Journal of the Textile Institute Proceedings

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GENERATION OF STATIC ON SOLID INSULATORS

PROFESSOR E. HONEGGER & P. S. H. Henry

To cite this article: PROFESSOR E. HONEGGER & P. S. H. Henry (1957) GENERATION OF

STATIC ON SOLID INSULATORS, Journal of the Textile Institute Proceedings, 48:1, P5-P25, DOI:
10.1080/19447015708688112

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Published online: 07 Jan 2009.

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 Generation of Static on Solid Insulators—Henry

Chairman : PROFESSOR E. HONEGGER

GENERATION OF STATIC ON SOLID INSULATORS
By P. S. H. HENRY

CONTENTS
Page
1. INTRODUCTION ... ... ... ... ... ... ... ... P5
2. THE CHARGE CARRIERS « • P6
3. EQUILIBRIUM OR NOT? • • P7
4. THE MODEL, AND " B A S I C " PROCESSES > • • « • * O

5. EQUILIBRIUM STATES
Introductory ... • • plO
"Basic" equilibrium processes • • ... Pll
"Special" equilibrium processes « •» ... Pl4
6. KINETIC STEADY STATES ^ . ,
Introductory ... Pl5
"Basic" kinetic processes ... ... Pl8
"Special" kinetic processes ... Pl9
7. DissiPATivE P R O C E S S E S ... P20
8. REFERENCES ... P22
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An account is given of what the author believes to occur when static

charges are generated on polymeric insulatirig surfaces by contact with other
surfaces. The subject is approached by trying to predict what will happen,
for subsequent comparison with experiment, rather than by taking existing
data and trying to explain them. The nature of the carriers of charge is first
considered, and it is suggested that adventitious ions attracted from the air
during previous periods of charging may play a large part. The importance
of recognizing the distinction between equilibrium and kinetic processes is !
stressed, and the dissipation of charge which occurs when the surfaces are ,
separated is discussed. A simple model is postulated and, on the basis of this,
six "basic" processes are predicted which are expected to occur with all
surfaces. Various other processes which have been suggested for particular
types of surface are discussed. Though other authors are quoted as may
be appropriate, the paper does not embody a review of the literature.
(This has been done recently in the Journal of the Textile Institute by Arthur'*.)

I. INTRODUCTION
* 'Static'' has acquired a richly deserved reputation for unpredictability.
This uncertain behaviour is no mere variation in amount ; it is the very
signs of the charges which confound us by reversing for no apparent reason,
often in the factory, and sometimes, it must be confessed, in the laboratory.
OD the lecture bench it achieves at last some degree of order, for here it can
he relied upon to do the wrong thing. This unreliability in itself should,
at least, give us a clue to the underlying processes. It has been common
in the past to put it down to varying contamination or state of strain in the
surfaces, and no doubt there is much truth in this, but these are facile
explanations not, as they stand, easily proved or disproved. I believe that
it is possible to be more explicit, and that little progress will be made until
this is done. # :. .. .
There has been an almost universal tendency in the past to regard the
separation of charge that constitutes "static" as a rather peculiar and
mysterious phenomenon for which an explanation must be sought, and
authors, with one or two exceptions, have championed one or other of the
several hypotheses against the rest. One of the aims of this paper is to
suggest that a quicker insight will be gained by starting at the other end :
we imagine two surfaces with available electrons or ions, and consider what
will happen when we bring them together and separate them. It is immediately
obvious that only in an exceptional case will everything be so balanced that
no particles transfer their allegiance from one surface to the other. Static
 Conference

now appears as a universal phenomenon, controlled by many circumstances,

which goes unnoticed as a rule only because most objects are sufficiently
conducting to ensure it a very brief life.
In what follows we shall be thinking mainly of contacts where one at
least of the surfaces consists of the type of insulator, or poor conductor,
familiar in the textile and plastics industries—polymeric materials, mostly
organic, and either not crystalline or only partly so. This class covers also
the great majority of substances used in practice as solid electrical insulators.
If we exclude powders and liquids from our discussion, it includes almost
all materials wliich give static trouble in industry and commerce.
Whenever possible we shall avoid committing ourselves as to whether
the charged particles whose movements we are discussing are electrons or
atomic or molecular ions. Often we shall have to make this distinction,
but we shall see that much useful discussion can be carried on without it.
To avoid frequent repetition of the phrase ''charged particles", we will
refer to them as "carriers" when we do not want to specify their nature.
Because of the nature of the materials, and the wish to avoid, where
possible, assumptions as to the nature of the carriers, we shall not employ
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the quantum terminology developed for use with conductors and crystalline
lemi-conductors except when speaking of such materials. We shall not,
for instance, speak of Fermi levels and conduction bands in our insulators.
We shall, however, use more general terms which do not exclude such energy
levels where applicable, and shall, in fact, find it useful to draw parallels with
phenomena occurring in metals which may reasonably be discussed in terms
of Fermi levels.

2. THE CHARGE CARRIERS

The fact that a separation of charge takes place when two surfaces are
brought together and separated may be otherwise described by saying that
some charged particles, be they electrons or atomic or molecular ions,
have crossed from one surface to the other, and it is easy to show that surface
charges of the observed order of magnitude require comparatively few
carriers to have made the crossing ; few, that is to say, compared with
the number of molecular groups or atoms exposed on the surfaces. For
instance, the charge density which is commonly quoted as being the maximum
that can be supported in ordinary air—8 e.s.u./cm^—requires about
2 electronic charges per W sq.A, an area which would contain at least
10^ atoms. That the charged particles have crossed the boundary suggests
that they were present before the contact, though this conclusion is not
inevitable, since there is the possibility that ions may be produced by friction
where none were before. This possibility will be discussed later. The mere
presence on an insulating surface of such particles is a matter of interest,
and one of the purposes of this paper is to emphasize the important part
they play.
1- Where one of the surfaces concerned is of metal, or an «-type crystalline
semi-conductor, there will be plenty of electrons available on one side of
the boundary, and, no doubt, they then play the preponderating part owing
to their inexhaustible supply and their great mobility. (See, however.
Harper's recent experiments^ in which he could not detect any charge
separation on light contact between metals and various organic insulators).
Where, however, we are concerned only with insulators and the textile type of
poor conductors, the availability of electrons is not obvious, and it may be
better to postulate the presence of ions on the surface. So far as I am aware.
 Generation of Static on Solid Insulators—Henry P7

