories scattering matrix parameters S are generally measured with

vector network analyzers or microwave n-ports. Therefore the vector

components of the total electric field given in eq (129) must be related to

scattering matrices [23].

Equation (129) may also be used to determine when dielectric samples are

not axially centered in a cavity fixture. For example, in an ideal TE^^^

cylindrical cavity there is no radial electric field unless either (1) the

sample is azimuthally inhomogeneous or (2) the dielectric sample is

65
homogeneous, but a nonuniform air gap exists around the sample placed within

the cavity (due to machining nonuniformities or eccentricity of the cylindrical waveguide) . With the aid of eq (129) one may determine which of the above

factors might be responsible for the presence of a nonzero radial electric

field (or degenerate transverse magnetic resonant modes)

.

4.4.2 Isotropy

A sufficient condition for (microwave and optical) isotropy is that

the material (1) have no long range order or lattice crystal structure

(amorphous), (2) be cryptocrystalline (such as fused silica or glass), or

(3) have a lattice crystal structure that belongs to the isometric system. In

isometric and noncrystalline substances the dielectric constant is the same in

all directions. Such substances are said to be electrically isotropic. In

all other substances the velocity of an electromagnetic wave varies according

to its direction of propagation in the crystal lattice structure; such

substances are said to be electrically anisotropic. An electromagnetic wave

entering a two-dimensionally anisotropic substance is split into two orthogonal waves traveling with different velocities. The substance thus has

different dielectric indices. In optics this difference in dielectric or

refractive indices is known as birefringence. Birefringence is usually quite

small (for quartz it is 0,009) but for some materials, such as calcite, can be

large (0.172).

The relationship between dielectric indices and crystal lattice structure

can best be visualized by drawing in all directions from the center of a

crystal lattice lines with length proportional to the dielectric constant for

that wave propagation direction. The resulting figure is known as the

66
dielectric indicatrix (figure 13) . For noncrystalline and isometric

substances the indicatrix is a sphere, since the dielectric constant is the

same in all directions. For substances whose lattice structure falls in the

tetragonal and hexagonal systems, the indicatrix is a rotation ellipsoid in

which all sections perpendicular to one axis are circular; this axis is always

the axis of symmetry of the lattice structure. All electromagnetic waves

traveling in the direction of this axis of symmetry have the same velocity,

since the electric field variations are in the plane of the horizontal axes,

which are equivalent in these systems. For this reason substances whose

lattice structures are in the tetragonal and hexagonal systems are said to

uniaxially anisotropic . For substances whose lattice structures fall within

the orthorhombic , monoclinic, and triclinic systems, the dielectric indicatrix

has lower symmetry. This is in agreement with lower lattice structure

symmetry; the indicatrix is now a triaxial ellipsoid. A distinctive characteristic of such an ellipsoid is that it has only two circular sections, all

others being ellipses. All electromagnetic wave propagation transverse to

these circular sections will have the same velocity regardless of electric

field behavior in these sections. The two directions at right angles to the

circular sections of a dielectric triaxial ellipsoid have the same dielectric

constant (in optics, these are termed the optic axes). Hence orthorhombic,

monoclinic, and triclinic substances may be said to be dielectrically biaxial.

The orientation of the dielectric indicatrix is always related to the

physical lattice sjmmietry. Only for triclinic substances can the position of

the three principal axes of the dielectric indicatrix be independent of

molecular lattice symmetry.

67
The dielectric properties of any substance are closely related to the

molecular lattice symmetry. As one might expect, many other physical properties also show a similar dependence upon lattice direction, among which are

thermal conductivity, compressibility, and thermal expansion. It is beyond

the scope of this overview to discuss the theory and techniques of determining

these physical properties relative to the (regular) molecular lattice

structure of the material. The fundamental point here is that the simplest

procedure by which one can obtain a dielectric reference material that is

electrically isotropic is to use known materials that have amorphous molecular

structures or that are c ryp toe rystalline (such as fused silica, fused titanium

dioxide, etc. or glass). The reason why materials are in the noncrystalline

isotropic state is that they are formed by rapid cooling or quenching from the

molten state such that a regular lattice structure framework does not have

time to develop on the molecular level. However, provided a crystalline

material falls within the isometric lattice system it will also be electrically (and optically) isotropic. Hence one could pick materials which fall

within the isometric system to ensure isotropy. In a similar way, uniaxial

(two-dimensionally anisotropic) dielectric reference materials or biaxial

( three -diraensionally anisotropic) dielectric materials can be taken from those

substances whose molecular lattice structures fall into tetragonal and

hexagonal or orthorhombic , monoclinic, and triclinic systems, respectively.

4.4.2.1 Isomorphism

Inorganic substances which have comparable lattice structure on the

molecular level will have comparable dielectric property behavior. Substances

with analogous formulas and in which the relative sizes of cations and anions

68
€x = €y = €z

(a)

^Z > €v > €:

Figure 13. The dielectric indicatrix for (a) isotropic, (b) uniaxial,

(c) biaxial substances. In (a) the indicatrix is a sphere,

in (b) the indicatrix is a rotation ellipsoid and in (c)

the indicatrix is a triaxial ellipsoid.

69
are similar usually have closely related molecular lattice structures. These

lattice structures are then said to be isomorphous , and the phenomenon is

known as isomorphism. As a result of similar internal structures such

substances crystallize with similar external forms. A sufficient condition

for isotropy is that the lattice structure belong to the isometric system. In

this case, all principal diagonal components of the dielectric tensor are the

same. An isomorph of a given material that falls within the isometric lattice

structure system would then be expected to possess the same characteristics of

isotropy that is requisite for a reference material or check standard. The

same statement can be made for uniaxially of biaxially anisotropic reference

materials

.

Isomorphism is widespread among inorganic materials and naturallyoccurring minerals and can be used as one basis of their classification. Many

isomorphous groups are known such as the spinel group (ABjX^ double oxide

structure, in which A is one or more divalent metals (Mg, Fe, Zn, Mn, Ni) , B

+ 4 is one or more trivalent metals (Al, Fe , Cr, Mn or Ti ) and X is oxygen.), the

+ 2 +2 garnet group (X3Y2 (8104)3 ^^ which X may be Ca, Mg, Fe , or Mn and Y may be

+3 +3 +3 +2 Al, Fe , or Mn )

, and the hematite group (XjOj in which X may be Al , Fe or Fe

+4 and Ti ). See tables 3, 4 and 5 for various isomorphs of these groups

together with chemical composition.

Note that all isomorphs of the spinel and garnet groups are electrically

isotropic. Similarly, corundum (or alumina), which is an isomorph of the

hematite group and which is widely used as a substrate material for high

frequency applications (due to its high permittivity, low dielectric loss, and

inert behavior when subjected to chemical, vacuum or thermal processing), has

a lattice structure which is inherently uniaxially anisotropic. Of course.

70
Table 3. Naturally occurring isomorphs of the isometric garnet group

ISOMORPH FORMULA

Almandite Fe3Al2(SiO,)3

Pyrope Mg3Al2(SiO,)3

Spessartite Mn3Al2( 5104)3

Grossularite Ca3Al2(SiO,)3

Andradite Ca3Fe2( 3104)3

Uvarovite Ca3Cr2(Si04)3

Table 4. Naturally occurring isomorphs of the isometric spinel group

ISOMORPH FORMULA

Spinel MgAl^O^

Magnetite Fe304

Chromlte (Mg.Fe)Cr204

Franklinite (Zn,Mn,Fe)(Fe,Mn)204

Hausmanite MnMnjO^

Chrysoberyl BeAl204

Table 5. Naturally occurring isomorphs of the hexagonal hematite group

ISOMORPH

Corundum (Alumina)

Hematite

Ilmenite

FORMULA

AI2O3

Fe203

FeTiO,

71
one way to create a type of "pseudo-isotropy" in a material such as alumina is

to take very fine particles of corundum and sinter them under high pressure

and high temperature so that microcrystalline anisotropy is "averaged" out in

the finished ceramic substrate. However, this is done at the expense of

surface finish (or roughness) of the microstrip transmission line product, and

surface finish is a major contributor to attenuation. In fact, a lack of

smoothness and flatness in an alumina ceramic controls the accuracy of

photolithography and ease with which components can be bonded to a completed

circuit on a microwave transmission line.

