Addition Agents For Negative Plates

A paper presented at the Ninety-second Gen.
eral Meeting held at Boston, Mass., Octo-

ber 17, 1947, J. N. Mrvudich presidln9.
ADDITION AGENTS FOR NEGATIVE PLATES OF

LEAD-ACID STORAGE BATTERIES
I. Introductory *
By EVERETT J. RITCHIE**
ABSTRACT
This paper discusses the addition agents that have been used in the
lead-acid storage battery in order to improve the functioning of the
negative plate. It discusses the factors leading to the search for addi-
tion agents (Section I), the methods of using them (Section II), and
places the agents in groups according to their function in the plate
(Section I I). The theory of expander action is discussed (Section III)
with reference to the particulate nature of the sponge lead, the crystal-
lization of lead sulfate, and the prevention of undesirable chemical side
reactions. The expanders prepared from plants and plant products are
considered (Section IV) under various heads such as lignin, cellulose,
humic type substances, and others. The practical use of expanders is
explained briefly (Section V). Charts showing the relation of some
of the patented materials are included. The bibliography lists many
addition agent patents and the addition agents are listed in an appendix.
I. INTRODUCTION
1. Purpose and Scope

This paper is the introduction to a series of papers which will deal
with the experimental results obtained from the testing of many pure
organic compounds and other materials as "expanders" in the negative
plates of the lead-acid storage battery. The objective of this introduc-
tion is to present a brief treatment of the general subject of negative
plate addition agents, the reasons why they have been needed, how they
are added to the plate and some of the ideas advanced to explain how
they function. Although "expanders" are perhaps the most important
class of addition agents, this paper will not linLit itself to them.
In this series of papers the use of tkc term "addition agent" will
refer to trace materials or minor constituents which have been added
to produce specific effects. The term "expanders" will be used as
designating a special group of addition agents that produce an increase
* Manuscript received July 28, 1947.
** Research Chemist, Research Laboratories, The Eagle-Picher Company, Joplin, Mo.
229
Downloaded on 2014-10-14 to IP 130.102.42.98 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use)
unless CC License in place (see abstract).
230 EVERETT J. RITCItIE
in the apparent volume of the negative active material after cycling

and which are intended to increase the low temperature, high discharge
rate capacity of the negative plate. Bulking agents, as sulfuric acid,
that make possible the production of low density active material will
not be considered as expanders.
2. Literature Sources
The literature on the subject of addition agents in negative plates is
limited to a few journal articles, the discussions in the patents, and
brief mention in the reference books on batteries and electrochemistry.
Many of the organic compounds tested as expanders in the systematic
study to be reported in the following papers were selected from the
patents listed in the bibliography. A critical reading of these patents
reveals that in the discussions and disclosures in the body of the
patents there exists a great deal of repetition, overlapping, and con-
tradiction. Although many of the early patents were very broad, they
did not prevent the later issuance of narrow and specific patents. They
did, however, form such a broad prior art background that the validity
of none of the expander patents has ever been tested in court. The
strength of many of these patents is open to serious question in the
absence of a significant court action of record. The claims themselves
were studied only as a source of information since the disclosures
made in the body of the patents, rather than the legal aspect of the
claims, is the primary interest in this paper. Legal interpretation of
the claims in most cases show technical distinctions.
3. Historical Background for the Use of Addition Agents

The story of the development and use of addition agents brings into
relief the faults and failings of the lead-acid storage battery and the
manufacturing difficulties encountered in its evolution. The develop-
ment from about 1881 when the pasted plate type of battery was
invented, almost simultaneously by C. A. Faure in France and C. H.
Brush in America, has been continuous along these major lines: (A)
mechanical design of grids, containers, separators, and parts; (B) con-
trolled production of lead oxides or other leady compounds for use as
the active material; (C) process engineering and the effect of manu-
facturing variables on the product; (D) addition agents to develop
specific desired properties.
The majority of the early storage batteries were in heavy-duty sub-
station service in heated rooms where they received regular attention.
Batteries designed to operate under these conditions were quite unsatis-
factory when used in other types of service. The installation of elec-
trical self starters on the early automobiles showed the lead-acid battery
of that period to be seriously limited in capacity at high rates of dis-
charge at low temperatures. The battery that has been developed to
meet the demands of the modern automobile is capable of functioning
effectively both as a source of high amperage current at low tempera-
tures for cranking the engine, and also for supplying current for
numerous accessories which, taken together, have a very considerable
watt-hour demand.
A D D I T I O N A G E N T S FOR N E G A T I V E B A T T E R Y P L A T E S 231
4. Type Failures Due to Active Material

Apart from purely mechanical causes, many battery failures due to
loss in capacity may be charged to either the positive or negative active
material Typical positive active material failures are of two types:
(A) The active material is too soft and sheds from the plate, and
eventually the sediment wells in the container bottom become full,
producing "shorts." The finely divided active material shed from the
positive plate will for a time be suspended in the electrolyte and will
contribute to the growth of lead sponge or trees on the negative plate,
which can also produce shorts. The capacity of the cell will decrease
as the positive plate sheds its active material. (B) When the active
material is too dense and hard, the changes in active material volume
upon cycling will distort the grid so that buckling occurs, causing
cutting of the separator and shorting of the cell.
Typical negative plate failures arise from changes in the physical
structure of the sponge lead active material. Under service conditions
the active material will shrink and crack and its texture, in the absence
of addition agents, will quickly become granular or sandy. In this
condition the negative plate will have lost much of its original capacity
at high discharge rates but may still have considerable capacity at
lower rates.
5. Reasons for Use of Addition Agents
Early battery manufacturers occasionally had difficulties of various
kinds and their engineers spent a great deal of time in searching for
addition agents which could be added to the active material to correct
any and all troubles. Mixing and forming liquids of many types were
used. Plate characteristics are now closely controlled by selecting and
maintaining the proper active material density in the plate during
manufacture and this is accomplished by the proper use of sulfuric
acid as a bulking agent. 229,
The most important reason for the modern use of addition agents in
negative active material is to increase the low-temperature capacity at
high discharge rates. Other reasons are to produce stronger plates, to
improve the adhesion of the active material to the grid, to increase the
electric conductivity of the active mass, to render control of the drying
operation in the manufacturing of plates less critical, to control on-
charge voltages, and to reduce positive-grid corrosion. It would be
very advantageous if agents could be found that would increase the
rate of diffnsion or reduce the viscositv of sulfuric acid at low tem-
peratures without any accompanying deleterious effects.
II. ADDITION AGENTS AND THEIR USE
1. Methods of Using Addition Agents

The manner in which an addition agent is used will depend on its
physical state and whether or not it is soluble in dilute sulfuric acid.
It may be added at almost any stage of the manufacturing process,
* S~ee bibliography at end of paper.
232 EVERETT J. RITCHIE
and may be added at one stage and later be entirely removed after
having left its effect on the physical structure of the active material.
The methods of addition are outlined here for various types of agents.
A. If a gas, it may be absorbed in the paste or plate at almost any
stage of manufacture. Carbon dioxide is a typical example and is
frequently added to the atmosphere of the plate drying oven to pre-
vent cracking.
B. If a liquid, or a solution of a soluble salt, it may be added to
(a) the active material when mixing the paste,
(b) if soluble in acid, it may be added to the pickling or dipping
acid,
(c) the forming electrolyte, or
(d) the finished battery electrolyte.
C. If a solid, it may be added as a finely divided powder to
(a) the dry active materials when making the paste, or to
(b) the compound from which (1) the container or (2) composi-
tion separators are made.
2. Addition Agents Grouped by Function

Addition agents may be grouped according to the desired effect they
are expected to produce in the battery. Some agents may produce
several effects and thus appear in several groups.
A. Addition Agents to Increase Plate Mechanical Strength. The
development of mechanically strong plates was attempted by the use
of three types of agents:
(1) The use of binders (such as plaster of paris, shellac, beeswax,
water glass, tar distillates, and rubber) which formed a porous net or
skeleton within the active material. While these agents did produce
strong plates, the presence of an appreciable amount of a noncon-
ductive inert material also reduced the capacity of the plate by reduc-
ing the amount of active leady material.
(2) Fibrous materials which would reinforce the active material
were used to prevent the development of cracks by shrinkage. Among
such materials, glass wool, hair, cotton fibers, asbestos, and feathers
were tried. Properly used, some real advantages are obtained by the
use of fibers for this purpose.
(3) Volatile or soluble addition agents were used which produced a
strongly bonded plate from which the agent itself was readily removed.
In this class belong such items as zinc sulphate, magnesium oxide and
sulfate, glycerine, glycol, aluminum sulfate, carbon dioxide, ammonia,
anamonium sulfate and sodimn bisulfate. Agents of this type are not
much used at the present time, but a large number of very good bat-
teries have been manufactured using such materials.
B. Addition Agents Which Increase Porosity of the Active Mate-
rial. According to the patents, the porosity of an active material mass
may be increased by one of several methods.
(1) Fibers which act as wicks to furnish capillary channels through
which the electrolyte may travel. The examples are those already
mentioned under reinforcing fibers.
A D D I T I O N A G E N T S FOR NEGATIVE BATTERY PLATES 233
(2) Porous particles such as wood dust and diatomaceous earth,

which tend to promote diffusion by preventing the sealing off of internal
pores or voids.
(3) The porosity of a plate is increased by the removal of an addi-
tion agent which is soluble and such materials as ammonium sulfate,
zinc sulfate, magnesium sulfate, sodium or potassium sulfates were
used.
(4) Materials such as wood dust which slowly decompose in contact
with the electrolyte and which thereby maintain a certain degree of
porosity by their removal were also used.
C. Addition Agents as Crystallization Nuclei for Lead Sulfate.
Addition agents crystallizing in the same system as lead sulphate and
with similar unit cell dimensions promote the deposition of lead sulfate
away from the sponge lead particles. These agents should have solu-
bilities of the same order as lead sulfate and barium and strontium
sulfates meet these requirements. The use of both normal and basic
lead sulfates in active material compositions has also been patented.
Their use in appreciable amounts permits a weaker mixing acid to be
used.
D. Addition Agents to Stabilize the Sponge Lead Structure. The
sponge lead structure of a formed negative plate resembles a gel in
a number of ways. Its particles grow with a resultant shrinkage in
its apparent volume and the production of cracks. Addition agents
which tend to stabilize the original structure or act as dispersing
agents for any large particles that are present may be either gels,
gel-forming materials or suitable compounds. Representative agents
that have been covered in the patent literature are as follows:
(1) Gels
(a) Inorganic; silica and alumina gels.
(b) Organic; glue, gelatine, starch and flour preparations.
(2) Stabilizers
(a) Pure compounds. The effect of certain inorganic ions is
disputed. Many pure organic compounds have been tested,
particularly the phenols and homologes.
(b) Naturally occurring substances.
(A) Without preliminary chemical treatment: The most
frequently used are plant materials of which a great variety
have been tested such as wood, straw, bark, hemp, cotton,
etc. Animal materials as wool, hair, and feathers have
been used.
(B) With preliminary chemical treatment: The above plant
and animal materials have been subjected to a large variety
of chemical treatments before use. The end product of
many such treatments as well as the reaction with the
electrolyte is a "humie acid" type of material.
E. Addition Agents to Reduce Sponge Lead Oxidation. The sponge
lead active material of the negative plate is very easily oxidized. The
presence of addition agents in the active material which are powerful
reducing agents may protect the sponge lead from oxygen or oxidizing
234 EVERETT J, R I T C H I E
compounds that may be present ill the electrolyte. Agents such as