no one has yet settled the question as to whether the current in textile poor
conductors, with its enormous dependence upon moisture content, is carried
by electrons or ions, but I believe that most opinion favours the latter.
The ions may be there as ionizing groups forming part of the substrate
(perhaps produced by oxidation), as impurities in the material, or by
deposition on the surface from the air or surrounding objects. Deposition
of ions from the air may be an important factor in determining the behaviour
of surfaces as regards static production ; any insulator during its history
will have become charged this way or that by contact with other bodies,
and each time it will start to collect ions of the opposite sign from the air
(air always contains a few ions produced by cosmic rays, carbon 14, etc.).
Many of these ions may be neutralized on reaching the surface, but, since
there is evidence (see later) that ions do not easily move along insulating
surfaces, owing to the presence of "traps", some of them may remain
permanently as ions. Thus, the surface will gradually acquire a miscellaneous
assortment of ions, whose nature will depend upon the previous history of
the surface. This may well be the principal form of contamination that
makes static behaviour so unpredictable.* ..-•..
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It has been shown by Bovvden^ that almost any rubbing process may
generate local temperatures high enough to decompose organic matter ;
and, since it is common for ionic groups to be formed when organic
compounds are decomposed by heat, this may be an additional source of
ions on the surfaces of insulators, and these freshly formed ions may play
a part in the charging of insulators by friction.
Presumptive evidence that ions rather than electrons play the predominant
part in particular cases has been provided by previous authors ^•'**^ who
found that acidic surfaces tended to become negative, and basic surfaces
positive when rubbed against a chemically neutral surface. The clearest
case was that of Medley, who used ionic resins in which one ion was part
of the substrate, and therefore fixed, whilst the other was hydrogen or
hydroxyl ion. The simplest explanation, as given by Medley, is that these
materials gave up some of their mobile ions to the other surface (filter paper)
in each case. Further evidence is provided by Coehn's First Rule^, for
what it is worth (it is by no means always obeyed). This rule states that,
when two substances are rubbed together, that having the higher dielectric
constant goes positive. Since a charged particle between two media is
attracted to that of higher dielectric constant, other things being equal,
this would suggest that the carriers in the cases examined by Coehn were
positive, and therefore not electrons. . , -j , ... .. ,
3. EQUILIBRIUM OR NOT? '
Given that we have two initially uncharged surfaces, either or both
having a supply of carriers, and that we bring them together and separate
them, with or without friction, let us consider what we should expect to
happen.
We must first distinguish between equilibrium states and kinetic effects.
When two surfaces are brought together and allowed to remain at rest, there
will, in general, be a tendency for carriers to transfer their attachment from
one surface to the other for various reasons to be discussed later, and a new
equilibrium distribution will be set up. Individual carriers may be crossing
over all the time as thermal agitation may dictate, but, on the average, they
•Experiments with polythene surfaces have not, however, given evidence of such
an effect. Further experiments are to be made with a more polar type of surface on which
the probability of ions recombining would be less.
 P8 Conference

will do so at equal rates in both directions, and the system, regarded

macroscopically, is at equilibrium in the same sense that the air in two
connected vessels is at equilibrium, although individual molecules are
perpetually passing from one to the other.
If now we cause the surfaces to slide over each other whilst still
maintaining contact, fresh phenomena may come into being which are
maintained only as long as the motion persists, depending, for instance,
upon the heating produced by friction. These we may call steady kinetic
phenomena, and, in cases where rubbing takes place, they will be superposed
on the equilibrium phenomena.
Finally, before the charges due to the carrier migration can be observed,
it is usually necessary to separate the surfaces from each other, and, if the
equilibrium distribution depends upon the distance between the surfaces,
there will be further crossing over one way or the other at a diminishing
frequency till the carriers can no longer get across. We shall see later that
this effect will usually, but perhaps not always, go in the direction of
decreasing the charges previously formed. After this, if the separation
is carried out in air, the field between the surfaces may set up cumulative
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ionization, and the resulting discharge will further diminish the charges.
These we will call dissipative phenomena.
If it be agreed that phenomena of these three classes take place, it is
evident that experiments involving the rubbing together of different surfaces
in air (the majority of past published work, in fact) will produce a mixture of
equilibrium and kinetic processes of such a nature as would render valid
comparison of results difficult even without disturbance by accumulated
ions or other forms of contamination. Obviously, to investigate one effect
we must try to get rid of the others. Thus, we may hope to eliminate the
equilibrium effects by rubbing (asymmetrically) two similar surfaces, or
the kinetic effects by bringing different surfaces together with as little friction
as possible. We can do little to eliminate the first stage of the dissipative
processes, but the discharge in air can be minimized by working in a high
vacuum, or at a high pressure, or by a combination of one of these methods
with the use of a thin insulating sample backed by a conducting plate at earth
potential to neutralize the field once appreciable separation has taken place,
as in Medley's recent experiments^

4. THE MODEL, AND "BASIC PROCESSES

Let us take the three stages in static generation (of which the second
may be missing) in order and discuss them separately. It will be convenient
for the discussion to use a simplified model which, admittedly, does not
correspond exactly to actual surfaces, but which must reproduce the most
important features of the actual case without rendering the analysis impossibly
complex. We will try to endow our model with such relevant properties as
are common to all the surfaces in which we are interested, whilst avoiding
in the first instance properties which are possessed only by a limited class of
surfaces. We shall not allow the model, for instance, to have piezo-electric
or pyro-electric properties, and we shall, at first, ignore any effects of surface
structure. If we do this, and work out the behaviour to be expected of the
model, we may call any phenomena thus predicted "basic" processes, for
we expect them to be present in all actual cases. We shall find 6 of these :
2 equilibrium, 2 steady kinetic, and 2 dissipative processes. We can then go
on to discuss the effect of introducing special properties into the model,
and phenomena thus predicted we will call "special" processes, which we
 Generation of Static on Solid Insulators—Henry P9

will expect to meet only in certain actual cases. This division, depending
as it does upon the degree of elaboration chosen for our basic model, and
therefore conditioned by the necessity for simple calculation, is bound to be
arbitrary, but it will be useful in clearing our ideas.
Two plane solid surfaces are imagined each of which may contain ions,
some being part of the substrate, others held on by the electrostatic forces
due to their charges. The surfaces may also have a supply of electrons from
the interior, though we shall be interested mainly in cases where at least
one of the surfaces has no such supply. At present, we will assume the surfaces
to be uniform, an ion having the same potential energy at any point upon it.
As long as the surfaces are plane and parallel it does not matter whether the
carriers can move over the surface or not, though a distinction has to be
made between those that are confined to the surface and those that can move
into the interior.
We now cause the surfaces to approach each other, whilst remaining
parallel, until they are close enough for ions or electrons to pass from one to
the other under the influence of thermal agitation with sufficient frequency
for equilibrium to be reached within a reasonable time. It is supposed,
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however, that each carrier can still be assigned to one surface or the other,
and that its potential energy is less on either surface than at intermediate
positions. We shall show later that, whether or not the surfaces approach
so close that carriers cannot be definitely assigned to a given surface, our
final interest is always in a state where the separation is sufficient for a marked
potential energy "barrier" to exist for the carriers between the surfaces.
Harper^ has discussed the probable magnitude of the greatest distance at
which electrons will cross over between two metal surf^aces with sufficient
frequency ; he estimates that this is 25A. The electrons are assumed to cross
by the process known as "tunnelling", and, since this process will not be
important for ions, the appropriate distance for them is probably much
less, say a few A.
We will suppose the potential energy of a single carrier at various
distances from one of the surfaces (in the absence of the other) to be given
by a curve such as that shown by continuous lines in Fig. 1, where the upper