Many other isomorphous groups are of practical importance in any study of

dielectrics. Some of these are the silica group, the rutile group or the

olivine-forsterite group. See tables 6 and 7.

Table 6 . Isomorphs of the uniaxially anisotropic tetragonal rutile group

ISOMORPH FORMULA

Rutile TiOj

Pyrolusite MnOj

Cassiterite SnOj

Plattnerite PbO^

Tapiolite FeTajOg

72
Table 7. Isomorphs of biaxially anisotropic orthorhomblc olivine group

ISOMORPH FORMULA

Forsterite (steatite) Mg^SiO^

Fayalite Fe2Si04

Olivine MgFeSiO^

Monticelllte CaMgSiO^

As we shall see later, titanium dioxide (rutile) in fused form has

ultra- low dielectric loss characteristics over a broad band in frequency, with

a high relative dielectric constant of 100. The olivine group, on the other

hand, is an example of a continuous solid solution primarily of forsterite and

fayalite. In sintered form as a ceramic, this isomorph presents itself as a

candidate dielectric reference material of very low loss (0.003 at 25''C) and

of constant dielectric constant (5.80) from 100 Hz to 10 GHz.

Of course, many of the sintered or fused forms of the above dielectric

materials (which are inherently electrically anisotropic on the basis of their

molecular lattice structures) can be used as "isotropic" dielectric reference

materials that are relatively dispersionless with respect to frequency and

temperature (from 100 Hz to 30 GHz, say). However, the electrical characteristics of these fused or sintered forms then become dependent on proprietary

manufacturing processes which are subject to change (and availability), and

the dielectric characteristics, including homogeneity and isotropy, of the

manufactured products are subject to validation and continuous quality

control

73
Isomorphism occurs because anions and cations of the same relative size

(that is, showing the same coordination) and in the same numbers usually

crystallize with the same lattice structure. Until the development of X-ray

diffraction techniques for the determination of crystal lattice structures, it

was somewhat of an enigma why materials that behaved dissimilarly chemically

could show complete similarity in crystalline structure. At first sight some

isomorphous pairs do not even have analogous formulas. Consider, for example,

the aluminum phosphate (AlPO^) mineral, also known as berlinite. Berlinite is

isomorphous with quartz; the true analogy is seen when the formula of quartz

is written SiSiO^. Both Al and P are similar in ionic size to Si and thus

can exist in a crystal structure in fourfold coordination with oxygen.

Consequently, AlPO^ can crystallize with the same structure as quartz.

Similarly, tantalite, FeT^g, is isomorphous with rutile, TiOj (TiTijOg) ;

the metallic ions are similar in size, and all show sixfold coordination

with oxygen.

In summary, materials belonging to the same isomorphous groups have the

same characteristic isotropy. Because the atomic weights and induced dipole

moments for differing isomorphous compounds are not the same, however,

isomorphous materials do not display the same complex polarizability on the

molecular (or macroscopic) level. A fertile area for future applied research

would be to measure the dispersive frequency- and temperature -dependent

characteristics of dielectric isomorphs and to relate the macroscopically

measured dielectric behavior to calculable atomic or molecular polarizability.

74
4.4.2.2 Polymorphism

Any discussion of dielectric isotropy or anisotropy in a search for

reference materials would be incomplete without mention of polymorphism.

Almost all elements or compounds can exist in more than one crystal form; this

phenomenon is known as polymorphism. Each form has different physical

properties and a distinct crystal structure. In other words, the atoms or

ions are arranged differently in different polymorphs of the same substance.

It is therefore not surprising that polymorphs of the same substance have

differing directional optical and electrical properties. A polymorphic

substance can be described as dimorphic, trimorphic , etc., according to the

ntamber of distinct crystalline forms. Polymorphism is an expression of the

fact that molecular crystal structure is not determined exclusively by

chemical composition, and there is often more than one structure into which the

same atom or ions in the same proportions may be built up. One example is the

relationship between diamond and graphite. In diamond each carbon atom is

linked to four other carbon atoms by homopolar bonds, all the linkages being of

equal strength and the crystal as a whole being a giant molecule (as in most

organic materials) . In graphite each carbon atom is linked to three other

carbon atoms by homopolar or covalent bonds, which results in the formation of

planar sheets of carbon atoms. These sheets are joined by weak residual van

der Waals forces. Diamond (C) falls in the isometric lattice system, whereas

graphite (C) falls in the hexagonal system. Diamond is therefore electrically

Isotropic and would make an excellent dielectric reference material were it not

for its extreme hardness. This example presents the greatest known contrast in

structure and properties to be found in any pair of polymorphous substances.

Other physical properties of materials such as hardness and mechanical strength

75
are generally determined by the weakest atomic bonds , which are the first to

suffer disruption under increasing mechanical or thermal strain.

Different polymorphs of the same substance are formed under different

conditions of pressure and temperature. The diamond- graphite equilibrium

curve, for example, is given in figure 14. Another example of the stability

relations between four polymorphs of quartz is shown in figure 15.

Whether or not a change from one pol3nnorph to another is reversible and

takes place at a definite temperature and pressure is a basis for the recognition of two types of polymorphism. When the change from one polymorph to

another is reversible, the polymorphism is known as enantLotropic; when the

change is irreversible, the polymorphism is monotropic . The pol)nnorphism of

quartz is enantiotropic; hence, at a pressure of 101 325 Pa,

867°C 1470'C

+- quartz tridymite * cristobalite .

However, the reaction rates for the quartz polymorphs are exceedingly slow.

Cristobalite is a common naturally occurring substance; because of its isotropy

(isometric system), mechanical stability and hardness, it would make a good

dielectric reference material in sufficiently pure form. Generally, high- low

polymorphs are characterized by the fact that the high- temperature forms have

higher symmetry (implying greater electrical isotropy) than the corresponding

low- temperature forms. In addition, high- temperature polymorphs of a substance

usually have more open lattice structures than low- temperature forms and

therefore have lower density. As an aside, if Che various polymorphs of rare

earth oxides are understood in terms of their lattice structures and molecular

76
" 100

gi 20

1000 2000 3000

TEMPERATURE (K)

Figure 14. Diamond- graphite polymorphous equlllbrlxim curve

2000

1713

o 1470

UJ

en 1000

573

1 r LIQUID

CRISTOBALITE

(Isometric)

TRIDYMITE

(Hexagonal

HIGH-QUARTZ (/3)

(Hexagonal, Trapezohedral)

LOW-QUARTZ (a)

(Trigonal, Trapezohedral

2000 4000

PRESSURE (kg/cm^)

6000

Figure 15. Stability relations for polymorphs of dry SiOj (silica)

77
polarization properties , it may be possible to predict high- temperature

superconducting properties from macroscopic dielectric measurements

.

4.4.3 Hardness

Machinability of a reference material depends on both Its hardness and

tenacity. The hardness of a material (or mechanical stability) Is generally

defined as its resistance to scratching, and relative hardness as a useful

diagnostic property has its origin (and reference materials) in systematic

mineralogy. It was given qualitative precision by the Austrian mineralogist

Mohs , who in 1822 proposed the relative hardness scale given in table 8.

Each of these minerals will scratch those minerals lower in the scale.

Table 8. Mohs' relative hardness scale

Increasing Hardness

t 10. Diamond, C

9. C o rundum , AI2O3

8. Topaz, Al2Si04(0H,F)2

7. Quartz, SiOj

6. Orthoclase, KAlSigOg

5. Apatite, Ca5(POj3(F,Cl,OH)

4. Fluorite , CaFj

3. Calcite, CaCOg

2. Gypsum, CaSO^ • 2H2O

4- 1. Talc, Mg3Si,0,o(OH)2

Decreasing Hardness

The scale that Mohs established is still used today in unaltered form and

is a tribute to his perspicacity. In his original description Mohs endeavored

78
to make the intervals on the scale as nearly equivalent as possible while at

the same time to select common minerals for the individual units . The

interval between corundum and diamond is greater than that between other units

on the scale, but minerals of intermediate hardness were (and still are)

unknown. Hardness varies somewhat with crystallographic direction, many

minerals being softer on cleavage surfaces than in other directions; therefore

finely crystalline specimens of inorganic materials are better used as

standards than coarsely crystalline minerals.