quinol, resorcinol, pyrogatlol and others have been used.
Related to the inhibition of oxidation are those patents which cover
mechanical designs sucla that the oxygen entrained in tile electrolyte
does not come in contact with the negative plate e:'a, and also the use
of activated carbon nL 192 in the positive plate to prevent the escape of
oxygen from it on charge.
F. Miscellaneous Addition Agents. Two types of agents that do not
fit in the above groups are here discussed:
(1) To increase electrolyte conductivity and the reactivity of the
active material.
Several attempts have been made to utilize the property of radio-
active materials to produce ionization in their neighborhood by means
of their emitted radiations. By continual radioactive bombardment the
electrolyte should, therefore, be more highly conductive and the active
material more reactive, permitting the battery to be discharged at higher
rates than normal. Radioactive materials have, therefore, been pat-
ented when incorporated in celluloid separators, sa insoluble glass mats, ~7
insoluble salts in the electrode,~2 and as soluble salts in the electrolyte.'-q`~
No information concerning the practical use of this development is
available to the author.
(2) To control "on-charge" cell voltages.
The presence of certain types of organic compounds in the negative
active material may cause the on-charge cell voltage to become much
higher than the normal 2.5 volts. This may be undesirable for two
reasons. If the voltage of the charging source cannot be increased,
it may be impossible to fully charge the battery, and if the charge
voltage can be increased, appliances or accessories such as lights may
be quickly burned out because of the higher line voltage. It has been
found that the addition of cobalt, nickel, or tellurium sulfate or other
salt to the electrolyte will reduce the on-charge voltage. The salts have
been tested when added to the active material,lal,~:~2,14T,1% and the
electrolyte~-%
II1. T H E M E C t l A N I S M OF EXPANDER ACTION
I. Introduction
A. Nature of the Improved Performance Due to E.rpander Use.
The high rate discharge capacity of a lead-acid battery having plain
litharge negatives is nmch less than the theoretical capacity and the
difference increases as the temperature of discharge becomes lower. 231
The use of expanders in the negative plates makes possible the dis-
charging of a larger percentage of the theoretical capacity of the bat-
tery. It should be emphasized here that the additional capacity does not
come from the expander per se but rather that the expander has made
the additional capacity available. The mechanism by which a small
amount of expander can double or triple the useful capacity of a battery
involves both chemical and physical phenomena.
B. Negative Capacity Limited by Polari:ation. A study of negative-
to-cadmlmn electrode potentials measured during high-rate low-tern-
A D D I T I O N A G E N T S FOR N E G A T I V E B A T T E R Y P L A T E S 235
perature discharge shows that the capacity is limited (with plain

litharge negatives coupled with average capacity positives) by the rise
in negative-to-cadmium electrode voltage. This increase in electrode
potential produces a corresponding drop in cell voltage and conse-
quently a rapid drop in current. If, after being discharged to any arbi-
trary limiting voltage, the battery, or cell, is allowed to stand idle for
some time, additional current may be drawn before the limiting voltage
is again reached. It is clear from these facts that the polarization of
the negative plate on discharge is the factor limiting the capacity under
these conditions? 3~ 24~
The explanation of expander action must show how small amounts
of added materials can reduce the polarization of the negative plate.
The polarization of the electrode is a direct result of the electrode
reaction that produces the current. When the rate at which the electrode
reaction proceeds is greater than the rate at which the reaction products
can be removed or diffuse away, the rate of the electrode reaction drops
and the current produced also drops. The zone about the electrode con-
taining the reaction products will then become a high resistance barrier.
Attempts to maintain a constant current flow by lowering the external
resistance in the discharge circuit will increase the potential difference
across the high resistance barrier in accord with Ohm's law. Thus the
increase in voltage noted in the negative-to-cadmium potential when
discharging at constant current can be used as an indication of the
degree of negative electrode polarization.
Lead sulfate is formed at the negative electrode during discharge.
The electrolyte in contact with the electrode furnishes the sulfate ions
and the maintenance of the flow of current becomes dependent on the
movement of sulfate ions toward the electrode by diffusion. This
results in the electrode being surrounded by acid which becomes more
dilute as the reaction proceeds.
The location and physical structure of the lead sulfate formed in
the reaction are important factors contributing to the polarization
voltage. It has been shown 246 that at low rates of discharge the lead
sulfate forms small separate crystals within the voids of the plate. At
high rates of discharge the lead sulfate apparently forms a thin film
or coating on the surface of the sponge lead particles and obviously
would produce a rapid increase in polarization voltage. Also, the
polarization would be increased at low temperatures because of the
reduced solubility of lead sulfate in sulfuric acid, and the increased
viscosity of the sulfuric acid which would reduce the rate of diffusion.
Willihnganz ~4s concluded from resistance data and microscopical
observations that the major factor in negative electrode polarization
was the production of a supersaturated solution of lead sulfate in
contact with the lead electrode. His work indicates that at high rates
of discharge the lead sulfate does not crystallize from solution as
rapidly as it is formed, giving an enormous increase in lead ion con-
centration. This may not be opposed to the findings of Clark and
Rowan 'a* who concluded fiom a radioactive tracer study that there
was little or no transfer of lead ions during the charge or discharge of
either plate. It is possible that the supersaturated lead sulfate solution
is confined almost entirely to the pores of the active material and hence
236 EVERETT J . R I T C t l I E
its migration would be on a micro scale which would not have been
measured by Clark and Rowan.
2. The Particulate Nature of the Sponge Lead

During formation the basic lead sulfate and lead oxides of a plain
litharge negative are almost entirely reduced to spongy metallic lead.
The properties of the negative plate are so closely related to the struc-
ture of the sponge lead that a detailed discussion is necessary. Three
aspects of the physical properties of this metallic sponge are (1) the
extent of the surface area of the particles, (2) the size of the particles
and the distribution of sizes, and (3) the nature of the voids between
the particles.
A. Surface Area. The low temperature high rate discharge capacity
delivered by a fixed quantity of negative active material is not greatly
increased by increasing its apparent surface. That is to say that the
capacity of the negative plates in a 13-plate S.L.I.* battery will be
almost the same as the capacity of the same weight of negative active
material in a 17-plate battery. It is true that the capacityof the 17-plate
battery as a whole will be somewhat higher because of more effective
utilization of the positive active material. The change from a 13 to a
17-plate cell represents an increase of 28.5% in negative plate area
and of 33.3% in positive plate area. This increase in negative plate
area produces only a small capacity gain for a given weight of negative
material.
Increasing the active surface area will reduce the polarization effect
at a given discharge rate by decreasing the current density per unit
of active surface. This will result in the electrode reaction being able
to proceed for a longer time before the products of the reaction form
an effective barrier. With more surface in contact with the electrolyte
the depletion of the acid at the electrode surface will take place more
slowly and, hence, diffusion will be more effective in removing reaction
products and bringing in fresh acid. The negative-to-cadmium voltage
will thus rise more slowly at low than at high current densities.
Since the total surface area of particles increases rapidly as the par-
ticles decrease in diameter, the extra capacity made available by ex-
panders may be a direct result of the tremendously increased active
material surface. The extent of the active material surface must not
be confused with apparent plate areas, and may be in the order of acres
rather than the square inches of apparent grid area.
B. Particle Size. The size of the sponge lead particles determine
the extent of the active surface area. If plain litharge negatives having
the same weight of active material are made from both coarse and fine
particle size litharges, the fine particle size litharge will have consid-
erably greater capacity at low temperatures and at high discharge rates.
In fact, a plain litharge negative made from a fume process litharge
may have greater capacity on its first discharge than one made from a
coarse litharge to which organic expander has been added. After a
* Starting, lighting, ignition,
ADDITION AGENTS FOR NEGATIVE BATTERY PLATES 237
very few cycles, however, the plain litharge negative will have lost
much of its original capacity while the negative made from coarse
litharge containing organic expander will improve for perhaps 50 to
100 cycles.
The following may be the mechanism by which organic expanders
can reduce the particle size of the lead sponge. The organic expander
is adsorbed on the surface of the lead particles during formation of
the active material. Upon discharge, the lead particles become partially
coated with a film of lead sulfate which is porous by reason of the
adsorbed organic expander. Upon charge, the lead sulfate is reduced
to metallic lead but a portion of it is separated from its original posi-
tion by a partial layer or film of the organic compound. Possibly the
organic agent forms an addition or adsorption type of chemical com-
pound with the lead. The organic agent itself is transported during
charge and discharge so that on charge the freshly reduced lead is
also covered with a partial coating of organic expander. Upon repeti-
tion of charge and discharge, the large grains are reduced in size and
the small ones are prevented from growing by the film of organic
substance on their surfaces. This view is supported by the fact that
cycling is necessary to develop capacity when a coarse litharge is used
with organic expander.
Microscopical and x-ray examination of negative plates (containing
organic expanders) after service show the lead particles to be extremely
fine. Birt, Pritchard and Daily say with respect to the results obtained
with their expander, T M "X-ray analyses on negative plates conclusively
show that the lead particles therein have a constant growth when no
agent is used, such growth gradually deteriorating the plate and lessen-
ing its electrical capacity. When lignin sulfonic acid is used as an
addition agent, in varying small percentages the growth of the lead
crystals is inhibited and substantially prevented throughout the life of
the battery plate."
The use of expanders in negative plates presents many features
which appear to be analogous to the organic addition agents that have
been used in electroplating baths for many years. Their function in
electroplating has" been to promote the formation of dense smooth
coherent deposits with good adhesion to the base metal and freedom
from the formation of crystal "trees." It has been established 228 that
these organic agents are adsorbed or plated out in the electroplated
film. A review of some of the literature on plating bath addition
agents 2~.7shows that many of the agents that have been used are closely
related to useful expanders.
It has been pointed out 235 that much of the shrinkage of the negative
active material occurs during charge, in other words, during the part
of the cycle in which metallic lead would be plating out if its ions were
present. In the plating bath the metal ions come from the soluble salts
in solution, whereas, at the negative battery plate the lead ions must
come from solid lead sulfate crystals in contact with, or only a short
distance from, the lead surface on which they will be plated. There is
a rather high concentration of metal or metal-bearing ions in solution
in a metal plating bath. In a lead-acid battery it has been shown "a~
that there is a very low concentration of metal ions in the electrolyte
238 EVERETT J. RITCI"IIE
during charge and very little ionic transfer of lead between the elec-
trodes ol- from point to point on the salne electrode if separated by
more than a minute distance. In either system the organic agents
operate to reduce the grain size of the deposit.
The action of a suitable agent seems to be specific. It does not
appear possible to predict from chemical or physical data which com-
pounds would be the better addition agents for any particular plating
bath or for use as an expander except that they are usually polar com-
pounds. That the structure and spatial arrangement of the compound
are important will be shown in the following papers of this series, As
expanders, some organic compounds are at their maximum efficiency
only when used in a narrow concentration range.
In the freshly formed negative plate it would be expected that the
distribution of particle sizes of the sponge lead would be very closely
related to the range of sizes in the litharge from which it was made.
This would be expected regardless of whether organic expander was
present or not and it is apparently true. In a plain litharge negative the
larger crystals or particles grow at the expense of the small so that
after cycling the particle size will become quite uniformly large. On
the other hand in the presence of organic expanders the fine particles
are stabilized and the large ones become smaller until they have become
uniformly minute. In either case the distribution of size is probably
narrow but may be somewhat broader for the plain litharge negative.
Direct determination of the particle size distribution of a lead sponge
has not been done to the author's knowledge except as it has been
estimated from microscopical studies.
C. Voids and Porosity. Small lead particle size and a large active
surface area can only be effective for the production of current if the
major portion of the surface is in contact with the electrolyte. This
necessitates a partial separation of the particles so that the apparent
volume of the sponge is considerably greater than the total volume of
the lead particles of which it is formed. The interstices between the
individual particles will be most effective when they are of such size
and arrangement that acid from outside the plate can readily travel into
the interior.
The "porosity" of the active material is the percentage of the total
apparent volume which is occupied by the voids. For a definite volume
of leady active material the porosity can only be increased by increasing
the total apparent volume, which will decrease the paste density. A
careful reading of the many patents which speak of "increasing poros-
ity" will show that many inventors actually had in mind the mainte-
nance of voids or diffusion channels in the active material, rather than
the production of a low density active material with a high percentage
of voids. Other patents are aimed at the production of many minute
voids rather than a smaller number of larger ones and this is also
spoken of as "increasing porosity."
The sulfuric acid molecule, or the sulfate ion, is hydrated or sol-
vated, 225, and as the degree of solvation is determined by temperature
and concentration its effective diameter will vary accordingly. This
means that a sulfuric acid molecule at ordinary temperatures could
pass with ease through a hole which would not admit it at lower tem-
peratures. Hence there is a definite lower limit to particle and pore
size which is related to the diameter of the hydrated sulfuric acid ion.
The rapid rise in the viscosity of sulfuric acid with decrease in tem-
perature is related to the degree of hydration but may also involve
molecular aggregates.
The total volume of the voids in the plate, expressed in per cent as
porosity, is important since it represents the storage of acid within
the plate and available to it for producing current the instant the circuit
is closed. If the plate porosity is too high, insufficient sponge lead will
be present to permit the platte to have the desired capacity. The oppor-
tunity for self discharge is said ~3~ to be greater with more porous
structures which permit greater active surface to be in contact with
the acid. The optimum negative plate will have a fine balance between
the total volumes of lead particles and voids, between the sizes of the
individual particles of lead and the voids, and the total active surface.
3. Lead Sulfate Crystallization Nuclei