Fig. 1
Potential energy of carrier between two insulating surfaces

dashed line gives the ' 'zero'' of energy—that of a carrier at infinity. We

are most interested in the difference in energy level between the " z e r o "
at infinity and the position of equilibrium. Unfortunately, the forces when
 Conference

the carrier is near to the surface, when most of the energy change takes place,
are not easy to calculate, but we shall not need to know the actual value for
the purposes of this paper. It may be of interest, however, to remark that,
in the absence of experimental determinations, a crude calculation suggests
that the value for a monatomic ion being removed from the surface of an
organic polymeric insulator will be of the order of 1 eV, certainly not less. *
A few data exist^ for the energy required to remove an extra electron from the
surface of crystalline insulators ; the values obtained were 4—5 eV. The
corresponding quantity for metals is, of course, well known, being referred
to as the ' 'work function'' and equal to the depth of the Fermi level below
zero energy (that of an electron at infinity). Values are of the order of several
electron volts, and are very sensitive to contamination.
When the surfaces approach each other, we may expect the two individual
curves to bend over and join to make the curve for the combined surfaces,
as shown dotted in Fig. 1. As long as the surfaces are still at a distance apart
great compared with atomic dimensions, we can calculate the shape of the
'*hump" of the curve from the distances and the dielectric constants of the
solids. More important would be to know its height above the positions of
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minimum potential energy, but this we cannot calculate unless we know

the latter. It is reasonable to suppose, however, that, as the surfaces approach
each other, the maximum will flatten out and its height above the minima
diminish. In the limit, we may imagine the maximum to vanish and the two
minima to coalesce, but, as mentioned before, v^e shall be more interested
in states of less intimate contact, when a position of unstable equilibrium
for the carrier still exists.
If there is more than one type of carrier concerned, a different potential
energy curve may be postulated for each, though the level of the central
maximum is likely to be nearly the same for all. In this paper, however,
we shall confine ourselves to the case where one type only is concerned,
whether it be electron or ion.
5. EQUILIBRIUM STATES
Introductory
The theory of charge separation on solid surfaces which has received
most attention—that of Helmholtz^®—postulates that it is an equilibrium
effect, taking place as soon as contact is made, which corresponds to the
phenomenon of contact potential difference in metals. Harper has shown
that the observed separation of charge when two metals touch lightly without
rubbing, and are separated again (one of them being very highly insulated
from earth), is in agreement with this idea, and requires no further hypotheses.
We need not at this point inquire what the theory amounts to in terms of
electronic or ionic motion ; that we shall do later in this paper. No
confirmation for insulators similar to that provided by Harper for metals
has been published. The difficulty is to measure the contact potentials for
insulators (or even perhaps to define them). It is possible to measure the
energy required to remove to infinity a surplus electron at rest on the surface
of an insulator, and, in fact, this has been done^ for a few insulators. With
metals, a knowledge of the work functions of two surfaces is enough to give
their contact potential to a sufficient degree of accuracy, but we shall see later
that this may not be true of insulators.
*This value is almost certainly too low. It was derived by assuming a uniform
dielectric {K = 2S) and a distance of approach of 2A. This procedure might give
correctly the average value over the surface, but, in practice, the ions will seek out points
where the potential energy is lowest.
 Generation of Static on Solid Insulators—Henry Pi i

The author has been able to demonstrate^^ directly a sudden change in

electric moment at the interface as an insulator and a metal come into
contact. This can be explained as a sudden transfer of charge across the
interface, as required by Helmholtz's theory, but it might also be due to a
sudden polarization, or rotation of polar bodies, without passage of free
charges. It is hoped to find out whether this change in electric moment is
correlated with the charges left on the two surfaces after separation.
Meanwhile, there is an important general point to be considered.
Whatever the actual mechanism, if equilibrium processes only are concerned
it follows that a self-consistent "electrostatic series" should exist; that is,
it should be possible to arrange a given set of surfaces in order in such a way
that any surface becomes positively charged when in contact with a surface
coming after it in the series. Many such series have been published ; but,
except where authors have quoted each other's lists, the order in which
particular types of surface have been placed has been variable. Further,
one author^2 who had published a particularly extensive list had the mis-
fortune (and the honesty) to find afterwards that he could arrange certain of
its members in an "electrostatic circle" such that each member went positive
in contact with its immediate clockwise neighbour. Such an arrangement is,
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of course, incompatible with the existence of a proper electrostatic series.

This observation suggests that, before a series can be accepted under particular
conditions, all possible pairs must be tried. This appears seldom to have
been done in the past.
Since the existence of a consistent series is a necessary consequence
of equilibrium phenomena, observations of inconsistencies show the presence
of non-equilibrium phenomena. Now most, if not all, previous series had
been obtained by rubbing, so the author^ ^ tried some time ago an experiment
in which 10 different sheet materials—conductors and different types of
insulator—were passed as "sandwiches" between rollers under conditions
which minimized rubbing (and eliminated the effect of contact with the
rollers). All feasible pairs were tried, and, out of 84 such pairs, only 3 were
inconsistent with the existence of a series ; and in 2 of these the charges
were so small as to be within the experimental scatter. The remaining
exception I believe to have an explanation which is given in the reference
quoted. The suggestion is that in the absence of rubbing a self-consistent
series is possible. Now let us return to our model.
* *Basic'' Equilibrium Processes . .
Let the surfaces approach each other gradually. As soon as they are
within effective tunnelling distance if the carriers are electrons, or the potential
energy hump has diminished sufficiently if they are ions, carriers which have
received a large amount of thermal energy will start to cross over from
that surface on which they have the higher potential energy. The process
may be thought of as thermionic emission occurring at room temperature
because the energy required to remove a carrier from each surface has been
reduced by the proximity of the other to a value which is not too great
compared with kT, where k is Boltzmann's constant, and T is the absolute
temperature.
As the surfaces come closer, carriers will be passing across in both
directions, but at first more rapidly from the surface on which they have the
higher potential energy. There will thus be a net transfer of charge from one
surface to the other, which will cause the two surfaces to become oppositely
charged, and will set up an increasing electrostatic field between them in
 P ' -i Conference

such a direction as to diminish the difference between the rates of transfer

in the two directions. As soon as this difference is zero, and carriers are,
on the average, crossing in equal numbers each way, the system will be at
equilibrium. It might, at first sight, be thought that this state would be
reached when the potential energy of the carriers was equal on the two
surfaces, but this is true, however, only if the carriers are equally abundant
thereon. To see this, consider two surfaces whose electrostatic potential
difference has been adjusted to cancel out exactly the difference in their work
functions, so that no work is done by the carriers in going to-and-fro between
them. If, now, one of the surfaces has more of the carriers per unit area
than the other, the numbers passing across per second will not be equal,
but will be proportional, other things being equal, to the numbers present
per unit area from which they come (we are here thinking of carriers confined
to the surfaces, but a similar argument applies to those—e.g., electrons—
which can penetrate the solid). The system will not, therefore, be at
equilibrium, but charge will be transferred from one surface to the other
until the effect of the resulting unbalance between the electrostatic potential
difference and the difference of work functions exactly counterbalances
that of the differing abundance of carriers on the two sides, so that equal
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numbers pass over in each direction per second. Equilibrium has now been
attained, and, if the bodies are both conductors, we say that their difference
in electrostatic potential is the "contact potential difference" which, in the
case of different metals, is commonly of the order ofa voltorso. The unbalance
between this and the difference in work functions is (in the case of conductors)
the Peltier potential difference, usually only a few millivolts between metals,
and we know that this is the only part of the electrostatic potential difference
against (or by) which work is done when a current flows across the junction
(the effect of the rest of the contact potential difference being cancelled out by
the forces responsible for the work functions). We may look upon the Peltier
potential difference as the result of different concentrations of electrons
capable of changing their state of motion in the two metals ; that is, of
electrons occupying states near to unoccupied states, and, therefore, at room
temperature, near to the Fermi level. These effective concentrations do not
differ widely from one metal to another, hence the small values for the
Peltier potentials. It is commonly stated, in fact, that the contact potential
between two metals is equal to the difference between their work functions ;
and this approximation is good enough for most purposes with metals.
With insulators and semi-conductors, the abundance ratio of the carriers
between one surface and another can be large, and the approximation is
DO longer good enough. As an example from semi-conductors, Goldsmid^^
found that a p-n junction in bismuth telluride had a thermoelectric power
indicating a Peltier potential of 73 mV ; this corresponds to an abundance
ratio of about 18 : 1.
Returning to our model, and assuming insulators on both sides, the
relative effects of the two determining factors—the difference in affinity for,
and the difference in abundance of, the carriers—can be shown very simply
by means of Boltzmann 's law for the distribution of particles between two
states of different energies.
Let eW-^ and eW2 be the amounts of work required to remove the carrier
in question (assumed, for simplicity, of one type only) from surfaces 1 and 2
to infinity, where e is the electronic charge. If the carriers are electrons,
Wi and W^, are the "work functions" of the surfaces, perhaps altered by
their mutual proximity.
 Generation of Static on Solid Insulators—Henry P13