Quantitative procedures for hardness determination have shown that the

intervals on Mohs ' scale are approximately equal, except between 9 and 10.

Thus, although it is qualitative, Mohs' scale is well suited for comparing

relative hardness in minerals and other materials and is unlikely to be

superseded. The fingernail has a hardness equal to 2 1/2 while a pocket knife

has hardness 5 1/2 . Minerals or materials of hardness 1 generally have a

greasy feel; those of hardness 2 can be scratched with the fingernail.

Materials of hardness 3 can be cut by a knife; those of hardness 6 and over

are not scratchable by a knife and, moreover, will scratch silica glass. A

set of small pieces of hardness points or conical pieces of standard minerals

set in brass rods are useful for determining material hardness.

With respect to the lattice crystal structure, hardness is the resistance

of the structure to mechanical deformation. The following relations hold

between hardness and lattice crystal structure:

(1) The greater the valency or charge of atoms or ions, the greater the

hardness

(2) The smaller the atoms or ions, the greater the hardness.

79
(3) The greater the packing density of atoms or ions, the greater the

hardness

.

The effect of ionic size on hardness can be clearly seen by examination

of isomorphous groups, where the lattice structure is the same for all members

of that group. The hematite group (see table 5) comprises oxides of trivalent

+ 3 +3 metals ranging in ionic size (see figure 17) from Fe (0.064 nm) to Al

(0.051 nm) ; hardness increases with decreasing ionic size, from 6 for hematite

to 9 for corundum (alumina) . Another example is in the calcite group which

+ 2 comprises carbonates of divalent metals ranging in ionic size from Ca

+ 2 (0.099 nm) to Mg (0.066 nm) . In this case calcite (CaC03) has a hardness of

3, whereas magnesite (MgCOg) has a hardness of 4 1/2.

Figure 16 illustrates the periodic table and gives both the charge and

atomic radius (in nanometers) of the common ions. From figure 16 we see that

for an element which can exist in several valence states (form ions of

different charge), the ionic radius decreases with increasing positive charge;

+ 3 +5 e.g., V : 0.074 nm; V : 0.059 nm) . Intuitively, this might be expected since

as electrons are lost the nucleus exerts a greater pull on those remaining,

decreasing the effective radius of the ion. This same rule is observed in

going across a horizontal row in the periodic table; the radius of the ions,

in general, decreases.

The effect of valency or charge on hardness can be seen by comparing

compounds with the same structure and similar ionic sizes. Soda niter (NaNOg)

and calcite (CaCOg) have the same structure, and the ionic sizes of

Ca (0.099 nm) and Na (0.097 nm) are similar. However, the hardness of soda

niter is 2 and that of calcite is 3 [24]. The difference in hardness is due

to differences in valence states.

80
Lastly, the effect of packing density has already been alluded to in

symmetry considerations of different polymorphs. For example, low- or highquartz has a greater packing density (2.65 g/cm^) than does tridymite

(2.26 g/cm^) , even through tridymite has greater lattice symmetry (less

electrical anisotropy) . Quartz has a hardness of 7, whereas tridymite has

a hardness of 6^5.

H He

l.i' B.- H3 C N6 0-' F- Nc 0.68 0.35 0.23 0.16 0.13 1.40 1.36

S" Na' Mi,'2 Al' Si* p6 0.30 ci- A 0.97 0.66 0.51 U.42 0.35 s-= 1.81 1.84 V Cr'' Mn« F<- Co' Cm' K' Ca' Sc' Ti< 0.59 0.52 0.60 0.64 0.63 Ni' 0.72 Zn2 Ga' Gc* .\sr' Se« Br- Kr

1.33 0.99 0.81 0.68 V3 Cr-^ Mn2 Fr2 Co' 0.69 Cu' 0.74 0.62 0.53 0.46 0.42 1.95 0.74 0.63 0.80 0.74 0.72 0.96

Sb'

Kl)' .Sr2 ^» 7.\' Nb'' \W' Ru« Rlv^ l><P .\i;" CcP Iiv^ Sn^ 0.62 Tc*^ I- Xc

1.47 1.12 0.92 0.79 0.69 0.62 0.67 0.68 0.80 1.26 0.97 0.81 0.71 .Sb' 0.56 2.16 0.76

La-^- Pb*

(:=' B,i2 1.14 Hf Ta'' W" Rc< Os^' Ii< I'l^ .\.i' Hi.' Tl' 0.84 Bi'

1 6' 1.34 l.ir^ 0.78 0.68 0.62 0.72 0.69 0.68 0.80 1.37 1.10 1.47 I'b' 0.96

0.85 1.20

Th' U^

1.02 0.97

Figure 16. The periodic table, giving the charge and radius

(in 10'^° m) of the common ions.

Since the bonding within the lattice structure of a material can be

different in different directions, the hardness of a material may be expected

to vary with direction. Such variations, though, are usually quite small.

81
Some degree of correlation exists between hardness and chemical

composition [24] as is given in table 9.

Table 9. Correlation between mechanical hardness and chemical

composition for inorganic compounds

HARDNESS

< 3 < 5 < 5

> 5h

< 5\

CHEMICAL COMPOSITION

Heavy metals (silver, copper, mercury, lead)

Sulfides (except those of nickel and iron)

Hydrates

Anhydrous oxides and silicates

Carbonates, sulfates, phosphates

The relevance of this discussion to the search for dielectric reference

materials is that materials are desired that not only are linear, homogeneous

and isotropic, but that have a hardness of at least 5^ on the Mohs Scale.

4.4.4 Tenacity

Tenacity of a material is defined as the resistance that material offers

to breaking, crushing, bending, or cutting. Most inorganic compounds or

minerals are brittle. In other words, they can be crushed to a fine powder.

This allows some degree of fusibility (e.g., fused quartz, alumina, rutile)

,

but at the expense of machinability . A few inorganics (native metals) are

malleable, which simply means their shape can be readily changed without

breaking; hammering or grinding causes the grains to be rolled out into

plates. A material is called elastic if after bending it springs back into

82
its original form. Reference materials will probably necessarily have a

tenacity which is brittle, albeit remain elastic.

4.4.5 Wettability

Both inorganic and organic materials exhibit marked differences in the

properties of their surfaces. One such property of great technical significance for a dielectric reference material is called the "wettability," that

is , the relative ease with which a surface of that material can be coated with

water. Lyophile materials are those which are easily wetted, and lyophobe

materials are those not easily wetted. The differences in surface wettability

have been applied for many years in the minerals extraction industries (e.g.,

for separation of lyophobe minerals such as diamonds from accompanying

lyophile minerals)

All degrees of wettability between extremely lyophile and extremely

lyophobe materials exist. Generally, materials with ionic bonding are

lyophile. Those with metallic or covalent bonding (such as sulfides or

plastics) are lyophobe. Diamond is an example of covalent bonding within an

isometric lattice structure and is lyophobe. Quartz, on the other hand, has

ionic bonding in silicon and oxygen tetrahedra and is lyophile. Most ceramics

also have ionic bonding and are lyophile. Ideally, a dielectric reference

material is a substance which is lyophobe, since a wettable material can

affect electrical property measurements (and performance in practice)

Because of these factors one might place priority on some organic materials

such as polytetrafluoroethylence (Teflon) or cross -linked polystyrene

(Rexolite) which exhibit covalent bonding structures. The problem here then

becomes one of thermal expansion over the temperature range of application;

83
however, these are problems of significance in application, and provided the

temperature is kept constant (and specified) , some of the organic materials

will be seen to be useful dielectric check standards.

4.4.6 Piezoelectric Versus Pyroelectric

Two other properties can be significant in a search for low- loss dielectric reference materials. One of these, pyroelectricity, results from the

fact that polarization changes can be induced by changes in temperature.

Pyroelectric materials, such as lithium sulfate, barium nitrite, and tourmaline, are commonly used in infrared sensing devices; these types of low- loss

materials, whose dielectric properties are strong functions of temperature,

usually occur in substances whose lattice structures have polar symmetry axes

.