It has been shown by x-ray diffraction methods 22~ that during dis-
charge lead sulfate is produced at the negative plate and 245 is assumed
to form a supersaturated lead sulfate solution before crystallizing. At
low rates of discharge this solution has time to diffuse into the voids
before precipitation can occur but at high rates diffusion does not
operate rapidly enough and the lead surface becomes coated with lead
sulfate.
By providing many crystallization nuclei of non-lead compounds it
is possible to reduce the degree of supersaturation at the lead particle
surface and to maintain the surface of the lead particles essentially
free of lead sulfate during the major part of a high rate discharge.
The effectiveness of the added material in acting as crystallization
nuclei is in direct ratio to the number of nuclei present. In other
words, the number of particles rather than their weight or volume is
the important factor. Several per cent of ground barites are required
to give the same benefit as a temh as much precipitated blanc fixe. It
is claimed that even less is required when the barium sulfate particles
apnroach colloidal dimensions. 149
It is possible that compounds exist which are not strictly isomorphous
with lead sulfate but which would play essentially the same role as
barium and strontium sulfates as crystallization nuceli. Such a com-
pound would have a crystallographic structure on one or more of its
surfaces which would be sufficiently like that of some face of lead
sulfate to permit the lead sulfate crystal to build on it. A typical
example of this phenomenon is the orderly formation of chalcopyrite
tetrahedrons on the surface of a sphalerite crystal although they are
not isomorphous. No compound so related to lead sulfate is known to
the author.
4. Prevention of Undesirable Chemical Side Reactions

The effectiveness of a lead-acid battery may be reduced by the
presence of certain undesirable side reactions. One of these is the
oxidation of the sponge lead of the negative active material by the

dissolved oxygen of the electrolyte while the cell is on open circuit.
This oxidizing effect is very apparent during the formation of a cell
having a large excess of negative active material, as the oxygen evolved
from the formed positive plate may almost completely stop the forma-
tion of the negative. The reverse phenomenon also occurs and a
balance between positive and negative active material is the best way
to avoid it.
At low temperatures the solubility of oxygen is high enough so that
the oxygen remaining in a liter of electrolyte at the end of charge
would be sufficient to oxidize a rather large area of the sponge lead
surface, and would do this on the more exposed active surfaces. This
possibly would represent a considerable loss in capacity at high dis-
charge rates and would show up on such characteristics as "five second
voltage."
The charging of a lead-acid cell at low temperatures at high current
densities leads to the production of appreciable concentrations of both
hydrogen peroxide and persulfate ion. 224 These products are probably
also present in small amounts at higher temperatures, and traces, even
if present for only a short time, would have considerable greater oxidiz-
ing effect on the sponge lead than could be ascribed to dissolved oxygen
alone.
It is possible that the sponge lead may be protected from attack by
these oxygen carriers if traces of compounds more easily oxidized than
lead are present in the sponge lead mass. The mechanism is possibly
related to that of the auto-oxidation inhibitors used in preventing
oxidation of many organic materials. The use of organic corrosion
inhibitors such as are used to protect iron when pickling to remove nfiU
scale may also be analogous. Many of the expanders have definite
reducing properties and some of them are also effective antioxidants
and corrosion inhibitors. Several series of compounds in which the
oxidation-reduction potentials fall in a regular series, show as ex-
panders an improvement in battery properties paralleling an increase
in reducing action. Such a series is catechol, resorcinol and quinol.
Most of the phenolic and many of the other organic hydroxyl com-
pounds are strongly reducing, and the presence of hydroxyl groups
can be demonstrated in the humic acid types of materials, lignin, cellu-
lose, starch and other plant materials.
IV. EXPANDERS DERIVED FROM PLANTS AND PLANT PRODUCTS
1. Introduction
Most of the common types of plant materials have been tried as
expanders. These materials also occur in modified forms as coal,
lignite, peat, muck and composted substances. By chemical action it is
possible to prepare from plants three types of materials that have been
more widely used as expanders than all others combined: the humic
substances, cellulosic materials, and lignin derivatives.
The pioneer workers in the chemistry of natural plant materials
assigned names to the products obtained by applying specific procedures
to certain raw materials. Later workers have applied these names to

classes of products of closely related nature and the original narrow
meaning has frequently been changed. In the patent literature related
to these expanders the terms are often used in a very restrictive sense
and yet in most cases they do not designate a chemical species.
In the study and interpretation of the patents of this field it has been
necessary to establish definitions for each type product based on the
procedure used in making it as well as on its properties. The chemical
operations that usually have been applied are extraction, hydrolysis, or
oxidation, and combinations of them. Extraction is usually a mild
hydrolysis. Hydrolytic procedures involve extraction in all operations
where a residue is left, and the treatment may vary in degree from
very mild to drastic. Some oxidation will usually accompany hydrolysis
but extraction may be so carried out that oxidation is very slight.
2. Expanders Derived From Wood

One of the first patents mentioning the use of wood as an addition
agent in negative plates is Tobiansky's of 1899Y* Later patents, based
partly on the particle size of the ground wood, were issued to Cham-
berlain 9~ and Willard. 9e The wood preferred in these patents is oak,
cypress or some wood containing relatively small amounts of wood
acids or resins.
In the preparations described below it is obvious that the ratio of
the products obtained and in some instances the nature of the product
itself will depend on the kind of wood used.
A. Lignin. The elementary composition of the lignin complex varies

with the source and with the method employed for its isolation. It
is agreed that methoxyl groups (OCHs) are present in the molecule
attached to an aromatic nuclei by an ether linkage. Hydroxyl groups
are present, perhaps entirely as phenolic though possibly also an enolic
or tertiary groups. The evidence for the presence of the ethylenic
linkage and the carbonyl group is contradictory341
The preparation of lignin and derivatives from wood may be done
in a number of ways which fall into two classes. The lignin may be
left as a residue after the hydrolysis and extraction of cellulose and
other constituents, or the lignin derivatives may be extracted and pre-
cipitated from solution. Both methods have been used in the prepara-
tion of battery expanders as:
1. The residue which remains after wood has been extracted with
cold, or hydrolyzed with warm, 72% sulfuric acid. TM
2. The precipitate obtained upon acidifying a solution of alkali
lignin. 14~
B. Lignocellulose. This is a naturally occurring complex of uncer-

tain composition and structure in which the lignin is chemically com-
bined with the cellulose, and perhaps other carbohydrates, through
ether or acetal linkages. Lignocellulose might be defined as a "de-
gummed" wood, in fact, the primary stage in the preparation of many
of the expanders from wood consists in treatment of the wood to

remove soluble gums, waxes, fats, oils, sugars, resins, and wood acids.
Wooden storage battery separators after treatment with dilute alkalies
are also lignocellulose or "degummed wood."
The use of lignocellulose as a battery expander logically includes
untreated wood of varieties low in the extraneous components, as well
as these preparations:
1. The residue remaining after wood has been extracted with steam.
hot water, or organic solvents as alcohol or benzene."' ~
2. The residue remaining after wood has been hydrolyzed with
dilute sulfuric acidY *
C. Lignosulfonic ~cid. In crude form this is the so-called "black

liquor" obtained as a by-product in the preparation of sulfite paper
pulp from wood. When wood is treated with a solution of calcium
bisulfite containing free sulfur dioxide, the lignin component of the
wood reacts giving a soluble material which is called lignin sulfonic
acid) 4~ Since it is available in large quantities, it has been much studied
in an effort to prepare effective expanders from it. These efforts have
been along three distinct lines, since the issuance of a patent covering
the use of the solids in the waste liquor ~ :
(1) The black liquor is essentially the solution of a calcium salt and
according to Birt, Pritchard and co-workers is not satisfactory for use
in a battery. Attempts have, therefore, been made by them to produce
a very pure lignin sulfonic acid. 15~ 151, 152, 158
(2) The lignosulfonic acid may be made to react with ammonia
J TREATMENT
. .rnoM
... I [ .U.S.E.D.w.oo.D
~ [ I ...E
.X
.T
.R
.OR
A
.C
.T
.. j [ HOBTAI
Y.~. .Y
k.(.0.~. T
. .~. FROM
E6Y I . . . . . . . ., s. . . 11
ALKALI LIGNIN
~ B E R r ET AL,
SC~_UT~ ~ 2.07g.20S
~CELLULOSES
A PENTOSAN~ THE C4~C~-
........... H ......... PORTION PRO0&JC T
KURFU~AL W A S RECOGN-
IZE0 By
,r SCHIEVr
U S 6~9,622
CELJ~Ut_OSE SOLUTION THE AL3~ALi LIGNqNS
e URONICAO0 ANO
IM~GNATE0 ~TH A N 0 OTHER ~ L U B L ~
COMPLCXC~. tROM SEA-
BARIUM SULFATE I~TS A~E NOT
~vEs THE ns
JOHNSTONE F~O~ T~E
~C~/~V~O
AL~INICACI0 IS 08TAINs
US 1,929.357 SCO~UM$ULFATE EXPANOE~ TP~I~NLEY, ET AL.
SOLUtlOIg u s 1,50~732
A 5 IN T R C A T E O 0~VT{ ALKALI CONTAIN5 RES~5,