.Let K be the average effective dielectric constant along a path across

the gap ;
and D the width of the gap ;
and n^ and n^ the numbers of carriers per unit area on surfaces 1 and 2
in the equilibrium state ;
and G and —a the total charge densities on surfaces 1 and 2.
Then, assuming zero external field, and taking the average value of the
field between the surfaces, the work required to take a carrier from surface 1
to surface 2 in the equilibrium state is equal to .

e ; (1)

Assuming, for the time being, that equal areas on the two surfaces have equal
statistical weights (we will discuss this later), Boltzmann's law gives

^ f O»Wn)e^W^/^ I
I kl j
Taking logarithms and rearranging a little, we get
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^ ^ e
!^]
n^
• (3)
The first terms inside the bracket represent the difference in affinity of the two
surfaces for the carriers, which is the basis of the Helmholtz theory of the
origin of static. They correspond to that part of the contact potential
difference between metals which is not due to the Peltier effect—to much the
greater part, in fact. The last term in the bracket represents what we may call
the "abundance effect". (We do not use the word "concentration" here
because it has too definite a meaning for our present purpose). It corresponds
to the Peltier potential difference between metals, but, as we have seen, it may
be much greater in magnitude.
It must be remembered that w^ and n^ in the equation refer to the numbers
of carriers present on the two surfaces in the equilibrium state, so that the
equation is not an explicit expression for the charge density in terms of the
initial quantities. There is a simple relation between ni and Wg on the one hand,
and the initial numbers of carriers and the charge separation on the other,
but the result of substituting this in Equation (3) is to produce an equation
not soluble in simple terms. If the number of carriers transferred is small
compared with those present on each surface, however, njn2 may be taken
as nearly equal to the ratio of the initial numbers of carriers present on the
two surfaces, and then Equation (3) becomes an explicit expression for the
charge separation. Obviously, we could not use this approximation, for
instance, where one of the surfaces was initially devoid of carriers.
While discussing the equilibrium state, it is interesting to work out the
effect of an external electrostatic field on the charge separation. The existence
of such an effect was demonstrated experimentally by Gill and Alfrey^®,
and measured by Medley^. If the field is uniform and normal to the surfaces,
and has the value £" in a vacuum, we must add —eEDjK to the work required
to take a carrier from surface 1 to surface 2. It is readily seen that this has
the effect of subtracting a quantity EjAiz from the charge separation per unit
area ; i.e., it so alters the charge separation as to cancel out exactly that
part of the electrostatic field in the gap which is due to the external field.
This is in agreement with the observed facts as determined by Medley.
 P'4 • Conference

No method of determining experimentally the equilibrium charge

separation between two surfaces whilst they are in contact has been described
in the literature yet. We shall see in Section (7) of this paper that observed
charges after separation of the surfaces may, or may not, be equal to the
equilibrium values during contact.
**Speciar* Equilibrium Processes
Electrochemical effects, as distinct from the Helmholtz mechanism,
have been suggested^-^^ as a cause of contact electrification. This theory,
presumably, implies that the surfaces are separated by an electrolytic medium,
that the substances present are capable of taking part in a chemical reaction
together, and that, whilst atoms can pass between at least one of the surfaces
and the medium, electrons cannot pass directly between the surfaces. An
electrochemical cell is not, strictly speaking, an equilibrium system, since
contact between the electrodes, i.e., an approach sufficiently close for the
direct passage of electrons, causes a current to flow and the chemical reaction
to take place. Since the cell is not at equilibrium, the potential difference
between the electrodes need not be, and usually is not, equal to their contact
potential difference. In our discussion hitherto, we have assumed an approach
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close enough for electrons to pass if there are any capable of moving ; in
such circumstances, the potential difference between the surfaces would be
expected to change as they approach each other from that of any cell initially
formed towards the contact potential difference to a degree depending upon
the electrical resistances of the parts, since a current would be flowing.
Harper^, experimenting with contacts between metals, found, however, that,
even when the contact was light, the observed charge separation was best
explained on the assumption that the metals acquired their contact difference
of potential. In the absence of further evidence, and in view of the fact that
contacts in the textile industry are probably usually firmer than those used by
Harper, it will be simplest to assume that electrochemical cells do not enter
into the problem, though it is not a theory that we can reject out of hand.
The piezo-electric effect has been suggested by Martin^^ as responsible
for contact electrification in the case of wool fibres. This could apply only
to crystalline, or at least oriented, materials, and by itself it could produce
only polarization, not an over-all charge. We have only to postulate the
passage of current from the surroundings to neutralize one end of a polarized
body, however, to explain the acquiring of a net charge by the latter.
The two respects in which our model differs most from actuality are
probably that the surfaces are supposed flat and uniform in affinity for the
carriers. Actual surfaces are not flat within the limits that concern us
(a few Angstrom units), and they will make close enough contact for carrier
transfer at particular spots only. The chief consequence of this is that it
introduces certain kinetic phenomena during rubbing which will be discussed
later. As far as equilibrium processes are concerned, the most obvious effect
of the rugosity is to reduce very greatly the effective contact area. If, as
seems likely, the contact spots are still large in diameter compared with the
distance between the surfaces, the total charge separation would be expected
to be proportional to their total area. (We assume one or both surfaces to
be that of^ an insulator which does not permit the carriers to move over its
surface.) Moreover, following the work of Bowden^, it is probable that the
total contact area for a given pair of surfaces without rubbing will be closely
proportional to the total normal component of force between them, except
perhaps for very light contact. Hence, we should expect that, in the absence
 Generation of Static on Solid Insulators—Henry PI 5

of rubbing, the total charge separation would be proportional to the

maximum total normal force between the surfaces. This refers, however,
to the charges as the surfaces first separate ; if partial discharge occurs later
by multiplication of ions in air, the proportionality would be destroyed.
The second discrepancy between our model and actual surfaces—the
assumption of uniform affinity for the carriers—is less easy to discuss, partly
owing to lack of the necessary data. There is no doubt that charged particles
will be more attracted to some spots on the surface than to others ; there
will be positions of specially low potential energy ( " t r a p s " in the language
of the semi-conductor world) which will be preferentially populated by such
carriers as exist on the surface to a degree determined by the depth of the
energy "well" and the temperature, according to the Boltzmann distribution
law. Observation shows that areas of charge deposited on the surfaces of
polythene^^, selenium^**, etc., do not lose their sharply defined edges for hours,
showing that diffusion along the surface does not occur under the conditions
used. This indicates that the depth of the traps must be large compared with
l/40th of an electron-volt ( = kT at room temperature). We do not know
how many of these traps exist per unit area, or what proportion of their
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number is liable to be occupied by carriers. My guess is that a common case