The other common phenomenon, piezoelectricity , results from the fact that

polarization charges can be created by directed pressure. The application of

piezoelectricity to radio with the use of quartz is well-known; here an

alternating electric field generated by the circuit is applied across a quartz

plate, properly cut and mounted and dimensioned so that one of its natural

frequencies of mechanical vibration coincides with the resonant frequency of

the circuit. The frequency of transmission or reception is therefore

stabilized and precisely controlled. In general, any material lacking a

center of lattice symmetry will be piezoelectric, although the effect may be

very weak. In dielectric metrology, samples are rarely placed under directive

stresses, although measurements may be taken at widely variant temperatures.

Therefore, as long as the candidate dielectric reference material is

homogeneous, linear and isotropic, has suitably low loss over a broad range

84
in frequency and temperature, and has adequate machinability , it may be

piezoelectric, but be minimally pyroelectric . The material must also not

undergo molecular polymorphism over small temperature ranges.

5. SUITABLE DIELECTRIC REFERENCE MATERIALS

Thus far, basic principles of dielectrics and requirements for reference

materials in terms of spatial homogeneity, isotropy, long-term stability, and

wettability (moisture absorption) have been reviewed. In addition, the

desirability of a dielectrically nondispersive, non-Debye material, both with

respect to frequency and temperature variations, has been indicated or, at

least, if the material is dispersive, that it be predictable in terms of

ambient conditions and frequency of the applied field. These concepts have

been looked at in the context of the chemical physics of materials.

Generally, the constitutive electrical parameters of materials are

measured by replacing vacuum or air with a specimen of known dimensions in an

electrical circuit and measuring appropriate changes in the circuit. The

sample holder is usually a lumped parameter circuit reactance or a section of

transmission line or cavity (open or closed) , and the observation may be of

resonance or of impedance. Actual measurements characteristically involve

three steps [25], namely, the solution of an electromagnetic boundary value

problem, the dimensional gauging of the system used, and the electrical

measurements on the system such as the complex impedance or the complex

resonant frequency of the system. It is beyond the scope of this Technical

Note to describe the standard configurations that are widely used in

dielectric and magnetic measurements except to say that these measurements

depend on the state of development of basic rf and microwave measurements --

85
impedance, attenuation, etc. Usually the dimensional gauging of the system

and small departures of the system from the form assumed in the initial ideal

boundary value problem are the limiting factors, as opposed to electrical

observations

.

As stated earlier, standard dielectric samples (or those whose dielectric

properties are characterized by well-known and precise limits of error) are

useful in a laboratory in order to improve or confirm the accuracy of the

measuring procedures and equipment used. Standardization of the permittivity

of a material and, concomitantly, the comparison of the measuring accuracy at

separate laboratories have the feature that the standard for the work is

assumed identical for all laboratories, being 6^ for the dielectric constant

of the vacuum [26].

Numerous dielectric measurements of various solid insulating materials

have been made by the National Institute of Standards and Technology and

Von Hippel [27]. These measurements were made with parallel-plate capacitors,

short-circuited transmission lines, and cavity resonators. Some of the

results of these dielectric measurements are shown in figure 17 on materials

that might prove to be useful low- loss reference standards over a broad range

in frequency and temperature. Data are summarized showing the material

composition, temperature, dielectric constant, loss tangent, frequency,

dielectric strength and dc volume resistivity (at 25°C), thermal linear

expansion (when known), softening point, and moisture absorption. Note that

these dielectric measurements for fused quartz, various ceramics and plastics

are given parametrically as a function of frequency at one temperature, 25° C.

All materials are low- loss and display no relaxation over the frequency range

of measurement, with the exception of barium titanate.

86
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On first examination, it seems that polytetrafluoroethylene (Teflon)

would make an ideal dielectric reference material for low- loss, low permittivity applications. Teflon has a dielectric constant close to 2.0 from

10 kHz to 25 GHz, a loss tangent < 0.0006 over the same frequency range and no

wettability. It is also nonflammable, completely inert to most chemicals, and

inexpensive. However, it has a relatively low softening point or glass

transition temperature [28] (~66°C). Furthermore, it has a high coefficient

of expansion (see figure 18), low fusibility, and exhibits strong degradation

in dielectric properties when exposed to ionizing radiation.

1.10

-1.02

1.00

40 80 120 160

TEMPERATURE (°C)

200

Figure 18. Thermal expansion of polytetrafluoroethylene as a

a function of temperature [27],

In fact, the deterioration of the insulating characteristics of plastics

(or most organic materials) in the presence of ionizing radiation is well

known. Only the polymer polystyrene (Rexolite), which is a high-molecularweight derivative of vinyl benzene [Cg Hj CH ^H2 3n (^^^^^ ^ is normally

88
greater than 500) , shows no permanent dielectric degradation after suffering

irradiation dosages as high as 300 C-kg"^ and dosage rates as high as 40 C-kg'^

per hour [27]. Polystyrene also can absorb some water, which accounts, at

least partly, for its loss tangent being an order of magnitude greater than

polytetrafluoroethylene and polyethylene. Polyethylene exhibits good low

permittivity, low loss dielectric reference material characteristics. The

problem with polyethylene, though, is not only its low melting point of 105° C,

but also the fact that it oxidizes at temperatures less then 80° C, becomes

brittle, and therefore loses its dielectric characteristics. Even when

stabilized against degradation by heat, polyethylene still deteriorates when

exposed to ultraviolet light [27] with consequent embrittlement and loss of

electrical characteristics.

CROSS-LINKED POLYSTYRENE (REXOLITE)

0.0021-

0.0010

w 0.0008 c 0.0006 ^ 0.00041-

0.0002

0.0001

1 1 1 1 1

I f-lOGHzI

~ 1 1 1 1 1 ~

20 40 60 80

TEMPERATURE (°C)

100 120

Figure 19. Temperature dispersive characteristics of cross-linked

polystyrene (Rexolite) at 10 GHz.

89
Of the organic solids shown, cross -linked polystyrene appears to have the

best characteristics for a low-loss, low permittivity dielectric reference

material (and check standard) . The temperature dispersive dielectric

characteristics of cross -linked polystyrene are shown in figure 19.

The dispersive dielectric characteristics of fused silica, alumina,

steatite, and titanium dioxide as a function of temperature [27] are shown in

figures 20, 21, 22, and 23, respectively.

£ 4.0 "^ 3.5

0.002

c 0.001 " 0.000

FUSED SILICA

T

f = 10 GHz

1 1

1 1 1 1 1 100 200 300 400 500 600

TEMPERATURE (°C)

Figure 20. Temperature dispersive characteristics of fused silica

at 10 GHz [25.26] .

Fused silica displays very low loss (tanS < 0.002) from 0°C to SOO'C

while at the same time exhibiting a constant dielectric constant of 3.82 over

the same temperature range. Apart from its tenacity (brittleness) fused

silica (in pure form) satisfies the preferred characteristics of a low

permittivity, low-loss dielectric reference material.

90
For a high dielectric permittivity and low- loss material, either alumina

with e = 9.48 (> 99.5% pure) or steatite (fayalite) with e' = 5.77 exhibits

notable characteristics. Alumina, however, has lower loss at temperatures

less than 150° C than does fayalite, although at 10 GHz fayalite 's permittivity

and loss tangent are approximately independent of temperature (from 0°C to

500°C). At much lower frequencies (< 10 kHz) fayalite becomes strongly

dispersive with temperature; therefore alumina is probably the better choice

for both a reference material and check standard.

For very high dielectric constant (~100) , fused rutile or titanium

dioxide behaves well as a reference material, as long as the temperature does

not exceed 250°C. Barium titanate also possesses a very high dielectric

constant (€' = 100 at 25 GHz); however, it also possesses a loss tangent of

0.60 at 25 GHz, has a ferroelectric perovskite lattice structure, and exhibits

nonlinearity and dielectric hysteresis. For a dielectric reference material

of very high permittivity and low loss, titanium dioxide would be the better

choice

91
ALUMINA (99.5 PERCENT)

0.5

0.4

0.3

c

03 0.2

0.1

0.0

100 200 300 400

TEMPERATURE (°C)

600

Figure 21. Temperature dispersive characteristics of alumina

(99.5% pure) at 1 MHz [26.27].