W~ SEPARATOR5 SOLUTION C ~ J M S , ~ ACIDS. ]D~F~CATIOM G~ARD
U $ 1.940.71al
SUGAnS, E~C
9~ C H ~ E n OR EXTRACT
U 5 2.36SJaO
.......... HOT WATER
..... H DISCARDED
I
Fzo. 1. Expanders prepared by the treatment of wood with alkaline and neutral
reagents.
ADDITION AGENTS FOR NEGATIVE BATTERY PLATE~ 243
under the proper conditions of pressure and temperature and the use
of this product has also been patented. 163
(3) Relatively pure metallic salts of lignin sulfonic acid have been
prepared and tested. Among these may be mentioned nickel, 147 cal-
cium,135 lead, J35, ~s0 and barium. 151
D. ,~llcohol and Phenol Li#nin. Lignin isolated without the use of
alcohol or phenol in the extraction contains only methyoxl groups. If
alcohol or phenols have been used, the final lignin product contains the
alkoxy or aryloxy groups used in its isolation, and a number of such
products have been prepared and patented. For use as battery expander
these lignins are obtained by hydrolyzing wood with a small amount
of hydrochloric acid in the presence of the deoired alcohol or phenol. 13~
E. Alkali Lignin. The preparation of paper pulp from wood by the
"soda process" involves cooking the wood with about 20% of its weight
of alkali for 4 to 6 hours at a temperature of 165 ~ to 175 ~ C. The
products are an impure cellulose or "soda pulp," and a black liquor
containing alkali lignin, degraded cellulose and carbohydrates, and the
sodium salts of various organic acids present or formed during the
cooking.
The alkali lignin in the caustic solution may be precipitated by
acidification and two fractions have been prepared and are identified as
alkali lignin A and alkali lignin B by their solubilities in dioxane-ether
and their ratios of phenolic hydroxyl to methoxyl groups238 The
battery expander based on alkali lignin 140 is a mixture of both alkali
lignins and also contains some of the lignin and cellulose degradation
products.
I R[$1OUE
fROM
TREATMENT F f HYOROt.ySATE
OR
EXTRACT I I PRECIPITATE
OBTAINEDFROM
HYDROLYSATEBy I [ PRECIPITATE
Is ]
LIGNIN I .....COLD H ..........
COLD WATER H I
WILLARD
u S I,So~ggO ~ DILUTE, MARE DEGRADED
DILUTE AND ~ HUMICSUBSTANCE

BO,L ~ REINHARDT
LICNOC[ L L U L O S C DILUTE ADD

ST EWA~ T. ET AL. ;~2SO4 HYOR~YSATE
U s 2.36~.634 BARtUM HUMATE
F.CINHARDT
U S 2,030,?i6
5UL~IT[ PULP BISULPITE SULFONIC ACID AN0 A(~I01FICATtON

, EXPANDER
I ......... H ...... AND 502
......
H .... ..................
OTHER COMPOUND5
it
OR AIX)ITIONOF
METAL IONS
J
h STEWART
u $ 2,022,482
8IRT, ETAL, US 2.217.786 r~4 HYDROt.YSATE BARIUM,

BIRT, CT AL. 0 5 2,217,787 BIRT, ET At.. U S 2,217.187
PR~TCHARD.ET-~..~U52,217~BI4 AND | CALCIUMAND t.EAD.
u s 2.32.%542 STEWART. US 2,022,482
LEA~CALGIUM FREE,
I BY AMMONIATION BIRT, ETAk. U.~ ~,217.706
WILSON, U $ 2,367,453 NICKEL
DAILY, U .~ 2,17~680
Fzo. 2. Expanders prepared by the treatment of wood by acidic reagents.
244 EVERETT 3. RITCHIE
F. Cellulose. "Alpha-cellulose, the more stable portion of cellulose,

is defined on the basis of its insolubility in 17.5% sodium hydroxide at
20 ~ C. It is not a definite chemical entity, but a convenient empirically
defined fraction of the cellulose. Repeated treatments with alkali in-
crease the amount of cellulose that goes into solution."t43
The alpha-cellulose fraction very closely resembles cotton fibers in
many properties. By analysis several commercial bleached paper pulps 2~s
showed the following alpha-cellulose contents:
alpha-pulp 93.4%, sulfite pulp 84.4%, soda pulp 71.1%,
kraft pulp 82.8%.
Cellulose is the subject of several expander patents, and several
refer to paper or paper pulp of various types in their discussion of
the prior art. One of the early organic expanders known as "goo
expander" was a modified cellulose prepared by soaking wood pulp in
strong sulfuric acid and precipitating the product by dilution with
water. Other cellulosic materials as newsprint, woodflour, and cotton
linters were also used. Under certain conditions of time and tempera-
ture the cellulose was degraded and brown products resembling natural
humic substances resulted. Cellulose is obtained as a by-product in the
preparation of lignin expanders from wood, or is claimed as a prime
product, in a number of patents. 9s, 101,13s,139,140.
G. Hydrate or Alkali Cellulose. The reaction between cellulose and
sodium hydroxide solutions of various concentrations and tempera-
tures produces a number of fractions termed "alkali-celluloses." Of
these, those fractions designated by Hess and Gundermann "7 as alkali
cellulose III and IV have lattice structures very close to that of hydrate
cellulose which is ordinarily called mercerized cellulose. The met-
~ 1 ALCOHOLS JT. DILUTE WITH' AJ~*-Ot'l(~ LIGNtN

....
c AT~,L'~T
............ H w.,,, H..,. .......
U.S. 2,0Tg,Z'07
]
LtGNOCELLULOSE .....
OR
HCI AS A EXCE.T~PHENOl. HISBERT, ~T At..

CATALYST PHENOL LIGNIN AND DILUTE U S 2.079,207
STILL RESIOUE
tMPORE e~NZCNE O~SCA~DEO
I '[ _
CELLULO$E TREATING WITH --
LIGNOCELLULOSE ? DILUTE NH40H, HYDROLYSATr
I W H WOO0
tl .........h
, WA~'I, ~ A T WIT
DILUTE H2SQ4t OrSCAROCD
,
FIG. 3. Expanders prepared by the treatment of wood with the use of organic
reagents,
cerization of cotton fibers by treatment with alkalis is a reaction which

consists almost entirely of colloidal and physical changes. The inves-
tigators are not in agreement on a complete explanation of the products
formed. Apparently cellulose absorbs sodium hydroxide from dilute
solutions from which the cellulose can be recovered without change in
chemical composition but with a permanent change in its space lattice.
From stronger solutions alkali celluloses are obtained which have a
larger space lattice and different chemical composition. The concen-
tration of alkali and temperature of treatment are the important factors
in determining the nature of the productY '9
A battery expander whose cellulose is probably hydrate cellulose,
although described as hydrocellulose in the patent description, was
made by treating wood with aqueous barium sulfide solution. This was
then treated with sodium sulfate solution to precipitate barium sulfate
throughout the organic mass. 12~ The alkali lignin and other soluble
derivatives formed by the alkali remain in the mass.
H. Hydrocellulose. The "hydrocelluloses" are heterogeneous, cold

water-insoluble mixtures of cellulose fission products resulting from
hydrolysis of cellulosic material in the presence of an excess of H-ions.
It is a mixture and no individual hydrocellulose has been isolated. The
original x-ray diffraction pattern is not modified but the cellulose has
been chemically degraded, mainly by a shortening of chain lengths.
Hydrocellulose is peptized and chemically degraded by treatment with
dilute alkalies. The reducing power of the hydrocellulose, as measured
by its copper number, increases with the degree to which it has been
hydrolyzed. The original value of the celluose is essentially zero and
the final product glucose has a copper number of about 300. 247
Hydrocellulose for use as a battery expander has been obtained by
diluting with water a solution of cellulose in warm strong sulfuric acid,
or by diluting a solution in cold strong acid that has been allowed to
age, as in the production of "goo expander." Extractions of wood
using warm dilute acids undoubtedly produce some hydrocellulose.
I. Oxycellulose. When subjected to oxidizing agents, cellulose yields

a mixture of compounds of which the water insoluble portion is termed
oxycellulose. It is not a homogeneous product and an almost infinite
number of products are theoretically possible. Two types are recog-
nized: R oxycellulose for the reducing type with relatively high copper
numbers and which is formed in an acid pH range; and the MB type
which is highly absorbent of basic dyes, is relatively low in copper
number, and is formed in an alkaline pH range. MB oxycellulose is
evidently formed by oxidation followed by reaction with alkali which
produces some shortening of chain length.
In the preparation of an R oxycellulose the development of reducing
power as shown by its copper number is obtained without any marked
shortening of ~he long chain rholecules differing from the hydroeellu-
lose preparations in which an increase in reducing power is accom-
panied by a reduction in chain length. The characteristic group in the
R oxycellulose is the carbonyl while in the MB type it is the carboxyl.
On hydrolysis they yield uronic acids, carbon dioxide, and furfural.
Neither furfural nor carbon dioxide are obtained from the hydrolysis
of hydroce]lulose prepared from cotton34T
Although some oxycellulose is almost certainly present in many ex-
pander preparations, it is not claimed in any of the patents and is
mentioned in only a few) 24' 125
J. Hemicelluloses. "The definition of the term hemicellulose is less
precise than that of most other plant constituents and has been based
largely on properties. It is usually restricted to alkali-soluble poly-
saccharides, hydrolyzable by dilute acids to component sugars and
sugar acids. This, however, is insufficient unless it be recognized that
an alkali extract of wood may contain polysaccharides of two funda-
mentally different types, sources and roles,"~4~ (1) amorphous poly-
saccharides that invariably contain uronic groups, and (2) short chain
polysaccharides derived from the cellulose itself and known as "cellu-
tosans." The first may be described as "poly-uronide hemicelluloses"
and is a very minor component of wood.
Alginic acid, which is an uronic acid obtained from seaweed, has
been patented for use as a negative plate addition agent. 1~ The cellu-
losans readily hydrolyze to yield pentosans and furfural. The presence
of furfural in battery expanders was recognized very early. 38
K. Analytical Data on Wood. The variation in analysis of several
species of wood are shown in Table I with respect to cellulose, lignin,
acetic acid (which is typical of a group of wood acids), and pentosans
which indicate the amount of hemicellulose and oxycelluloses in the
wood. It was compiled from data given in "Wood Chemistry," by
Wise, pages 658, 660, and 661.
TABLE I
Acetic Total
Wood Acid Pentosans Cellulose Lignin
Western Yellow Pine 1.09% 8.97% 57.41% 26.65%
Western White Pine 1.03 10.19 59.71 26.44
Tan Bark Oak 5.23 19.59 58.03 24.85
Balsa 5.80 18.51 54.15 26.50
White Oak 2.87 23.30 50.88 31.88
Cypress 0.55 11.85 52.02 33.91
I.. Charts Showing Relation of Several Expander Patents. The
materials covered in several of the expander patents based on wood
derivatives are so related that their essential features can be presented
in chart form. This has been done in Fig. 1, 2 and 3. These figures
make no attempt to give details of the preparations and for them the
patents must be studied. The charts are self-explanatory, and show
the inventor's name and patent number under the corresponding prep-
aration.
3. Expanders from Humic Substances