is that in which there are many deep traps, only a small proportion being
filled. In this case, the correct value to take for the energy of a carrier
on the surface, when working with the model, is that of a carrier in a trap.
If the traps were shallow enough for thermal agitation to maintain a small
population of carriers on the surface outside the traps, it would be more
appropriate to use the energy of the free carriers for the model (but better
still to do a more elaborate calculation), but we should expect such a surface
to have conducting properties and to allow diffusion along it of carriers.
The presence of the carriers in traps would affect the statistical weights
to be allotted to unit area of each surface in working out the Boltzmann
distribution. In the simplest case, with traps numerous and deep enough
to capture the whole population of carriers, the weights would, presumably,
be proportional to the number of traps per unit area, and Equation (1)
would then contain, instead of the ratio of carriers per unit area, the ratio
of fractions of the total numbers of traps occupied.
Apart from any discrepancies between the model itself and actuality,
we have made an assumption in working out Expression (1) which will often be
wide of the mark. We have assumed that each carrier is acted upon by the
average electrostatic field reckoned over the whole area between the surfaces.
In effect, we have supposed the charge to be smeared evenly out instead of
concentrated at points. If the carriers are sparse enough for the mean distance
between them to be greater than the distance between the surfaces, the field
will be very large in the neighbourhood of each carrier, but smaller than the
average over most of the area ; and this smaller field will not be proportional
to the first power of a. The work done when a carrier crosses over will then
depend largely upon whether we have to imagine it as leaving behind an
oppositely charged " h o l e " or not. In this paper, however, we are concerned
only with a qualitative description of phenomena, and further consideration
of this case will be deferred to a more thorough working out of the theory,
which is in progress.
6. KINETIC STEADY STATE
Introductory
It is an observed fact that rubbing between two surfaces has a large
effect on the charge generated, usually increasing it, occasionally reversing
 Pi6 . • Conference

the sign. Indeed, for a long time, it seemed to be the opinion in most quarters
that friction was necessary for the production of static, which was often
referred to as "frictional electricity". This was probably due to the use of
insensitive instruments, and to the absence of experiments done under
conditions which give large charges without friction. When charges were
detected in the aj^parent absence of friction, this was sometimes explained
by the statement (no doubt containing much truth) that it is impossible to
bring surfaces together and separate them without some friction. The opposite
point of view was, however, expressed by Helmholtz^^, who suggested that the
effect of friction was merely to increase the total areas of the surfaces which
had been in true contact with each other. It is hard to controvert arguments
of the former type, simply because it is hard to separate two surfaces with the
absolute certainty of no tangential motion between them. At the same time,
it seems unsatisfactory to attribute to casual friction the large charges which
can be produced when two surfaces have been in close contact over a wide
area without overt friction. The point of view of Helmholtz, though probably
containing more truth than the opposite view, again does not seem enough
by itself. Several experimenters^^-^--^'-^--* have reported the reproducible
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charges which can be observed when two apparently identical surfaces are
rubbed together, and the present writer^ ^ has emphasized the part played by
asymmetric rubbing in such phenomena. Shaw"^ attributed the effect to
differing states of strain set up by the friction, thus making the surfaces, in
effect, different materials, after which the Helmholtz mechanism produced
the charges. This again involves an ad hoc assumption difficult to prove
or disprove, and, whilst it is not impossible that a state of strain might change
the charging properties of a surface, one would not expect such an effect
to be large, except perhaps with ionic crystals. It seems better, therefore,
to suppose that at least the major part of the effect is due to a mechanism
involving the asymmetric rubbing as such, the more especially since, as will
be shown below, such an effect would be expected even if no experiments
had been done. Experiments by Shaw^^, which were supposed to establish
the reality of the strain effect, were done by rubbing the outer surface of a
bent specimen against a straight specimen of the same substance, and the
results could equally well be explained by the marked asymmetry of the
rubbing process thus produced.

Fig. 2
Asymmetric rubbing

In the author's experiments^^ on the rubbing together of like surfaces,

the asymmetry of the rubbing was found to play an essential part ; that is to
say, one surface must be rubbed over the same small area all the time whilst
the other is rubbed over a wider area, as shown diagrammatically in Fig. 2.
(Of course, there must be asymmetry somewhere if separation of charge is
 Generation of Static on Solid Insulators—Henry P17

to occur.) When the roles of the two surfaces were reversed, the rubber
becoming the rubbed, the signs of the charges reversed regularly, so that the
rubber was always positive (or, less commonly, negative). From these
observed facts and the knowledge that the apparently symmetrical rubbing
of two fiat surfaces together is usually, in fact, the asymmetric rubbing of high
spots on each against the other, it was deduced that such a process, though
usually reported as giving irregular small or zero charges, should actually
produce quite high local charges, probably arranged as spots of one charge
and streaks of the other. If the two surfaces are similar, these would roughly
cancel out when the over-all charge is measured, but should be separately
observable by suitable means. Experiments were accordingly tried by two
methods : the use of a small screened probe connected to an electrometer, and
the "finger-printing" method in which oppositely charged coloured powders
are scattered over the surface and become attached to points of opposite
charge. Both methods were successful in detecting patches of opposite charges
on flat pieces of ebonite, Perspex, and polythene which had been rubbed
against identical pieces. Fig. 3 shows a photograph, about 2^ times life size.
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1cm.

• ^ -. '-—' '•^."v " * '

Fig. 3
Distribution of opposite charges on polythene sheet rubbed on piece of the same material

of a dusted piece of polythene sheet. The dark spots (red powder) show places
of positive charge, and the grey areas in the print (white powder contaminated
by a little of the red) indicate negative charge. It also was to be expected from
the observed facts relating to asymmetric rubbing that, if we have two pieces
of the same material, differing only in that one has a smooth surface and the
other a rough, they would give a regular charge separation on being rubbed
together, since the rubbing points would mostly be on the rough surface,
and the rubbed tracks on the smooth. This is in agreement with observations
of other experimenters^^ who have reported that rough and smooth surfaces
of the same material behaved as if of different materials.
It is reasonable to suppose that the same kind of thing would happen
if surfaces of different materials and different degrees of roughness were rubbed
together. The frictional effect would then be superposed on the equilibrium
separation of charge. If the two effects produced charges of opposite signs,
one would expect to get a combined effect whose sign depended upon the
 ^' *^ ' Conference
degree of friction. This reversal of sign is, in fact, sometimes observed in
practice ; for instance, the sign of the charge on a cellulose acetate fibre
warp running through glass guides during section warping has several times
been noticed to change when the mill was speeded up after slow rotation
by hand.