92
10

9

o 8

w 7-

6-

<X5

03

0.010

0.008

0.006

0.004-

0.002-

0.001

STEATITE 410 (FAYALITE)

1 1 1 1 1

f=10GHz

1 1 1 1 1

100 200 300 400 500

TEMPERATURE (°C)

600

Figure 22. Temperature dispersive characteristics of steatite

(fayalite) at 10 GHz [27].

93
TITANIUM DIOXIDE (RUTILE)

100 200 300 400 500 600

TEMPERATURE (°C)

Figure 23. Temperature dispersive characteristics of fused titaniiam

dioxide (rutile) at 1 MHz.

94
6 . CONCLUSIONS

Because dielectric components are critical to the performance of all

electronic equipment, a national need exists for improved dielectric materials

and precision measurement methods. Reference materials serve as basis points

for measurement accuracy standards. Ideal dielectric reference materials

should be electrically and magnetically linear, homogeneous, and isotropic.

It is best that they also have low thermal expansion coefficients, high

softening temperatures, and both chemical and mechanical stability, while

still being machinable and readily available.

To characterize properly the electromagnetic nature of any material, it

is necessary to understand and determine the fundamental physical processes

that govern electromagnetic behavior and that define the constituent electric

and magnetic properties. Materials polarize in an applied electric field.

The principal polarization mechanism depends on the frequency of the applied

field and may be electronic, atomic, dipolar, or interfacial in nature. The

electric polarizability of a material defines that material's complex

dielectric constant which is, in general, expressed in complex form as the sum

of the real effective permittivity and loss factor. For uniaxially or

biaxially anisotropic materials, the dielectric constant is a 3 x 3 complex

tensor. If the material attenuates electromagnetic waves propagating through

them, both the real effective permittivity and loss factor become functions of

frequency, or are dispersive. It is important to understand frequencydependent behavior of a dielectric if it is to be used as a standard reference

material

Polarization, or charge separation in material media, is physically

damped in the rf and microwave regions by relaxation processes. Analogous to

95
a R-C ladder lumped parameter circuit, the time-constant distribution function

quantifies a material's intrinsic relaxation and allows the derivation of

analytic relations between permittivity and loss tangent as a function of

frequency. These dispersion relations were derived for a Debye material

(single relaxation) and for a material that has an infinitely broad,

continuous distribution function (no relaxation) . It was shown that suitably

sampled measurements of £' and €" may be fruitfully used to indicate whether a

single or multiple distribution of relaxation times exist in a dielectric

material and, if a distribution exists, the symmetry of that distribution.

Once a material has been classified as a Debye material, for example, only the

low- and high-frequency complex permittivity measurements are needed to

completely characterize that material over all frequencies.

The derived dispersion relations in section 4.3 reveal a change in real

effective permittivity that varies linearly with the loss tangent and that

varies logarithmically with change in measurement frequency for either a

material characterized by single relaxation or no relaxation. These effective

permittivity- loss tangent relations are very useful for determining the

broadband dispersion characteristics of a dielectric reference material from

limited measurement data or, for that matter, predicting the dielectric

behavior of any material, even at frequencies where measurement data are not

taken. They are also useful for determining which modal roots are valid in

dielectric cavity or waveguide measurement fixtures, identifying discrepancies

and errors in reported dielectric measurements, and indicating where peak

absorption frequencies occur in lossy materials.

96

I
Generalized relationships between the real effective permittivity, e'(w),

and loss factor, e"(w), for any dielectric material possessing an arbitrary

number of relaxation times of any distribution asymmetry were derived. The

loss factor as a function of frequency can be determined by the Hilbert

transform of discretely sampled permittivity values. Similarly, the real

effective permittivity as a function of frequency is equal to the Hilbert

transform of the loss factor plus the high-frequency (optical) limit, e^.

Numerical Hilbert transform results indicate that measurements taken over

three decades in frequency suffice to predict either the real effective

permittivity from the loss factor or the loss factor from the real effective

permittivity in the dipolar relaxation regime, with an error bound less than

two percent. This was true as long as discretized data are obtained over the

range 0.1 < ojT < 10, where T is the principal relaxation time of the

dielectric. The Hilbert transform relationships are valid for rf, microwave,

mm, and IR frequency ranges. The only presuppositions are that the dielectric

material behave linearly in the presence of an electric field, the dielectric

is causal (does not polarize before stimulus of the electric field) , and the

constitution of the dielectric does not change within the time of observation

(as, for example, some polymorphic materials do change with variations in

temperature) . The Hilbert transform relations are quite useful in the

characterization of reference materials in the following two ways. First,

uncertainty in loss measurements (for both low- loss standard reference

materials and absorbent materials) is usually much greater than the uncertainty in real effective permittivity measurements. Therefore precise

measurements of real effective permittivity over a range in frequency can be

97
used to determine the loss factor as a function of frequency. Second,

prediction of absorbent dielectric characteristics can be made from out- of

band measurement data. In the search for dielectric reference materials, the

effects of temperature variations are quite important in the determination of

softening points that can lead to volumetric creep phenomena or in the

determination of expansion and contraction characteristics of the material

under study. Expansion or contraction of a dielectric reference material can

lead to serious air gap errors in precision dielectric measurement fixtures if

not accounted for. Hence (linear) thermal expansion coefficients less than

10"^/K are preferred. In addition, fundamental changes in a material's

polarizability or loss occur as a result of differing temperature -dictated

energy states of the material. It is vital to know the fundamental behavior

of the complex dielectric constant as a function of temperature, particularly

if that material is a reference standard. Stated differently, if the polarizability of a material can be related to the known activation energy of that

material at a given temperature and under the influence of a time -varying

electric field, then a means for predicting the dielectric behavior of that

material as a function of temperature can be gained. In order to accomplish

this, a bistable model of an elementary dipole within a dielectric whose

molecular groupings could be characterized by well-defined, permanent dipole

moments was considered. Consideration of the probability of a jump by a

charge in a double potential well led to a relation which describes the

dispersive behavior of a dielectric as a function of absolute temperature,

frequency, activation energy, and the dipolar polarizability of the material.

The temperature -dependent relaxation time follows Boltzmann's law, and a

marked similarity was noted in the differential equation for the dipolar

98
polarization of a dielectric medium as a function of temperature with that

derived for Debye dielectrics, as a function of frequency of the applied

electric field. The derivation given in section 4.3.5 for the effect of

temperature on dielectric properties is limited to dielectric materials where

the interaction between individual dipoles can be neglected and for conditions

where pE << kT (nonsuperconducting states), where p is the dipole moment, E is

the applied electric field, k is Boltzmann's constant and T is absolute

temperature

The temperature -dependent dispersive effects on dielectric behavior using

the bistable model are an important area for further research and laboratory

examination. The same material dielectric property measurement made at a

given temperature and frequency could be expected for a different combination

of temperature and frequency. The limitations of the bistable model,

noninteraction of individual molecular dipoles, and temperature domain

(particularly near critical superconducting states) remain to be determined.

In the past, homogeneity of any dielectric reference sample was determined by

making many measurements on samples of the same material produced by the same

manufacturing process. These measurements were then compared with those made

at other laboratories where different fixtures were used. Generally,

corrections that are due to departures of the actual fixture from the

idealized theoretical model of that fixture are made to dielectric measurement

data. It is important to be able to distinguish deviations from homogeneity

in a candidate reference material from fixture measurement inaccuracies.

Therefore an approach for examining the influence of deviations from

homogeneity on a precisely specified electromagnetic field structure was

99
outlined. This approach replaces the sample with an effective scattering

current. Sample geometry, impressed field structure of the measurement

fixture, and frequency of excitation are all arbitrary. The dielectric sample

under test can be considered as a superposition of electric dipole

distributions, and the total electric field at any point exterior to the

sample may be written as sum of the impressed field in the sample plus a

convolution integral of the tensor Green function with the scattering current

that defines the sample. The convolution integral reduces to only an

integration over the sample volume, where the spatial distribution of 6', e"

is arbitrary. The equation for determination of the complex dielectric

constant at any frequency and for any sample point is a Fredholm integral

equation of the second kind. If the dielectric sample under test displays

low loss, it may be possible to determine the permittivity distribution

independently of how the sample was machined by making use of the Born

approximation (field within sample approximately equal to incident field).