A. Introduction. Fertile soils contain humus, a peculiar type of
organic matter, in addition to the mineral components. The humus has
its origin in the microbial degradation of plant tissues under conditions
ADDITION A G E N T S FOR N E G A T I V E B A T T E R Y PLATES 247
of both aerobic and anaerobic attack. These materials play a very

important role as soil colloids and also as buffers for preventing sudden
and large changes of pH in the soil. Obviously an infinite variety of
products and intermediate stages are possible when the large variety
of starting materials and conditions which would obtain in various
places are considered.
The exact nature of humus and the preparations and compounds
that can be made from it has been the subject of much study and
controversy. From humus the following type compounds have been
isolated: paraffine hydrocarbons, sterols, fats, waxes, esters, organic
acids, aldehydes, carbohydrates, lignins, organic nitrogenous compounds
as proteins, peptones, amines, and purine bases, and organic phospho-
rous compounds. Even with this array of identified compounds there
will remain on analysis 40% to 50% of the original carbon content
unaccounted for in insoluble and unidentified fractions. Humus repre-
sents the degradation products of the cellulose, lignin and other com-
ponents of the original plant. Since lignin is more resistant to the
humification processes than the cellulose or carbohydrates the humus
will bear a closer relation to lignin than to cellulose. Most of the
eventual degradation products of cellulose are either volatile or water
soluble and are removed. The composition of humus will, therefore,
change with its age and will vary with the source materials and the
conditions of humification.
The similarity of natural humus to the artificial humic materials
prepared in the laboratory has been recognized. However, these mate-
rials are not necessarily identical and their composition will vary with
the method of preparation. The whole situation on the nomenclature
has become so involved that Waksman has concluded24*:
"One may, therefore, feel justified in abandoning without reserva-
tion the whole nomenclature of 'humic acids,' beginning with the
'humins' and 'ulmins,' through the whole series of 'humus,' 'hymato-
melanic,' 'crenic,' 'apocrenic,' and numerous other acids, and ending
with the 'fulvic acid' and 'humal acids,' the last additions to the list.
These labels designate, not definite chemical compounds, but merely
certain preparations which have been obtained by specific procedures.
The only name warranting preservation is H U M U S , because of its
historical importance; it should be used to designate the organic matter
of the soil as a whole. 'Humus substances' or 'humic matter' can
be used to describe humus complexes as a whole; the general implica-
tion would thereby be made that they are comparable to plant, animal,
and microbial substances."
The battery expander patents based on humic matter owe whatever
validity they may have to the method of preparation described for the
materials claimed. Claims based on the definition of a preparation by
name, as for example, humic acid, or ulmic acid, are probably of little
value because of the chemical indefiniteness of the name. The strong
patents of this group will be the narrow ones which claim only the
product obtained by following a specified procedure and which make
little or no attempt to assign a name to it. The various preparations
do differ widely in properties and it is the system of nomenclature
which is the source of much confusion.
B. Classification. A classification which is primarily of historical

value rather than furnishing data for the identification of specific
chemical compounds is as follows:
Soluble in alkali
Not precipitated by acid.
Crenic acid.
(Also called apocrenic and fulvic acid.)
Precipitated by acid.
Product of anaerobic microbial attack.
Humic acid (black bodies).
Product of aerobic microbial attack.
Ulmic acid (brown bodies.)
Soluble in alcohol.
Hymatomelanic acid.
Insoluble in alkali.
Humins.
C. Preparation and Use. Artificial humic substances can be pre-
pared by the oxidation of phenols and their homologs and the degrada-
tion of carbohydrates, lignin, or lignocellulose. Humic materials also
may be extracted from plant or woody substances that have undergone
attack by micro-organisms such as composts or artificial manures, tan-
bark, peat, soils, and lignite coal. The controlled pyrolysis of carbo-
hydrates such as starch or sugar to give a caramelized product will
also produce materials closely resembling certain humic materials.
The first users of humic materials as addition agents in negative
plates were probably Pescetto in 1898, 37 Schanschieff in 1899,35 and
Butler and May in 1902. 51 Pescetto reacted sugar with strong sulfuric
acid and called the product ulmate of ulmin. Bijur in 19086o found
that the efficiency of Plantfi negatives could be improved by dipping
them in a sugar solution, drying, and then baking at a sufficiently high
temperature to "carbonize" the sugar. Many of the other early patents
discuss the preparation and use of carbon under such conditions that
their actual product was almost certainly a humic material rather than
actually elemental carbon.
The use of plant materials containing lignin or carbohydrates of
any kind in a storage battery where the primary effect of the sulfuric
acid is accentuated by alternate oxidizing and reducing conditions,
gives rise to the formation of materials identical with or closely related
to the natural humic materials. The use of materials such as sugar,
starch, humie materials, carbohydrates, phenols, tannin, wood, cork,
straw, barks, seaweeds, grasses, etc., were all disclosed in patents
before 1900. Although it is true that many of these early patents
describe these materials as binders or porosity producing agents, the
explanation in the patents is not too important for our present con-
sideration, since the simple mentioning of these materials as having
value when used in small amounts in the active material is of itself
important.
The effect of plant decomposition products was recognized by Leon
Gagnaux in 1909 and published in 1928. The original article was not
available but the abstract in Chemical Abstracts is of sufficient impor-
ADDITION A G E N T S FOR N E G A T I V E B A T T E R Y PLATES 249
tance to warrant copying in full. TM "Process for maintaining or restor-

ing the activity of negative plates in lead storage batteries." "Treatment
of organic substances such as resins, starches, oils, fats, hydrocarbons,
etc., with hot concentrated H2SO4 yields products which, when added
to the electrolyte in storage batteries (about 2 to 4 g./L), maintains,
increases or restores the activity of the negative plates. The method
of treatment may vary with the nature of the substance, e.g., phenol
need only be heated to about 75* C to form phenolsulfonic acid which
is much more efficient for the purpose than phenol, while resins must
be heated above 100" C. The activity can be repeatedly restored by
repeated additions. The latter have no harmful effect on the positive
plates, but on the contrary retard their disintegration. The unsul-
fonated material can be incorporated into the plates in the course of
manufacture, either alone or in conjunction with the inert fillers gen-
erally used, and they are then sulfonated during the charging of the
battery. Negative plates prepared by the Plant~ process can be treated
either by reducing in an electrolyte containing a certain amount of the
sulfonated products, or by immersing after reduction in a concentrated
solution of the unsulfonated product, drying, and then immersing in
H2SO, at a high enough temperature to carbonize and sulfonate the
substance."
Fig. 4 shows diagrammatically the relation between the various ex-
pander patents based on humic matter. The three corners of the
triangle represent preparations separated by their different solubilities.
Opposite the three sides of the triangle are the three methods of pre-
paring or isolating humic substances. Connecting the portions of the
diagram are lines on which are given the name of the inventor and
rULVIC ACID
SOLUBLE IN ALKALIS AND
ACID$
REJNHARDT RE~
HARNERAND CARNEy
SCMAgFFER AND ~ _ 7
HARNER REINHAROT
u S 2J3oJo5 u $ 2.030,7~S
u . s P~I~oJc~ u S 2.o30.7}7
.~OLU(~.E IN ALKALI , ~ ULMIC A C I O PESCETTO U S. 6 1 4 ~ 1 | IN'~OLUBL~[ tN ALKALI

!
.E ........IN ALCOHOL
SOLUBLE B..... 11sPRECIPITATED
o.-, .........
BY ACIDI ~CHANSCHIEFF U,.~ 619.622
SCHANSCHIr-rF U S 621,150
flR'INHARDT I U ~ ~8~7,846
ROWLET U..S,1~79,63B
ROWLEY U S |079839
LIGNOCELLULOS[ ,~ ETC, BY
I...............- I
CHEMICAL AN0 MICR0~AL
ATTACK. .....
Fz~. 4. The relations of the expander patents based on humic matter.
250 EVERETT J. RITCItIE
the corresponding patent numbers. The triangle itself represents un-

differentiated humus or humlc matter.
4. Expanders from Destructive Distillation of Wood and Coal

Although of no great practical importance, it is rather interesting
that many of the classes of compounds produced by the destructive
distillation of wood and coal have been patented for use as battery
addition agents.
V. PRACTICAL USE OF EXPANDERS
At the present time the negative plate compositions in common use

for S.L.I. negatives will contain: Barium sulfate, usually as blanc fixe,
0.3% to 3.0%. Lampblack, a grade that is relatively oil free and is
readily wetted by water or dilute sulfuric acid, 0.05% to 0.30%.
Organic expander, usually a modified wood or plant product, 0.05%
to 1.0%. Lead oxides, or other leady materials, form the remainder.
In this range of compositions the solids of many formulations will fall
close to the following: blanc fixe, 0.50% ; lampblack, 0.20% ; organic
0.30%; leady materials, 99.00%.
The use of lampblack appears to be of value in the clearing of the
negative plate on formation. It may give the active material the neces-
sary electric conductivity during the early part of formation in which
its permeability to acid is at a minimum. Towards the end of forma-
tion the lampblack appears to help in the removal of the gray surface
film occasionally encountered. Lampblack is also used in some battery
manufacturing plants largely to help prevent mistaking unformed
negative plates for positives. This is especially true when using some
leady oxides or when the positive formulation has little or no red lead.
The use of organic materials with barium sulfate has proven to be
especially advantageous since the barium sulfate seems to stabilize the
good effect of the organic addition agent over a longer period of useful
life than if the barium sulfate were absent.
VI. SUMMARY
From the foregoing discussion the action of expanders may be sum-

marized as follows: Their primary function is to prevent the growth
of the original lead particles during charge. This is evidently accom-
plished by an adsorption or plating out of the agent on the lead particle
during charge which prevents lead sulfate from precipitating on the
lead particle during discharge. This causes a reduction in raze of the
original particles when the plate is subjected to alternate charge and
discharge.
The role of the barium sulfate is to provide numerous nuclei for
the formation of lead sulfate crystals away from the lead particles.
This reduces the degree of supersaturation of the lead sulfate solution
in contact with the lead particles.
A possible secondary function of the expander is to provide protec-
tion from undesirable side reactions such as that due to oxygen or
oxidizing compounds in the electrolyte.
Through the use of expanders the polarization of the negative elec-

trode is kept at a lower value at all current densities over a wide range
of temperatures than if no expander is used. This reduction in polari-
zation voltage greatly increases the available energy at high current
densities and at low temperatures.
With respect to the preparation of active expander materials these
facts appear to be outstanding. Most plant and many animal sub-
stances have been used with marked success with slight differences in
degree rather than kind of improvement. When subjected to chemical
attack these materials split or degrade into a number of fractions to
which names have been given but which are not always chemical
entities of definite structure and composition. If the chemical attack
is severe, many of the fractions are converted to soluble or gaseous
components, and residues which on further treatment yield substances
of the humus type.
Apparently it makes little difference to the battery whether the
chemical degradation of the original plant substance occurs entirely or
only partially outside of the battery plate. The essential performance
difference will be the number of cycles necessary for the raw plant
material to produce the necessary amount of active agent in the plate.
The effectiveness of finely ground wood, straw, cereal hulls, and
barks is well known, likewise the residue from treatment of these
materials with alkali (cellulose) with acid (lignin) or from microbial
attack (humic type substances). It is recognized that the reaction of
the raw plant materials with heat, with hot strong sulfuric acid, or
with the acid electrolyte of the functioning battery produces dark
colored degradation products of the humic substance type. These dark
colored degradation products of plant substances, the oxidation prod-
ucts of aromatic hydroxy compounds, and the materials extracted from
natural humus substances as lignite, peat and composts all have a very
similar beneficial effect on the negative plate. It is relatively unimpor-
tant from a performance point of view whether the dark colored
degradation products are added to the plate as such or are formed
in situ from raw or partially modified plant substances.
VII. HISTORICAL AND ACKNOWLEDGMENTS
The author's interest in the subject of negative plate addition agents