"Basic" Kinetic Processes

Several hypotheses have been advanced by previous authors to explain
frictional charging effects, but all that the author can remember invoked
special properties of the surface, such as pyroelectricity, or properties of
greater generality but postulated for the purpose, such as a pre-existing
"double layer" on the surface. These, probably important in special cases,
will be dealt with in the next section. The author has recently^^, however,
put forward a theory concerned with asymmetric rubbing which involves
no hypotheses not already contained in our simple model. The phenomena
described would occur with any pair of surfaces bearing charged particles
capable of transfer from one surface to the other, subject to asymmetric
rubbing ; and it may therefore be added to our short list of " 'basic'' processes.
It depends upon the temperature gradient across the interface at any points
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where rubbing is taking place. The work of Bowden^ has shown that large
rises in temperature occur locally in almost any rubbing process, and, where
a given spot on one surface is continually being brought against fresh unrubbed
places on the other (and this is what we mean by asymmetric rubbing),
there will be a large temperature gradient maintained across the interface.
This will cause any mobile particles to travel more frequently from hot to
cold than in the reverse direction, with a resultant flow from hot to cold.
This process is analogous to thermal diffusion in gases and to part of the
Thomson thermoelectric effect in metals. If the mobile particles are charged
and predominantly of one sign, there will be a net transfer of charge from
one surface to the other which will continue until the increasing electrostatic
field due to the charge built up on the "rubbing" surface balances the
thermal effect and stops further charge transfer. The existence of such
an effect has been verified experimentally by Bowles^" at the Shirley Institute,
using a method involving an extremely brief contact of two like surfaces
brought initially to different temperatures. A further, and perhaps closer,
analogy with well known phenomena is given by imagining two thermionically
emitting surfaces facing each other and maintained at different temperatures.
A net transfer of charge would occur owing to the greater emission of the
hotter surface. In the case of our insulators, the effective work function of
each surface may be considered as having been reduced by the proximity
of the other, so that emission occurs at room temperatures. This analogy
must not be taken as meaning that the phenomenon is necessarily electronic—
atomic ions would behave in the same way if available.
We can insert this process into our model by assigning different
temperatures to the two surfaces. This is, perhaps, a little artificial, but it
will enable us to make a simple calculation which should predict some
features of the process for comparison with experiment. Since the system is
not at equilibrium, we can no longer use Boltzmann's distribution law in
its rigorous form. What we do is to write down expressions for the rates at
which charged particles leave unit area of each surface, and set these equal
for the steady state. For this purpose, we may use the statistical methods
which have been employed, for instance, in the theory of the thermionic
effect and of adsorption on to solids from gases, or the simpler, if less rigorous.
 Generation of Static on Solid Insulators—Henry Pig

method which has been used successfully for so many purposes by

To adapt the latter method for our purpose, we work out a hypothetical
undisturbed equilibrium distribution for the carriers between one of the
surfaces and the position of maximum potential energy between the surfaces
(the "activated state" of Eyring), and use this, together with a value for the
mean component of velocity of the carriers normal to the surfaces, to give
the rate of passage through the position of maximum potential energy.
We need not concern ourselves with the details here ; suffice it to say that
both methods give a rate of passage of carriers per unit area in each direction

proportional to T^ exp < "' ^ > where V,,^—V^ is the energy required

to take a carrier from the surface it is leaving to the position of maximum

potential energy, and (JL is a numerical exponent which depends upon the
statistics appropriate to the carriers on the surface. We will consider here
only the case where the surfaces are alike, so that [i. is the same for both.
As soon as a separation of charge has taken place an electrostatic field equal
to A-KcjK is set up as before, and we must add the work done against this to
Vjn—^i- Let the final position of maximum potential energy be at distances
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Di and Do from surfaces 1 and 2, where D^ -\- D2 = D ; it has been displaced

from its initial position by the electrostatic field. Then, omitting constants
which cancel out, we have for the steady state

On rearranging this, putting V^—V^=^V,,,—V2 = e{W—W^X writing

Sr for ^ 2 - ^ 1 , T for ^{T^ + To), and taking ^TjT small, we get, to the first
order of small quantities
e{W-
+
^+ kT
The first term in the brackets—that involving \L—indicates an effect analogous
to thermal diffusion, or to part of the Thomson effect in metals. (The other
part of the Thomson effect corresponds in our case to a term depending
on a change of W with temperature. It is small in the case of metals, and
it was not thought worthwhile inserting in the above expression). It is
independent of the forces between the carriers and surfaces, and of the
numbers of carriers present, providing that this is sufficient to maintain
approximate equality between the numbers on the surfaces. The second
term in the brackets is proportional to the energy " h u m p " to be surmounted
by the carriers in crossing over, and therefore increases with distance between
the surfaces and would vanish with perfect contact. It may perhaps be thought
of as a distillation of carriers over from the hot surface to the cold.

"Speciar' Kinetic Processes

Two mechanisms involving the rubbing that have been proposed in
the past to account for charge separation will be discussed briefiy.
Martin^^ and FrenkeP^, independently, pointed out that the local high
temperatures generated by rubbing (not in this case the temperature gradient)
would produce polarization in materials showing the pyroelectric effect.
This could produce local electrostatic fields and induce transfer of charge
either through a poor conductor or across a boundary, and so result in the
over-all charging of a body. A pyroelectric effect can be shown only by
materials which are crystalline or whose molecules are preferentially orientated.
 Conference

Martin was able to show the existence of the pyroelectric effect in the keratin
of wool fibres.
Shaw"^^ and Freundlich^^, independently, have attributed charge separa-
tion to an electrical "double layer" existing at the surface of the solid before
contact (distinct, therefore, from the double layer formed astride the
boundary after contact in the Helmholtz theory). It is supposed that
asperities in one surface sliding over the other have the effect of partially
skimming off the top layer. The components of the double layer are thus
separated, leaving both surfaces charged. Obviously, this theory would be
quite at home when dealing with asymmetric rubbing phenomena. Electrical
double layers are known to exist at the surfaces of many solutions, and are
implicit in the structure of certain faces of ionic crystals. It is much less
easy to postulate their presence on polymeric insulating materials, except
such as might be due to the presence of casual ions, a possibility which we
have included under "basic" phenomena.
Several authors, in particular Shaw, have pointed out that rubbing two
surfaces together may alter one or both of them by rubbing off a surface
layer (e.g., oxide or grease), or by producing a state of strain, so that it now
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behav:id as a different substance. This would account for separation of charge

between like surfaces on asymmetric rubbing, and was the explanation given
by Shaw-^ This would be expected to give irreversible results, whilst the
thermal gradient effect gives reversible results. It should, therefore, be possible
to distinguish between the two effects by experiments in which care is taken
to rub exactly the same areas on each surface each time.