Iterative Born techniques may be used to solve for the complex permittivity

when sample losses are not low. The same analysis can provide corrections to

measurement data when an otherwise homogeneous sample is not axially centered

in a cavity or waveguide fixture, or when a nonuniform air gap exists around

the sample within either of the above fixtures. Similarly, the effects of

eccentricity of a cylindrical waveguide or axially nonorthogonal endplates on

a resonating fixture can be determined by the same equations.

One of the last primary characteristics of an ideal dielectric reference

material is that the complex permittivity be the same in all directions, or

that the reference material be electrically isotropic. A sufficient condition

for isotropy is that the material have no lattice structure (or be amorphous)

,

100
be cryptocrystalline (such as fused silica) , or have a lattice crystal

structure that belongs to the isometric system. Similarly, materials whose

lattice structures are in the tetragonal and hexagonal systems are intrinsically uniaxially anisotropic, and those whose lattice structures fall within

the orthorhombic , monoclinic, and triclinic systems are biaxially anisotropic.

Knowledge of the molecular lattice structure allows the choice of a reference

material which, in terms of its directional electrical properties, is

intrinsically isotropic or has well-defined anisotropy. This is an important

point since inorganic substances which have the same lattice structure on the

molecular level will have the same directional dielectric property behavior.

Substances with analogous formulas and in which the relative sizes of cations

and anions are similar usually have closely related lattice structures and are

said to be isomorphous. An isomorph of a material that falls within the

isometric lattice structure system would be expected to possess the same

characteristics of isotropy that is requisite for a reference material or

check standard. Because the atomic weights and induced dipole moments of

differing isomorphous compounds are not the same, however, isomorphous

materials are not expected to display the same complex polarizability

Any discussion of dielectric isotropy or anisotropy in a search for

reference materials would be incomplete without mention of poljonorphism.

Polymorphism is an expression of the fact that molecular crystal structure is

not exclusively determined by chemical composition, and there is often more

than one structure into which the same atom or ions in the same proportions

may be built up. The change from one polymorph to another is largely dependent on temperature and pressure conditions and may be reversible or irreversible. Dry quartz, for example, has lattice structures that may be isometric,

101
hexagonal, or trigonal, depending on the temperature and pressure conditions.

The important point here is that it is desirable not to have a reference

material which is polymorphic over small temperature ranges.

At present a type of "pseudo-isotropy" is enforced on many dielectrics

used in application that are otherwise intrinsically anisotropic. For

example, alumina (corundum), which is an isomorph of the hematite group, is

widely used as a substrate material for high frequency applications (due to

its high real effective permittivity, low dielectric loss, and inert behavior

when subjected to chemical, vacuum or thermal processing), and has a lattice

structure which is inherently uniaxially anisotropic. By taking very fine

particles of corundum and sintering them under high pressure and high temperature, the microcrystalline anisotropy is "averaged" out in the finished

ceramic substrate. However, this is done at the expense of surface finish of

micros trip transmission line product, a major contributor to attenuation.

Secondary characteristics of a reference material, such as its

machinability , chemical inertness, and moisture absorption, are also important

considerations. The machinability of a material depends on both its hardness

and tenacity. Several relations hold between hardness and lattice crystal

structure. First, the greater the valency or charge of atoms or ions, the

greater the hardness. Second, the smaller the atoms or ions, the greater the

hardness. Third, the greater the packing density of atoms or ions, the

greater the hardness . Dielectric reference materials should have a hardness

of at least 5h on the Moh scale. Correlations between mechanical hardness and

chemical composition for inorganic compounds quite naturally lead to the

choice of anhydrous oxides and silicates as candidate reference materials

102
(as opposed to carbonates, sulfates, phosphates, or sulfides). Most inorganic

compounds, on the other hand, are brittle. This allows some degree of

fusibility, but at the expense of machinability . Reference materials will

probably have a tenacity which is brittle yet be elastic. A final characteristic of an ideal dielectric reference material is that it be a substance

which is lyophobe , since a wettable material can affect electrical property

measurements. Solids with covalent bonding (such as diamond) are lyophobe and

generally chemically inert, as are many organic materials such as polytetrafluoroethylene or polystyrene. Generally, however, materials with ionic

bonding are lyophile (wettable) , and the problem with most organics is their

temperature coefficient of expansion, as well as deterioration in the presence

of ionizing radiation. Hence compromises must be made in the secondary

characteristics of machinability, wettability, and possibly dispersion to give

proper emphasis on electrical linearity, homogeneity, and isotropy.

Numerous dielectric measurements on solid insulating materials have

been made. These measurements were made with parallel -plate capacitors,

transmission-reflection and short-circuit lines, and cavity resonators. Data

indicating the material composition, temperature, real effective permittivity,

loss tangent, thermal linear expansion, softening point, and moisture absorption were compiled. All materials studied were low- loss and displayed

negligible relaxation over the frequency range of measurement, with the

exception of barium titanate.

On first examination, it appeared that polytetrafluoroethylene would make

an ideal dielectric reference material for low- loss, low permittivity applications. Polytetrafluoroethylene has a dielectric constant close to 2.0 from

103
10 kHz to 35 GHz, a loss tangent < 0.001 over the same frequency range and no

wettability. It is also nonflammable, completely inert to most chemicals and

of low cost. However, it does have a relatively low softening point, high

temperature coefficient of expansion, low fusibility and exhibits strong

degradation in dielectric properties when exposed to ionizing radiation. The

deterioration of the insulating characteristics of plastics (or most organic

materials) in the presence of ionizing radiation is well known [27] . Only the

polymer polystyrene shows no dielectric degradation after being exposed to

high radiation. Thus, of the organic solids studied, cross -linked polystyrene

appears to have the optimal characteristics for a low- loss, low effective

permittivity dielectric reference material (and check standard)

.

Of the inorganic materials studied, fused silica exhibits very low loss

(tan 8 < 0.002) from O^C to 500°C while at the same time displaying a constant

dielectric constant of 3.82 over the same temperature range. Apart from its

brittleness, fused silica (in pure form) satisfies the characteristics of a

low real effective permittivity, low- loss dielectric reference material. For

a high dielectric constant and low- loss material, alumina (99.5 percent pure,

with e' = 9.48) exhibits notable characteristics and, because of its lower

loss at temperatures less than 150"*C, is probably a better choice for a

reference material than are the steatite ceramics. Lastly, fused rutile or

titanium dioxide behaves well as a reference material for very high dielectric

constant (-100), as long as the temperature range does not exceed 250°C.

In summary, this technical report has addressed itself to the national

need for enhanced dielectric metrology and reference materials , as well as to

desired properties of reference materials. Fundamental electromagnetic

104
characteristics of all materials that relate to polarization mechanisms and

both frequency- and temperature -dependent relaxation processes were reviewed.

Since inhomogeneous materials result in a complex coupling of all electromagnetic field components upon which the constituent dielectric properties are

defined, an approach for analyzing the effects of inhomogeneities in an

arbitrary measurement fixture was presented, with suggestions for the

determination of the complex permittivity of a sample which has spatial

variance. Fundamental electromagnetic concepts of isotropy and uniaxial or

biaxial anisotropy were also reviewed with a special emphasis on the chemical

lattice physics. All of these considerations together with measurement data

could be used to choose suitable dielectric reference materials to be chosen.

In addition, a number of fundamental areas that deserve further

investigative effort, both for the advancement of broadband dielectric

metrology and for understanding dielectric behavior of materials in electromagnetic fields, became evident. These are suimnarized below and given as

recommendations for future work in applied dielectric metrology.

(1) Measure dispersive frequency- and temperature -dependent

characteristics of dielectric isomorphs and relate macroscopically

measured dielectric behavior to calculable atomic or molecular

polarizability

(2) Determine validity of relations between real effective permittivity

and loss tangent for lossy dielectric materials which exhibit Debye

and non-Debye relaxation mechanisms. From these relations examine

the predictability of dielectric properties at high frequency (nontransition state) from measured properties at lower frequencies, a

105
classical metrology problem. Clearly, broadband techniques of

dielectric metrology would be part of this effort.