began while a graduate student at Indiana University under Professor
O. W. Brown during 1932 to 1934. This interest developed into a
systematic testing program of pure organic compounds carried out in
the Research Laboratories of the Eagle-Picher Lead Company at
Joplin, Missouri, during 1935 to 1938. The program resulted in the
selection of one pure organic compound for use as an expander, which
has been in commercial use for about eight years for specific purposes.
Because of the prior art situation, no patents were issued on this
development.
The author wishes to express his appreciation to the Eagle-Picher
Company for permission to publish this work. To his co-workers and
the Research Management for their helpful suggestions and criticisms
the author is grateful.
252 EVERETT J. R I T C H I E
BIBLIOGRAPHY
List of Patents
U. S. Patents U. S. Patents
1. 267,275 E. T. Starr 78. 1,085,707 E. W. Smith
2. 268,308 E. T. & E. E. Starr 79. 1,105,499 R. Drambourg
3. 282,414 Chas. J. VanDepoele 80. 1,133,641 E. Hancock & D. David
4. 290,941 E. T. Starr & W. J. Peyton 81. 1,164,464 C. C. Carpenter
5. 292,469 W. E. Case 82. 1,182,513 H. G. C. Thofehrn
6. 295,456 E. T. Starr & W. Peyton 83. 1,217,738 J . H . Flannery
7. 327,341 E. T. & E. E. Starr 84. 1,284,426 W. Morrison
8. 336,101 E. M. Gardner 85. 1,291,167 E. J. Rueb
9. 344,957 S. Farbaky & S. Schenek 86. 1,306,214 R. J. Crowley
10. 357,642 W. H. Tasker & T. J. Jones 87. 1,317,082 M. Hartenheim
11. 372,468 Carl Hering 88 1,342,953 W. Gardiner & W. H. Duggan
12. 398,194 I. A. Timmis 89. 1,374,076 W. H. Grimditeh
13. 422,308 F. M. Lyte 90. 1,379,900 R. W. Chamberlain
14. 427,785 J,. F. McLaughlin 91. 1,405,702 W. H. Wood
15. 429,272 Carl Hering 92. 1,405,703 W. H. Wood
16. 434,458 D. Pepper, Jr. 93. 1,416,195 E. Hacking
17. 466,138 H. G. Morris & P. G. Salom 94. 1,416,761 G. Steerup
18. 480,575 G. Gaudini 95. 1,427,970 G. W, Plels, Sr. & Jr.
19. 493,817 L. Bristol 96. 1,432,508 T. A. WiUard
20. 496,517 R. T. E. Hensel 97. 1,432,845 H. L. Edney
21. 512,823 A. Hough 98. 1,432,937 W. H. Wood
22. 517,427 W. A. Boese 99. 1,433,136 F. M. Holmes
23. 524,710 D. G. Fitz-Gerald 100. 1,481,947 W. H. Wood
24. 535,541 A. Hough 101. 1,505,990 T. A. Willard
25. 538,628 Win. L. Silvey 102. 1,508,427 H. G. Wagner
26. 554,280 S. Hammaeher 103. 1,508,732 F. C. Thornley et al.
27. 556,782 M. Sussmann 104. 1,516,373 L. deM. Cattley
28. 565,140 Geo. H~ber 105. 1,536,064 R. C. Benner & J. H. Fink
29. 566,231 W. Schiller & A. Heinemann 106. 1,555,438 J'. Sato
30. 566,531 W. Petsehel 107. 1,559,471 A. Strasser
31. 578,870 S. Hammacher 108. 1,570,115 W. H. Wood
32. 578,887 R. Linde 109. 1,572,586 H. G. Wier
33. 586,627 S. A. Rosenthal 110. 1,585,034 Geo. A. Howland
34. 588,905 S. Hammacher 111. 1,585,035 Geo. A. Howland
35. 589,842 H. Leitner 112. 1,590,605 E. Taylor
36. 608,614 C. Marsehner 113. 1,603,291 D. Pepper
37. 614,339 F. Peseetto 114. 1,607,920 J. Sato
38. 619,622 Alex. Sehansehieff 115. 1,649,280 R. C. Benner & L. C. Werking
39. 621,150 Alex. Sehanschieff 116. 1,654,779 R. C. Benner & J. H. Fink
40. 623,195 A. Werner 117. 1,667,435 R. R. Openheim
41. 625,287 C. Brault 118. 1,668,801 J. H. Calbeek & J'. A.
42. 636,938 Ed. Blaines Sehaeffer
43. 660,228 E. A. Sperry 119. 1,687,307 R. Oppenheim
44. 664,023 P. Marino 120. 1,688,399 W. L. Reinhardt
45. 668,356 P. E. Placer 121. 1,718,139 W. H. Grimditch
46. 681,329 B. Kilettner 122. 1,788,571 W. Gardiner & H. D. Staley
47. 686,679 L. Paget 123. 1,817,846 W. L. Reinhardt
48. 703,875 W. E. Winship 124. 1,826,724 R. N. Chamberlain & F. Booss
49. 706,444 C. T. J. Oppermann 125. 1,859,581 J'. H. Calbeek
50. 713,020 E. A. Sperry 126. 1,879,638 W. H. Rowley
51. 715,016 H. W. Butler & J'. H. May 127. 1,879,639 W. H. Rowley
52. 717,107 W. Morrlson 128. 1,906,784 ~. Caden
53. 723,327 E. A. Sperry 129. 1,929,357 J. O. Johnstone
54. 723,328 E. A. Sperry 130. 1,940,714 E. A. Giard
55. 724,619 A. Sehmidt-Predari 131. 1,944,065 R. N. Chamberlain
56. 733,918 S. A. Rosenthal 132. 1,944,066 R. N. Chamberlain
57. 740,034 J. T. Niblett 133. 1,963,468 G. Krgnzlein et al.
58. 778,894 C. ]. Reed 134. 1,975,544 H. R. Harner&T. W. Carney
59. 815,628 E. L. Opp.ermann 135. 2,022,482 Alex. Stewart
60. 845,391 Joseph Bijur 136. 2,030,716 W. L. Reinhardt
61. 854,940 H. Fredet 137. 2,030,717 W. L. Reinbardt
62. 875,213 H. Rodman & G. Howard 138. 2,035,315 H. R. Harner & M. F. Chubb
63. 896,981 L. Fiedler 139. 2,079,207 H. Hibbert & W. L.
64. 900,898 NL C. Thiellet & M. ]. Denard Relnhardt
65. 905,599 Ed Sokal 140. 2,079,208 H. Hibbert & W. L.
66. 911,141 Q. Marino & E. W. Barton- Reinhardt
Wright 141. 2,100,914 J. A. Orsino
67. 916,576 W. Morrison 142 2,101,326 ~C" L. Woodbridge
68. 917,787 W. Morrison 143. 2,107,937 . A. Hall
59. 935,316 W. Morrlson 144, 2,130,103 J. A. Sehaeffer & H. R.
70. 938,312 W. Gardiner Harrter
71. 944,822 H. Rodman 145. 2,130,I04 J'. A. Sehaeffer & H. R.
;'2. 994,451 J. E. Frederiekson Harner
73. 995,162 A. E. Lawerenee 146. 2,130,105 J. A. Sehaeffer & H. R.
74. 997,984 B. Ford Harner
75. 1 004,793 V. deKaravodlne 147. 2,178,680 R. A. Daily
76. 1,023,861 P. Marino 148. 2,182,479 J. O. Johnstone
77. 1,051,261 A. Ricks 149. 2,191,231 A. P. Hauel
ADDITION A G E N T S FOR N E G A T I V E BATTERY P L A T E S 253
U. S. Patents British Patents
150. 2,217,786 H. B. Birt & Win. C. 188. 155,944 T. A. Willard, 1/6/21
Pritchard 189. 196,127 H. G. Wagner, 2/6/22
151. 1,217,787 It. B. Birt, W. C. Pritchard 190. 208,744 F. C. Thornley et al., 7/26/22
& R. A. Daily I9I. 210,777 A. Tribelhorn, 10/9/24
152. 2,217,814 W. C. Pritchard & R. A. 192. 235,530 Soc. Anon. Le. Carbone,
Daily
153. 2,233,281 O. W. Brown & J. H. 6/14/24
Patterson 193. 250,985 G. Fromont
154. 2,246,222 C. A. Rodgers 194. 267,205 H. Leitner, 12/7/25
155. 2,251,399 R. M. Cole 195. 272,550 W. J. Plews, 6/12/26
156. 2,253,247 J. A. Orsino 196. 275,392 W. Haddon & J. M. Burnett,
157. 2,290,496 B. H. Schubert 7/7/26
158. 2,325,542 W. C. Pritchard & R. A. 197. 280,197 M. Kugel, 11/6/26
Daily 198. 312,851 B. Heap, 7/2,6/28
159. 2,326,689 B. H. Schubert 199. 324,163 I. G. Farbenind, 11/20/28
160. 2,326,690 B. H. Schubert 200. 334,711 C. F. Judd et al., 9/9/29
161. 2,365,600 A. W. Schorger 201. 343,048 A. G. Owens, 10/9/29
162. 2,365,604 A. Stewart & E. Willihnganz
163. 2,367,453 H. D. Wilson 202. 312,851 B. Heap, 7/26/28.
1,64. 2,389,832 F. J. Williams & J. A. Orsino 203. 467,696 Owens-Illinois, 6/22/37
Canadian Patents
Belgian Patent 204. 213,717 W. Gardiner & W. H. Duggan,
165. 374,748 C. F. Judd et al., 12/31/30 10/11/21
British Patents 205. 219,532
T. A. Willard, 6/13/22
I66. 5,521 Grant & Jones, 1881 206. 226,227
W. H. Wood, 11/21/22
167. 12,824 R. Tamine, 9/26/84 207. 241,186
C. J. Johnson, 7/1/24
1,68. 7,733 Chadlera & Thorman, 1885 208. 241,734
E. Hacking, 7/22/24
169. 13,092 W. R. Lake, 11/11/87 French Patents
170. 2,368 M. Bailey & I. Warner, 2/16/88 209. 633,006 P. Pettinelli, 4/20/27
171. 9,854 L. Bristol, 7/6/88 210. 634,479 Silica Gel. Corp., 5./16/27
172. 11,004 C. Rousseau, 6/27/91 211. 637,152 C. J. V. Fery, 10/30/26
173. 11,532 W. A. Boese, 6/20/92 212. 642,038 D. DeGiovannini, 10/6/27
I74. 20,596 S. Hammacher, 4/13/94 213. 679,772 E. Gay, 12/17/28
175. 4,610 W. A. Boese, 6/15/95 214. 683,750 I. G. Farbenind A.G.,
176 9,937 S. Hammacher, 9/21/95 10/22/29
177. 18,430 F. Pescetto, 11/6/97 215. 690,409 K. Nauman, 2/21/30
178. 5,826 Alex. Schansehieff, 1/5/98 21.6. 737,947 L. Garnot, 9/25/31
179. 13,826 L. Tobiansky, 9/16/99
180. 6,786 F. J. Gerad, 3/29/66 German Patents
181. 23,413 H. Leitner, 10/22/06 217. 199,590 A. Ricks, 7/6/06
182. 27,215 Q. Marino & E. W. Barton- 218. 202,836 Akkumulatorenfabrik, |/29~/08
Wright, 11/29/06 219. 488,454 I. G. Farbenind A.-G.,
183. 8,284 M. C. Thiellet & M. J. Denard, lO/27/28
4/9/07
184. 27,976 H. deLamlnere, 7/28/10 Japanese Patents
185. 2,269 H. F. Joel, 10/25/12 220. 35,232 Y. Nakazawa, 10]29/19
186. 4,843 A. Ricks, 2/27/12 221. 35,162 Y. Nakazawa et aL, 10/I6/19
187. 15,327 Des Litzneris (nee Tailhardier 222. 42,362 G. Shimazu, 4/20/22
du Plaix), 7/3/13 223. 92,865 S. Kubota, 9/19/31
Literature References
224. W. D.Bancroft, Trans. Electrochm, Soc. 71, 195 (1937).
225. J. Barborovsky, Trans. Electrochem. Soc. 75, 283 (1939).
226. C. S~ Barrett, lnd. Eng. Chem. 25, 297 (1933).
227. R. L. Bateman and F. C. Mathers, Trans. Electrochem Soc. 64, 283 ('1933); G. Fuseya
and M. Nagano, Trans. Electrochem. Soc. 50, 235 (1926), 52, 249 (1927); F. C.
Mathers and R. B. Forney, Trans. Electrochem. Soc. 76, 371 (1939); R. Taft,
Trans. Electrochem. Soe. 63, 75 (1933).
228. W. Blum, A. O. Beckman and W. R. Meyer, Trans. Electrochem. Soc. 80, 253 (1941).
229. O. W. Brown and E. H. Kooten, Trans. Electrochem. Soc. 77, 329, (1940); O. W.
Brown, R. L. Shelley and E. W. Kanning, Trans. Electrochem. So=. 64, 355 (1933);
C. C. Carpenter, U. S. Pat. 1,416,787; M. F. Chubb and H. R. Harner, "Storage
Battery Paste Preparation and Control," a bulletin from the Eagle-Picher Research
Laboratories, Joplin, Mo.; L. H. Flanders, U. S. Pat. 1,228,546 and 1,228,547;
Win. Silvey, U. S. Pat. 538,628; Chas. Sorley, U. S. Pat. 423,091.
230. J. T. Burt-Gerrans and H. R. Hugill, Trans. Royal Soc. of Canada, Section I I I (3),
19, 26 (1925); E. Willihnganz, National Battery Manufacturers Association Minutes
(October, 1942).
231. M . F . Chubb and H. R. Harner, Trans. Electrochem. Soc. 68, 251 (1935); G. W. Vinal
and C. L. Snder, Trans. Electrochem. Soe. 53, 233 (1928).
232. G. L. Clark and R. Rowan, J. Am. Chem. Soc. 63, 1299 (1941).
233. 233. Chas. J. V. Fery, U. S. Pat. 1,371,746; Brit. Pat. 275,750; 395,276.
234. Leon Gagnaux, Bull. Soc. Ind. Mulhouse, 94, 192-4 (1928), also Chemical Abstracts, $2,
3845 (1928)
235. A. P. Hauel, Trans. Electrochem. Soc. 78, 271 (1940).
236. A. P. Hauel, Trans. Electrochem. Soe. D, 79, 268 (1941).
237. K. Hess and J. Gundermann, Ber. 70B, 527 (1927).
238. O. W. Hisey, "Wood Chemistry," Edited by L. E. Wise and published by Reinhold
Publishing Corporation, Chapter 22 pp. 71.6-733 (1944)
239. Ed. C. Jahn, "Wood Chemistry," Chapter 8, pp. 191-200.
254 EVERETT J . R ] T C H I E
Literature References
240. A. G. Norman, "Wood Chemistry," Chapter 9, pp. 252-271.
241. Max Phillips, "Wood Chemistry," Chapter 10, p. 295.
242. Max Phillips, "Wood Chemistry," Chapter 10, p. 334.
243. A. J'. Stamm, "Wood Chemistry," Chapter 7, p. 153.
244. S. A. Waksman, "Humus," published by The Williams and Wilkins Co., p. 62 (1936L
245. E. Willihnganz, Trans. Electrochem. Soc. 79, 243 (1941).
246. E. Willihnganz, National Battery Manufacturers Association Minutes (May, 1940).
247. L. E. Wise, Trans. Electrochem. Soc. 73, 79 (1938); "Wood Chemistry," Chapter 6,
pp. 137-152.
248. L. E. Wise, "Wood Chemistry," p. 752.
NOTE: The discussion of the chemistry of wood derivatives and humus has been based on
the detailed treatment to be found in "Wood Chemistry" edited by L. E. Wise, and
"Humus," written by S. A. Waksman and to which specific references have been made.
APPENDIX
Addition Agent Listing