7. DISSIPATIVE PROCESSES
In the theory of our model, it will have been noticed that a, the charge
per unit area, occurs multiplied by Z), the distance between the surfaces.
The reason for this is readily seen ; the surface charge density builds up
until the extra energy required to take a carrier across against the resulting
electrostatic field so adjusts the rates of passage of carriers in the two directions
that they become equal. Now the extra energy in question is proportional
to the distance D and to the field, which is itself proportional to the charge
density, and it hence varies as GD. If the equation contains no other
quantities strongly dependent upon Z), as is true of the equilibrium (but not
of the thermal gradient) equation, it follows that the equilibrium charge
density is inversely proportional to the distance between a given pair of
surfaces. If then we have reached equilibrium at some close distance, and
start to move the surfaces apart, the net rate of passage of carriers across
the gap will at first adjust itself in such a way as to reduce the charges so that
they remain inversely proportional to the distance. As the gap widens,
however, the rates of passage in each direction will rapidly diminish owing
to the increasing energy ''hump" between the surfaces, and a point will
be reached at which the net rate of passage can no longer provide the current
necessary to make the charge densities keep pace with the increasing gap.
After this point is reached, little further change in the charges will occur,
and the remaining charges will be those observed on the separated bodies,
providing that no further charge is lost by processes to be described later.
The above description is that appropriate to carriers of atomic or molecular
size ; the corresponding process where the carriers are electrons has been
discussed in detail by Harper^. Electrons are able to cross the energy "hump"
between the surfaces even if they lack the equivalent thermal energy
by the process of "tunnelling", whose frequency depends upon the
 Generation of Static on Solid Insulators—Henry P21

width of the gap rather than upon the magnitude of the potential energy
hump. The general results are similar to those for ions, and Harper concludes
that, over the practical range of velocities of separation of the surfaces, the
value of the velocity makes a negligible difference, and that the passage of
electrons across the gap may be regarded as stopping at a width of 25 A.
Since this paper was written for the Conference, the present author has
made a simple calculation corresponding to that of Harper, but for atomic
ions when the occurrence of "tunnelling" would be negligible. The result
gives the maximum energy barrier that would be surmounted with sufficient
frequency by the ions during separation of the two surfaces, rather than the
maximum distance. It works out as 1-0 eV at 2 0 ^ , and this value is grati-
fyingly insensitive to the assumptions made, as was Harper's result. Since
1 eV is also the value estimated earlier in this paper for the energy required
to move an ion from an isolated dielectric surface, it might appear at first
sight as though ions could jump across any gap between such surfaces.
This seems unlikely, and the probability is that the estimate in Section 4
for the energy required to remove the ion was too low for the reason given
in the footnote on page 11. Calculation of the distance over which the ions
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can jump will have to await better data for these energies of removal,
preferably derived by experiment.
The fact that the observed charges after separation will not correspond
to the closest distance of approach but to a wider gap occurring during
separation is the justification for assuming in our model that the carriers
could be definitely assigned to one surface or the other.
The dissipative process discussed above ceases when the gap exceeds
a value to be measured in Angstrom units. If the separation takes place in
air or other gas another dissipative process may start as soon as the gap is
several times the mean free path of the gas molecules. If the electrostatic
field is high enough, multiplication of stray ions in the gas by collision
will occur, and a silent discharge will be started which will reduce the surface
charges till the field is no longer sufficient to maintain the discharge. If the
separating surfaces may still be considered as parallel, the field between
them in the absence of comparable charges elsewhere will be approximately
given by 4KG. NOW, for gaps in air of the order of a centimetre at normal
pressures, a discharge will start if the field exceeds 30,000 volts/cm. This gives
an upper limit for the final surface charge density in air of about 8 e.s.u.,
or 3 X 10-® coulombs/cm-, a value which is often quoted as the highest
surface charge density which can exist in air at normal pressures ; and in
most circumstances this is a useful rule. The matter is not as simple as this,
however, even approximately. The rule that the field in air near to the
surface of a charged body is given by Aiza, true enough if the body is a
conductor, may not give even the right order of magnitude for the field near
to a charged insulating surface, where we must take other neighbouring
charges into account. For instance, if the insulator is a thin sheet in contact
with an earthed conductor, the field due to the charge on the insulator is
largely cancelled out by that due to the induced charge on the conductor—
a fact which often interferes with the detection of static in the mill, but of
which Medley" has made good use. Another limitation to the rule arises
from the fact that appreciable multiplication of ions in air by collision
requires that the field should exist over a length many times the mean free
path of the molecules (which is about 10'^ cm in air at normal pressures).
Even at a gap of 1,000 times the mean free path, i.e., /oth mm, the air will
support 95 KV/cm instead of only 30 KV/cm. Accordingly, the discharge
 Conference
between two surfaces does not start until they are separated by many times
10-^cm in air. This consideration is of textile importance in connection with the
attraction, and increased friction, between two rubbing surfaces due to the
separation of charge between them. We now see that this charge, and the
forces produced, are not necessarily limited by the silent discharge. Another
example of this effect which may be of textile interest is that the field round
an isolated charged filament or yarn is limited in extent by the dimensions
of the object, with the results, as quoted by Medley^\ that a filament can
support a higher charge density on its surface in air than can a larger body.
One case in which we can apply a form of the original rule with certainty,
however, is that of a free charged sheet of insulating material. Application
of Gauss's law shows that the surface charge density of both sides taken
together cannot exceed 16 e.s.u. without producing a field greater than the
limiting value on one side or the other.
Finally, we must mention subsequent leakage of the charge along the
"insulator" itself. This is of great textile importance, as it is the factor
which has most effect in determining whether static gives trouble in practice.
It has been discussed elsewhere by the author^^, and in great detail by Medley ^\
and we need not repeat the discussion here, except perhaps to comment
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on the apparent paradox of charge on a material, which is passing through

a machine, leaking away along the material to the very roller whose contact
produced the charge. This is a notion which many find hard to swallow,
and an alternative method of regarding the phenomenon (which does indeed
occur) may help. Once a steady state has been reached, the material leaves
the rollers with the amount of charge that it would normally receive from
them, but this charge has arrived there, not from the rollers, but by conduction
back along the material from parts which have gone before. Since the
material already has the " r i g h t " quantity of charge as it leaves the rollers,
the latter do not impart any more charge to it. There is a region of charge
on the "down stream" side of the rollers which is stationary in space, but is
continually travelling back through the material under the influence of its
own field at exactly the speed at which the material moves forward. Medley
has discussed this fully in the paper referred to.
Dissipation of static by intentional ionization of air hardly comes
within the province of this paper ; but it may be of interest to say that the
amount of ionization occurring everywhere due to cosmic rays, slight
radioactivity, etc., would suflice to discharge the static on a warp sheet in the
loom in a week or so if the warp were such a good insulator that no other
leakage occurred.

ACKNOWLEDGEMENT
I wish to thank my colleague Mr. W. H. Bowles for many stimulating
discussions which have helped in the writing of this paper.
Shirley Institute,
Didsbury,
Manchester 20.

REFERENCES
^ W. R. Harper. Proc. Roy. Soc, A. 1953, 218, III.
2 See, e.g., F. P. Bowden and D. Tabor. "The Friction and Lubrication of Solids.
Chap. 2, 1950 (Oxford : Clarendon Press).
»O. Knoblauch. Z. P/ns. Chcm., 1902. 39. 225.
" P. E. Shaw and C. S. Jex. Proc. Row Soc, A. 1928, 118. 97.
' J. A. Medley. Nature, 1953, 171, 1077.
 Generation of Static on Solid Insulators—Henry P23