(3) Examine dielectric equivalence of frequency -dependent dispersion and

temperature -dependent dispersion for ionically bonded solid materials. If possible, relate these properties to lattice structures of

high- temperature superconductors

.

(4) Most international comparisons of dielectric measurements involve a

prior check on the homogeneity of the subject reference material by

taking a number of individual sample measurements. However, future

assumptions about dielectric homogeneity are always subject to the

nonchangeability of proprietary manufacturing processes. This is

undesirable both from a point of view of future availability as well

as quality control of a proprietary manufacturing process. In

addition, most metrology techniques involve the solution of

electromagnetic boundary value problems where the sample geometry

must be precisely machined so as to fall within the idealized

surfaces of an orthogonal coordinate system. This ensures

separability of the electromagnetic field components in subsequent

computation of complex permittivity, as well as independence of

components of the polarization field from each other. In this case,

dielectric material characterization is subject to the precision

with which the geometry of the measuring fixture and sample are

known (as opposed to actual measurements of attenuation, impedance,

etc.), which again is undesirable. It should be possible, in

principle, to characterize the spatial homogeneity of a dielectric

material independently of that material's geometry, as long as the

106
field of the exciting source and system characteristics of receiving

probe(s) are known (measured). A fundamental dielectric metrology

problem would be to examine the precision with which the dielectric

properties of an inhomogeneous dielectric can be measured in a

specified source field, over a broad range in frequency.

(5) Intrinsically anisotropic dielectric materials are commonly fused or

sintered [29] under high temperature to form a macroscopic "pseudoisotropy" that is subject to proprietary manufacturing processes,

where quality control is uncertain. The metrology problem of

general electromagnetic field interaction with either a uniaxially

anisotropic or biaxially anisotropic material needs to be examined,

so as to ascertain when principal directions of anisotropy can be

determined, what the nature of dielectric anisotropy under carefully

controlled conditions is on electromagnetic field behavior, and how

best to implement laboratory measurements.

(6) Error budgets for all existing dielectric metrology techniques need

to be developed over broad ranges in temperature and frequency.

Dielectric substrates used in printed circuit patch antennas must

have real effective permittivities uniform to ±0.01 over 3 to 30 GHz

bandwidths in order not to suffer phasing errors greater than 2°

(phasing errors of multi-element antenna arrays can routinely be

measured to 0.1°). This implies dielectric measurements should be

made that are accurate to ±0.5 percent --an accuracy which is very

difficult to attain [22] and which must necessarily be demonstrated

by proper quantification of the error budget for the particular

measurement technique

107
REFERENCES

[1] Jackson, J. D. Classical electrodynamics. John Wiley & Sons, Inc.,

N.Y. ; 848 p. ; 1975.

[2] Nussbaum, A. Electromagnetic and quantum properties of materials.

Prentice -Hall, Inc., Englewood Cliffs, N.J.; 1966.

[3] Maxwell, J. C. A treatise on electricity and magnetism. Dover Publ.;

1891.

[4] Wagner, K. W. Erklarung der dielectrischen Nachwirkungs worgange auf

Grund Maxwellscher Archiv. Electrotechnik, v. 2: 371; 1914.

[5] Hasted, J. B. Aqueous dielectrics. London: Chapman and Hall: 302 p.;

1973.

[6] King, R. W, P.; Smith, G. S. Antennas in matter. MIT Press,

Cambridge, Mass.: 868 p.; 1981.

[7] Dukhin, S. S. Dielectric properties of disperse systems,

in Matijevic, E. , ed. , Surface and colloid science, v. 3. New York,

N.Y.: Wiley Interscience , 83-166; 1969.

[8] Sluyers-Rehbach, M. ; Sluyters, J. H. Sine wave methods in the study of

electrode processes, in Electroanalytical Chemistry, v. 4, A. J. Bard,

ed. New York, N.Y. : Marcel Dekker: 1-128; 1970.

[9] Debye, P. Polar molecules. New York, N.Y. : Chemical Catalog Co.; 1929.

[10] Smyth, C. P. Dielectric relaxation times in molecular relaxation

processes. London: The Chemical Society; 1-14; 1966.

[11] Wyllie, G. Dielectric relaxation and molecular correlation in

dielectric and related molecular processes. London; The Chemical

Society; 1972.

[12] Cole, K. S.; Cole, R. H. Dispersion and absorption in dielectrics.

J. Chem. Physics, 9: 341-351; 1941.

[13] Davidson, D, W. ; Cole, R. H. Dielectric relaxation in glycerol,

propylene glycol, and n-propanol. J. Chem. Phys . 29: 1484-1490;

1951.

[14] Williams, G. ; Watts, D. C. Non-sjrmmetrical dielectric relaxation

behavior arising from a simple empirical decay function. Trans. Faraday

Soc. 66: 80-85; 1970.

[15] Jonscher, A. K. The interpretation of non- ideal dielectric admittance

and impedance diagrams. Phys. Stat. Solutions (a). 32: 665-676; 1975.

108
[16] Jonscher, A. K. The universal dielectric response, a review of data and

their new interpretation. Chelsea Dielectrics Group, University of

London; 1979.

[17] Dwight, H. B. Tables of integrals and other mathematical data. The

Macmillan Company, New York, N.Y. ; 1972.

[18] Carton, C. G. The characteristics and errors of capacitors used for

measurement purposes. J. lEE, v. 93, Part II, 398-408; 1946.

[19] Lynch, A. C. Relationship between permittivity and loss tangent.

Proc. lEE, V. 118, n.l, 244-246; 1971.

[20] Kittel, C. Thermal physics. John Wiley & Sons, Inc., New York, N.Y.,

418 p. ; 1969.

[21] Tai, C. T. Dyadic Creen's functions in electromagnetic theory. Intext

Educational Publishers, Scranton, Pennsylvania, 246 p., 1971.

[22] Levine , H.; Schwinger, J. On the theory of electromagnetic wave diffraction by an aperture in an infinite plane conducting screen.

Comm. Pure andAppl. Math., Ill, 355-391; 1950.

[23] Kerns, D. M. Plane -wave scattering-matrix theory of antennas and

antenna- antenna interactions. NBS Monograph 162, 162 p.; 1981.

[24] Dana, J. D. A system of mineralogy, ed. 7; vol 1, 2, 3; New York,

Wiley.

[25] Bussey, H. E. Measurement of properties of materials: a survey.

Proc. IEEE, v. 55, n. 6, p. 1046-1053.

[26] Bussey, H. E, ; Gray, J. E.; Bamberger, E. C; Rushton, E. ; Russell, G.;

Petley, B. W. ; Morris, D. International comparison of dielectric

measurements. IEEE Trans. Instr. Measure, v. IM-13, n. 4, p. 305-311;

1964.

[27] Von Hippel, A. R. Dielectric materials and applications. MIT Press,

Cambridge, Massachusetts, 438 p.; 1954.

[28] Zallen, R. The physics of amorphous solids. John Wiley & Sons, N.Y.

304 p. ; 1983.

[29] Kolar, D. Sintering -- theory and practice. Materials Science Monograph

V. 14, Elsevier Press, New York; 1982,

109
APPENDIX

RELAXATION IN DIELECTRICS WITH A SINGLE RELAXATION TIME

In this appendix the polarization response of matter on a molecular scale

is considered. From eq (3) we have a definition for the static dielectric

constant in terms of the static value of the polarization P^, where

e, - 1 = P,/E (A-1)

and e^ is the static permittivity of a material in a static electric field E.

If we consider a parallel plate capacitor (whose plates have area A that are

separated by distance d) which is filled with dielectric material, then the

polarization P^ implies a dipole moment of the dielectric in the whole of the

capacitor that is

M3 = Pg Ad . (A- 2)

Hence P^ can also be defined as a dipole moment per unit volume, Dipole

moment signifies the product of charge and distance and is a concept that will

prove important for the interpretation of dielectric properties on a

microscopic scale.

From a perspective of macroscopic properties, eq (A-1) gives a relationship between P^ and the electric field E in equilibrium. If E changes with

time, P at any given moment will generally differ from Pg(E). A trend toward

equilibrium, however, implies that P will approach P , and an assumption about

the rate of P as a function of time will yield a differential equation for

P(t) . The simplest assumption is to take the time rate of approach to

equilibrium proportional to the distance from equilibrium, that is,

^ _dP^ ^ _ p^^^ ^ ^^3^

dt ^

110
where the relaxation time T is constant.