The following list of materials and compounds was compiled from the patents
of the bibliography and the numbers following the name o f the agent refer to
the patents listed therein. The attempt was made to list most of the patents
that refer to an agent as well as those patents claiming that agent as their own
invention. In some cases the reference patent may point out the deleterious
effects produced by the use of a particular agent and many of the items listed
are very injurious. Most patents discuss the prior art to a greater or less extent
and the mention of the use of certain agents as a part of the prior art is
frequently of considerable importance.
The listing is believed to be fairly complete, at least as far as U. S. patents
are concerned, It is probable that additional agents would have been found by a
thorough study of the foreign patents. The abstracts of the Journal of the
Chemical Society, and the Chemical Abstracts were checked. The list should
prove useful as an index of the patent references on the listed agents.
Acetic acid--38, 68, 128, 178 Aprocrinic acid--137

Acetone--68 Apocunic acid--123
Acrolein--35 Aryloxy lignin--139
Acrylic acid--35 Asbestos--19, 33, 64, 106, 114, 185, 193
Agar agar--223 Asobotoxin--32
Albumen--77 Athamantin--32
Alcohol, Ethyl--122, 116 Axiol--32
Alcohol, Methyl--116 Bagasse--157, 160, 161, 162
Alcohol lignin--139 Baphiin--32
Alginic acid--103, 153, 190 Barium acetate--221
Alizarin--54 Barium carbonate--221
Alkali lignin--140 Barium humate--136, 137
Alkali thiosulfate--55 Barium lignosulfonate--151
Alkoxy lignin--139 Barium peroxide--220
A l o i n - - 3 2 , 153 Barium persulfate--81
Alumina gel--119 Barium saccharinate--221
Aluminum sulfate---85, 86, 97, 131 Barium sulfate--62, 67, 71, 81, 115, 129, 133,
Amber--36, 153 136, 137, 149, 153, 193, 198, 218
Ammonia--41, 75 Bark--153, 162, 179
Ammonium alginate--103 Beeswax--4, 153
Ammonium carbonate--10 Benzoic acid--215
Ammonium chloride--9, 110 Beta naphthol--153
Ammonium chromate--10 Betulin--32
Ammonium hydrosulfide--61, 153 Bismuth oxide--122
Ammonium hydroxide--53, 110 Bitumen--49
Ammonium hymatomelanate--144 Black sulfite liquor, ammoniated--163
Ammonium persulfate--222 Black sulfite liquor, dehydrated--135, 156
Ammonium phosphate--10, 43, 50 Bone ash--79
Ammonium sulfate--12, 21, 24, 33, 50, 53, Bone meal--M, 99
54, 68, 75, 88, 89, 95, 102, 105 Botuline acid--32
Anemonin--32 Brazilin-Brazilone--I 55
Anthracene--173, 175 Brazil wood--155
Anthracene, disulfonic aeld--22 Brom nltrotoluene--28
Anthracene, monosulfonic acid--22 Butyric acid *
Anthraquinone, disulfonic acid--22 Butyric acid esters--34
Anthraquinone, monosulfonic acid--22 Cadmium sul fate--40
Anthrol--175 Calcium acetatc--116
Antimony--131 Calcium humate--136, 137
Antimony oxide--25, 174 Calcium hydroxide--55
Antimony sulfate--131 Calcium nitrate--41
Antimony sulfide--131 Calcium phosphate--41, 147
Apoerenic acid (Aprocrenic)--13G 162 Calcium sulfate--I, 14~ 41, 62, 702, 131, 153