RE¥ERENCES—continued
« A. Coehn. Ami. Phys., 1898, 64, 217.
" J. A. Medley. Brit. J. Appl. Phvs., 1953, Suppt. 2, 28.
« W. R. Harper. Proc. ROY. SOC, A. 1951, 205, 83.
» P. Tartakovsky. Z. / Plivs., 1929, 58, 394.
*" H. Helmholtz. Ann. Phys., Lpz., 1879, 7, 337.
" P. S. H. Henry. To be published.
1- P. E. Shaw and C S. Jex., Proc. Rov. Soc, A. 1928, 118, 108.
" P. S. H. Henry. Brit J. Appl. Phvs., 1953, Suppt. 2, 31.
'* P. S. H. Henry. Brit. J. Appl. Phys., 1953, Suppt. 2, 78.
" H. J. Goldsmid. J. Electronics, 1955, 1, 218.
" E. W. B. Gill and G. F. Alfrey. Nature, 1949, 163, 172.
1' A. Coehn and A. Lotz. Z.f Phvs, 1921, 5, 242.
^8 A. J. P. Martin. Proc. Phys. Soc. , 1941, 53, 186.
" A. H. Bowles. Shirley Institute. Private communication.
^" Various writers on xerography ; e.g., R. C. MacMaster. Non-Destructive Testing.
1951, 10, 8.
2^ P. E. Shaw. Proc. Phvs. Soc, 1927, 39, 449.
" P. E. Shaw. Proc. Rov. Soc, A. 1929, 122, 49.
==> W. A. D. Rudge. Proc. Rov. Soc, A. 1914, 90, 256.
-* E. W. B. Gill. Nature, 1948, 162, 568.
" P. E. Shaw. Proc Rov. Soc, A. 1918, 94, 16.
-« P. S. H. Henry. Brit. J. Appl. Phvs., 1953, Suppt. 2, 6.
-" A. H. Bowles and P. S. H. Henry. To be published.
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=* See, e.g., "The Theory of Rate Processes." S. Glasstone, K. J. Laidler, and

H. Eyring. 1941. (New York : McGraw-Hill).
2» J. Frenkel. /. Phvs. U.S.S.R., 1941, 5, 25.
^'"H. Freundlich. "Colloid and Capillary Chemistry." 3rd Edn. 1926, 284.
(London : Methuen).
" J. A. Medley. Brit. J. Appl. Phvs., 1953, Suppt. 2, 23.
3= D. F. Arthur. / . Texf. Just., 1955, 46, T721.

DISCUSSION
Professor Honegger welcomed the delegates on behalf of the Swiss Textile
Organizations and, in particular, conveyed a message from Dr. Ernst,
President of the Swiss Society of Textile (Themists and Colourists, who was,
unfortunately, compelled to be in Florence in readiness for the forthcoming
Conference of Textile Chemists and Colourists.
The Textile Institute was nearly 50 years old. When it was founded,
the production of man-made fibres on a commercial scale had scarcely begun.
The past 50 years had seen the development of textile science and it was true
to say that the Textile Institute had had much to do with this ; it had
provided a platform for scientific discussion and its Journal had become
the leading scientific periodical of the textile industry in the world. One
could not look back over the development of the Institute without admiring
the foresight and wisdom of its founders.
Today, in all countries, there was complaint of a shortage of scientists.
Even the new, and perhaps more attractive, branches of science had difficulty
in finding recruits. The textile industry, in particular, the oldest industry
in the world, was suffering from this shortage, but the Institute and its
Journal had done much to form a focal point round which an important
branch of modern knowledge had crystallized. Thus, at the same time,
much was being done to make textile science attractive to scientifically
minded young men, and hence to favour recruitment of the right type of staff.
Static electrification was a phenomenon that had long been recognised,
but it had sprung into prominence with the development of man-made fibres.
If the difficulties caused by static were to be overcome, a knowledge of its
fundamental causes was essential ; and this formed the subject of the opening
paper.
 P24 • Conference

Dr. V. E. Gonsahes asked if Dr. Henry had any ideas on how the amount
of energy required to remove a charged particle from a surface could be
measured. This was surely very difficult.
Dr. P. S. H. Henry agreed that, although one or two people (notably
Tartakovsky) had measured the amount of energy required to remove electrons
from an insulating surface, he had no suggestions to make regarding the
possibility of doing the same for atomic ions.
Physicists had calculated that, of the energy required to remove atomic
ions from crystals, 90% was due to electrostatic attraction, the remaining
10% being attributable to overlap forces and van der Waals' forces. It was
not possible, however, to treat polymers in the same way.
Dr. H. Weigaml referred to cellulose acetate fibres lubricated with a
mixture of a mineral oil and a tertiary ester of phosphoric acid, this ester
being an incompletely esterified one. The degree of free acid content might
be defined by the acid number (mg KOH/g ester). This value had been varied
between 17 and 68. If there was any truth in the theory that static electricity
depends on the movement of ions, then the electrostatic charge should be
related to the acid number. It had been found, however, that, although
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an electrostatic field of —31 volts per cm was associated with an acid number
of 17, the field associated with acid number of 68 was not smaller, but was
equal to —46 volts per cm. FurthcrFiiore, in the case of an acid number of
20 units, replacement o^ the hydrogen ions by ions of increasing size, such
as lithium, sodium, potassium, ammonium or triethanolamine, did not result
in a corresponding increase of the electrostatic field but in a very irregular
change.
Dr. P. S. H. Henry said that he would have expected this result. The
hydrogen ions would pass over from the surface of the cellulose acetate
leaving a negative charge and, consequently, an increase in negative charge
would be expected from an increase in the number of hydrogen ions able to
migrate. Mr. Medley had published work in Nature in which he indicated
that small hydrogen and hydroxyl ions readily passed to other surfaces.
Mr. J. A. Medley said that it was very difficult to generalize about the
size and the sign of static charge being generated. His main interest lay in wool,
and thus in substances containing the - C O - N H - group which were high
in the triboelectric series, in contradistinction to the cellulose acetates and
pure hydrocarbons which usually assumed a negative charge. He suspected
that this was due to the tendency of the -NH group to become positively
charged by gaining a proton or perhaps by losing an electron.
Dr. P. S. H. Henry thanked Mr. Medley for these observations.
Mr. K. W. Mieszkis asked if Dr. Henry could give any information about
the possibility of avoiding static by processing blends in which the components
are chosen from two ends of the electro-static series. Some three or four
years ago there were reports from U.S.A. that by processing a blend of nylon
with Terylene it was possible to obtain static-free yarn.
Dr. P. S. H. Henry said that he had no information about this interesting
possibility.
Mr. J. H. MeGuire asked whether, in the case of equilibrium states,
change of temperature of entire surfaces would change the order.
Dr. P. S. H. Henry pointed out that Equation (3) for the equilibrium
charge density contained one term which was temperature-dependent and
one which was not. If these should be of the same order of magni^tude,
a change in temperature could reverse the sign of the charge, and hence
the orders in the series.
 Generation of Static on Solid Insulators—Henry P25

Dr. W. Sprenkmann, referring to a table listing test results found on an

acrylic fibre treated with an anti-static agent, which were evaluated in the
fibre department of M/s. Hansawerke Luerman, Schuette & Co., Bremen,
drew attention to the Allowing facts. Reversal in sign and the magnitude
of charges depended
1. on the density of the reviving agent (given in terms of temperature of
the reviving baths at (a) 35°C and (b) at 65°C,
(The absorbed quantity of the anti-static agent at the above
temperatures was kept at even level by modifying the roller pressure.)
2. on the contents of moisture of the treated fibres adjusted by applying
different drying temperatures, as was proved in the test series at 35''C.
The results showed that the effectiveness of some anti-static agents might
be varied by applying different temperatures in the reviving batches.
Dr. P. S. H. Henry said that in such complicated circumstances it was not
possible for him to comment at short notice.
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