A small modification may now be made in eq (A-1) . As discussed earlier,

several mechanisms of polarization operate in a dielectric. One of these is

electronic polarization, which involves resonance phenomena and is responsible

for the optical refractive index. This polarization responds to a changing

electric field in negligible time at all frequencies used for electrical

measurements. In order to separate this polarization out of eq (A-1) we write

P + P

^s - 1 = ° E

"^

. (A-4)

where P^ refers to the static orientation or "dipolar" polarization and P^ is

the optical polarization that defines an optical dielectric constant 6^ by the

simple relation,

e^ - 1 = n^ - 1 = ^ . (A-5)

where n is the refractive index of the material. As an aside, there is some

ambiguity with regard to the frequency at which n should be measured, since

frequencies generated by microwave oscillators can be as high as 100 GHz,

where resonance phenomena just begin to appear. Generally, the optical

refractive index is measured for frequencies of 100 - 1000 THz . For practical

purposes, however, it is usually, satisfactory to consider e^ as the square of

the refractive index measured at frequencies from 10 GHz to 1 THz.

From eqs (A-4) and (A-5),

(£3 - e^) E(t) = Pd , (A-6)

and we may rewrite eq (A- 3) as

r iiZii^ . P . (P, + P^)

dt S ^ D (»'

111
or

. ^££(l> . p„(e) dt

dPo(t)

dt

+ P^Ct) =

P - P s oo

(€3 - e^) E(t) (A-7)

The right side of eq (A-7) is the equilibrium value of Pp corresponding to

E(t), and eq (A-7) is analogous to a simple lumped parameter network

computation of the charge on a capacitor in series with a resistor. For a

periodic electric field E(t) = E^ e2^^ , the solution to eq (A-7) may be

written immediately for the dipolar polarization,

PoCt)

(e. - e^)

1 + jWT

^

E„ e

jwt

(NO INITIAL POLARIZATION) (A-8)

as long as the dielectric has no polarization as a result of its previous

history. Here the asterisk * represents a complex quantity. When the

dielectric in question is polarized at t = as a result of its previous

history, the general solution for dipolar polarization may be written.

PoCt) = Po^

t/T

1 + JWT ° E„ e

jwt

(DIELECTRIC HAVING INITIAL POLARIZATION VALUE Pq)

(A-9)

For time -varying field measurements the first term of eq (A-9) can be

neglected in comparison to the second. Ignoring the first term yields from

basic principles the complex dielectric constant

For Pq = 0,

C (w) - Co

e (a;) - e„

K (<^) E(w)

^S - ^oo 1 + jWT

(A-10)

(A-11)

112
or

e*(o}) = e'(u) - je"(w) = e^ + f^

" .^^ (A-12)

which is identical with the Debye relaxation eq (19), where

e'(a;) = e^ + ^^-^-TT (^-^3)

and

e"(a;) = (e, - €_)a;T/(l + w^t^) . (A-14) oo

Equations (A- 13) and (A-14) are called the Debye equations since they were

first derived by Debye [9].

Generally, one measures the permittivity €' (oj) and the loss tangent

tarn = —-^—f , so that

e'(w)

tan5 = : = —^ 50^ (A-15)

2r2 ^'('^) ^S + ^00 '^'^

It is instructive to plot e' (uT) , e"(u}T), and tan5(a;T) for a dielectric which

behaves in a Debye fashion. Consider, for example, a dielectric with e^ and e

measured at 6 and 2, respectively. If the dielectric behaves in a Debye

manner, figures A-1 and A-2 show how e^ and 6^ behave as a function of WT . It

is not difficult to show that the maximum of e'^(wT) occurs at wT = 1 and has a

magnitude of (e^ - e^)/2. The inflection point of ep(a;T) also occurs at

WT = 1 and for a Debye dielectric always has a magnitude at this inflection

point equal to the arithmetic average of e and € . The maximum loss tangent,

however, does not coincide with the maximum of e'^(ujT) as indicated in

figure A- 3. Instead, the maximum value of tanfi for a Debye dielectric occurs

at wT = yCg/e^ (always at a radian frequency greater than the reciprocal of

the relaxation time) and has a predictable magnitude of (6^ - e^)/2e , where

€ is the geometric mean of e^ and 6^,

113
o

o

O h

" 3

o

o o o o o

<x> LD

^

CO C\J

o

o

O

u

o

0) H

•rl

u

o

IM

b-3

O

O

•HO

IM

O

{fl Q

2 ^

ow

o

••-I %

a; BQ

so

0)

a

114
o 1 1—

uM

—

Q) i-l

0) o h4

— t-H 1MJ

(4-1 , 3 — y / c1 / s A ^ 1 o f- — 1 T 1 r-l 3

«fl

— \ ^ * — \ 4J

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116
NIST-114A

(REV. 3-89) U.S. DEPARTMENT OF COMMERCE

NATIONAL INSTITUTE OF STANDARDS AND TECHNOLOGY

BIBLIOGRAPHIC DATA SHEET

PUBUCATION OR REPORT NUMBER

NIST/TN-1338

2. PERFORMING ORGANIZATION REPORT NUMBER

3. PUBUCATION DATE April 1990

4. TITLE AND SUBTITLE Dielectric Characterization and Reference Materials

5. AUTHOR(S)

Richard G. Geyer

6. PERFORMING ORGANIZATION (IF JOINT OR OTHER THAN NIST, SEE INSTRUCTIONS)

U.S. DEPARTMENT OF COMMERCE

NATIONAL INSTITUTE OF STANDARDS AND TECHNOLOGY

2<»iTMfa83»fflfeMftc«<»sac BOULDER, COLORADO 80303-3328

7. CONTRACT/GRANT NUMBER

8. TYPE OF REPORT AND PERIOD COVERED

9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (STREET, CITY, STATE, ZIP)

10. SUPPLEMENTARY NOTES

DOCUMENT DESCRIBES A COMPUTER PROGRAM; SF-185, FIPS SOFTWARE SUMMARY, IS ATTACHED.

11. ABSTRACT (A 200-WORD OR LESS FACTUAL SUMMARY OF MOST SIGNIFICANT INFORMATION. IF DOCUMENT INCLUDES A SIGNIFICANT BIBUOGRAPHY OR

LITERATURE SURVEY, MENTION IT HERE.)

Dielectric reference materials are analyzed with respect to fundamental requirements of

linearity, homogeneity, and Isotropy. Generalized frequency- and temperature-dependent

dispersion relations are presented which allow the prediction of broadband dielectric

behavior from limited measurement data, determination of valid modal field structure in

cavity or waveguide fixtures, and identification of discrepancies and errors in measurement data. An approach for examining the influence of deviations of sample homogeneity on

a precisely specified electromagnetic field structure is outlined, and sufficient conditions for isotropic, uniaxial, or biaxial anisotropic dielectric behavior are reviewed

in terms of a material's chemical lattice physics. These characteristics direct the

choices of suitable reference materials useful for confirming or improving the accuracy

of dielectric measurements.

12. KEY WORDS (6 TO 12 ENTRIES; ALPHABETICAL ORDER; CAPITALIZE ONLY PROPER NAMES; AND SEPARATE KEY WORDS BY SEMICOLONS)

anistropy; Debye material; dielectric; dispersion; homogeneity; microwave complex

permittivity; reference materials; relaxation

13. AVAILABIUTY UNUMITED

FOR OFFICIAL DISTRIBUTION. DO NOT RELEASE TO NATIONAL TECHNICAL INFORMATION SERVICE (NTIS). X

ORDER FROM SUPERINTENDENT OF DOCUMENTS, U.S. GOVERNMENT PRINTING OFFICE, WASHINGTON, DC 20402. ORDER FROM NATIONAL TECHNICAL INFORMATION SERVICE (NTIS), SPRINGFIELD, VA 22161. ELECTRONIC FORM

ir us GOVERNMENT PRINTING OFFICE: 1990—775-628/25117

14. NUMBER OF PRINTED PAGES

124

15. PRICE



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