Camphor--45 Hydrate cellulose--129
Cantharidin--32 Hydrocellulose--129
Carbon--5, 8, 14, 16, 18, 35, 38, 39, 106, 153 Hydrofluoric acid--52
Carbon dioxide--23 Hydrogen peroxide--84
Cardol--32 Hydroquinone- - t23, 153
Caro's acid--222 Hydroquinone-diisobut ylene condensation
Carotin (Carotene)--32 product-- 153
Caryophylin (Carophyllin)--32 Hymatometanic acid--144, 162
Caspaicin--32 Ilixanthin--.32
Castor oil, oxidized--66, 182 Infusorial emth--10, 57, 88, 94, 99, 204
Catechol--123 Iron dust--ll0
Celiuloid--207 Iron oxide--154
Cellulose--28, 65t 98, 112, 123, 153 lvain--32
Cellulose, mercerized--129 Jute--101, 139, 157, 160
Cellulose, soluble--120 Kaolin--218
Charcoal--39, 42, 51, 79, 117, 178, 192, 209, Keratin--19, 92
211, 212 Kieselguhr--see Infusorial earth
China clay--65 Lactic acid *
Chrysophanin--32 Lactucin--32
Citric acid--178, 215 Lampblack--70, 78, 95, 106, 114, 115, 122,
Coa1--123 136, 137, 2t8
Coal, brown--101, 123, 136, 137 Laserpitin--32
Cobaltous sulfate--124, 131, 132 Lead acetate--15, 16, 63
Coconut hulls--162, 212 Lead alginate--103
Coke--2, 18, 25, 70. 153, 178 Lead chloride--13, 20
Collodoin--97 Lead dust--65, 76, 78
Columbin--32 Lead hymatomelanate--144
Copper sulfate--110 Lead lignosulfonate--150
Cork--153, 179 Lead nitratc--ll, 13
Corn cobs--139, 140, 157, 160. 161, 162 Lead oxalate--I 6
Cornin--32 Lead peroxide, reclaimed--154
Corn stalks--144, 145, 146, 161, 162 Lead phenylate, basic--26, 31, 176
Cotoin--32 Lead phosphate--197
Cotton--2, 7, 98, 170 Lead sulfate, normal--56, 75, 104, 109, 125
Cowhide, oak tanned--141 Lead sulfate, basic--ll8, 146, 148
Crenic acid--123, 136, 137, 162 Lead sulfide--17
Cresol--123, 175 Leather--141
Creosote--174, 176 Leaves--144, 145, 146, 162
Cubelin--32 Lecithin--180
Cuprene--191 Lignin--101, 123, 135, I53, 156, 161, 162, 163
Date stones--212 Lignin, alcohol--139
Degummed wood--98 Lignin, alkali--140
Dextrin--223 Lignin, snlfonie acid--135, 158, 163
Dinitro benzene--28 Lignin sulfonie acid, pure--150, 152, 158
DiDhthalie acid--174 Lignite--101, 123, 137, 163
Eloexantine--32 Lignocellulose--123, 161, 162
Ethylene glycol--133. 199, 214, 219 Lignone--212
Feathers-~-19, 92, 153 lAgno-protein complex--144
Fe]ters waste--100 IAgustron--32
Folters wool--100 Limonin--32
Filter paper--98 Linseed oil--35
Flax--101 I,ogwood extract--155
Flour--166 Lutidin--34
Formaldehyde--69 Maclurin-Morin--155
Formic acid--39, 69, 178 Magnesium nitrate--41
Fossil gums--36, 153 Magnesium oxide--8, 45, 79, 105
Fuller's earth--99 Magnesium phosphate--41
Furfural--38, 153 Mae-nesium sulfate--21, 23, 24, 41, 108, 131.
Gantisin--32 193, 194
Gardenin--32 Maleie-acid hydroquinone condensation
Gelatine--20, 64, 183, 223 product--153
Glass wool--77, 143, 203 Manganese oxides--3, 29, 67, 174
Glucose--117, 194 Mangostin--32
Glue--20, 120 Mercerized cellulose--129
Glycerine--29, 35, 45, 48, 69, 76, 79, 85, 97, Mercury--6, 88
122, 187. 194, 213 Mercury bisulfide--70
Grains--179 Mercury bisu]fite--207
Graphite--44, 73, 74, 79, 136, 137, 153, 218 Mercuric sulfate--217
Grasses--153, 179 Mercurous nitrate--142
Gum arabic--40 Meta~allic acid--169
Gum tragacanth--181 Metallic lignosulfonates--150, 151
Guncotton--44 Molasses--35, 194
Hair--19, 59, 91, 92. 100, 153, 171, 172, 206 Molybdenum trioxide--70
Hematine-Hematoxylin--155 Molybendum sulfide--70
Hemieelluloses--134, 144 Muck--123
Heml>---101, 126, 127, 139, 153, 157, 160 Nails (of mammals)--92
Hoofs--92 Naphthalene--45, 174, 175, 176
Horrt--92 Naphthalene sulfonic acid--174
Hulls, cereal--162 NaphthoI--175
Humie acid--123, 134. 136, 137. 156. 161,162 Newsprint--161
Humlc substance--123, 126, 127, 162, 163 Nickel liznosul fonate--147
Humin--38, 123, 134 Nickel silicate--164
H~mUS--157, 159~ 160 Nickelous sulfate--131
256 EVERETT J. R I T C H I E

Nitrobenzene, mono---28 Seoparin--32
Nitro cellulose--193 Scrophularin--32
Nitro cellulose, mono--28 Seaweed~153, 168, 179
Oil of birch* Seawrack--168
Oil of resinous trees* Seeds--153, 179
Old fustic--155 Seignette salt--184
Olive husks--212 Shellac--4, 153
Olivin--32 Silica flour--99', 136, 137, I53
Organic ligneous compounds--157, 159, 160 Silica gel--119, 195, 210
Osage--155 Slag wool--33
Oxalic acid 84 Smilacin--32
Oxycellulose---126, 127 Snake oi1--111
Pachymose--32 Sodium--107
Paper--98 Sodium alginate--103
Paper pulp--90 Sodium bicarbonate--97
Paraffin--93, 119, 175 Sodium bisulfate--105
Peat (Peat moss)--123, 137, 157, 159, 160, Sodium borophosphate--138
162, 163 Sodium carbonate--72
Persulfuric acid--222 Sodium ehlorate--111
Phenol--26, 31, 63, 77, 123, 174, 175, I76, 186 Sodium chloride--8, I0, 58, 111
Phenol lignin--139 Sodium chromate--10
Phenol sulfonic acids--174 Sodium hydroxide--23
Phloroglucinol--123 Sodium hymatomelanate--144
Phosphoric acid--215 Sodium nitrate--41
Phthallic acid--176 Sodium phosphate--41
Phthalie acid-hydroquinone condensation Sodium plumbate--ll, 13
product--153 Sodium potassium tartrate--184
Phsyalin--32 Sodium silicate---20, 46, 64, 76
Picolin--34 Sodium sulfate--10, 41, 50, 105, 108, 193
Pikrolichenin--32 Sodium tartrate--184
Pikrotoxin (Picrotoxiu)--32 Sodium thiosulfate--55
Pitch--93 Starch--45, 76, 123, 166
Plaster of Paris--see calcium sulfate Straw--101, 144, 145, 146, 153, 157, 160, 161,
Potassium bioxalate--30
Potassium bichromate--64 1,62, 179
Potassium bisulfate--lOS Strontium humate--136 137
Potassium chloride--10 Strontium sulfate--62, 193
Potassium chromate--10 Sugar--38, 40, 58, 60, 121, 123, 169, 201
Potassium hydroxide--23 Sugar, sulfates--126, 127
Potassium nitrate--41 Sugar sulfonates--126, 127
Potassium persulfate--222 Sulfur---4, 79, 153, 165, 196, 200
Potassium phosphate--41, 43 Talc--95, 218
Potassium silicate--46, 76 Tan barl~-144, 145, 146, 153, 1'62
Potassium sulfate--lO, 41, 43, 46, 50, 105, Tannin--150, 175
193 Tar--28, 32, 194
Potassium tartrate--184 Tar, distillate residues--34, 173
Potatoes--80 104, 153 Tartaric acid--39, 178
Protein--77, 134 Tellurium sulfate--164
Protein, from microbial action--134 Terpentine--94
Pumice stone--9, 14, 27, 65 88, 106, 153 Tulucinin--32
Pyridine--34, 186 Ulmate of ulmin--37, 169, 177
Pyrocatechin--175 Ulmic acid~123, 134, 136, 137, 162, 169
Pyrogallic acid--175 Urea sulfate--56
Quasin--32 Uric acid--128
Quercitin-Ouereitone-- 155 Viscin--32
Q uercitron--155 Waste sulfite liquor--159, 160
Quinol--123 Water glass--20, 46, 7,6, 207
Radium-barium sulfate---82, 83, 87. 216 Wood, degummed 98
Rags, cotton--98 Wood, flour (and sawdust)--2, 90, 96, 98,
Resorcin---123 102, 135, 144, 145, 146, 153, 157, 160, 161,
Rosin--4, 167 162, 179, 188, 189, 193, 205
Rubber---27, 33, 117 Wood, alkali extract of--130
Salicylic a c i d - - I l l , 186 Wool, pulled--9'1
Santonin--32 Wool, sheeps--59, 91, 100, 153
Sawdust--see wood flour Zinc, dust--47
Scales, fish--92 Zinc sulfate--30, 58, 113
9L Lyndon, "Storage Battery Engineering," p. 185, McGraw-Hill Book Co. (1911).
R e s u m e n del artfculo: " A d i t a m e n t o s para Electrodos Negativos

de Acumuladores de Plomo."
Se ha preparado una bibliografla y lista completa de las sustancias,
denominadas ensanchadores, que se han afiadido a acumuladores para
mejorar el funcionamiento de los electrodos negativos. Las ventajas
que pueden acarrear incluyen aumento de capacidad el~ctrica a tem-
peraturas bajas y corrientes elevadas, mayor fuerza mac~inica, mejor
adherencia a la rejilla de plomo, conductibilidad el~ctrica m~ts elevada
de la masa activa, regulaciGn m~is f~icil de la desecaciGn de la masa,
limitaciGn del voltaje durante carga, y reducciGn de la corrosiGn de la
rejilla positiva. Se describe el empleo pr~ctico de los ensanchadores.

Addition Agents For Negative Plates

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Addition Agents For Negative Plates

Uploaded by

Copyright:

Available Formats

A paper presented at the Ninety-second Gen.

eral Meeting held at Boston, Mass., Octo-

ADDITION AGENTS FOR NEGATIVE PLATES OF

1. Purpose and Scope

in the apparent volume of the negative active material after cycling

3. Historical Background for the Use of Addition Agents

4. Type Failures Due to Active Material

II. ADDITION AGENTS AND THEIR USE

1. Methods of Using Addition Agents

2. Addition Agents Grouped by Function

(2) Porous particles such as wood dust and diatomaceous earth,

compounds that may be present ill the electrolyte. Agents such as

perature discharge shows that the capacity is limited (with plain

2. The Particulate Nature of the Sponge Lead

3. Lead Sulfate Crystallization Nuclei

4. Prevention of Undesirable Chemical Side Reactions

oxidation of the sponge lead of the negative active material by the

IV. EXPANDERS DERIVED FROM PLANTS AND PLANT PRODUCTS

to certain raw materials. Later workers have applied these names to

2. Expanders Derived From Wood

A. Lignin. The elementary composition of the lignin complex varies

B. Lignocellulose. This is a naturally occurring complex of uncer-

of the expanders from wood consists in treatment of the wood to

C. Lignosulfonic ~cid. In crude form this is the so-called "black

A 5 IN T R C A T E O 0~VT{ ALKALI CONTAIN5 RES~5,

DILUTE AND ~ HUMICSUBSTANCE

LICNOC[ L L U L O S C DILUTE ADD

5UL~IT[ PULP BISULPITE SULFONIC ACID AN0 A(~I01FICATtON

8IRT, ETAL, US 2.217.786 r~4 HYDROt.YSATE BARIUM,

Fzo. 2. Expanders prepared by the treatment of wood by acidic reagents.

F. Cellulose. "Alpha-cellulose, the more stable portion of cellulose,

~ 1 ALCOHOLS JT. DILUTE WITH' AJ~*-Ot'l(~ LIGNtN

HCI AS A EXCE.T~PHENOl. HISBERT, ~T At..

tMPORE e~NZCNE O~SCA~DEO

cerization of cotton fibers by treatment with alkalis is a reaction which

H. Hydrocellulose. The "hydrocelluloses" are heterogeneous, cold

I. Oxycellulose. When subjected to oxidizing agents, cellulose yields

3. Expanders from Humic Substances

of both aerobic and anaerobic attack. These materials play a very

B. Classification. A classification which is primarily of historical

tance to warrant copying in full. TM "Process for maintaining or restor-

.~OLU(~.E IN ALKALI , ~ ULMIC A C I O PESCETTO U S. 6 1 4 ~ 1 | IN'~OLUBL~[ tN ALKALI

Fz~. 4. The relations of the expander patents based on humic matter.

the corresponding patent numbers. The triangle itself represents un-

4. Expanders from Destructive Distillation of Wood and Coal

At the present time the negative plate compositions in common use

From the foregoing discussion the action of expanders may be sum-

Through the use of expanders the polarization of the negative elec-

VII. HISTORICAL AND ACKNOWLEDGMENTS

The author's interest in the subject of negative plate addition agents

Addition Agent Listing

Acetic acid--38, 68, 128, 178 Aprocrinic acid--137

Addition Agent Listing

Addition Agent Listing

9L Lyndon, "Storage Battery Engineering," p. 185, McGraw-Hill Book Co. (1911).

R e s u m e n del artfculo: " A d i t a m e n t o s para Electrodos Negativos

You might also like