CHAPTER -I

General Introduction

1*1 What is Reclaimed Rubber ?

The term “reclaimed" can be applied to any material

prepared out of an unusuable product of its kind, and the

former becoming in consequence, a usuable item. The adopted

term for such process of preparation has. been familiar as

“reclaiming". Reclaimed rubber is thus a usable product

obtained by treatment with any of the several reclaiming

processes of scrap rubber goods. Recovered this way the resul­

ting rubberlike product has otherwise been historically named

as "reconverted", "regenerated", "rejuvenated" or "renovated"

rubber*

1,2 Scraps for reclamation

The object of recovering rubber from used rubber goods

was thought originally to supplement the import of raw rubber.

Although such scrap rubber historically came from boots and

shoes, soles and heels, fire and airbrake hose, bicycle and

solid truck tyres, high grade mechanical goods and several

other items, the present source is mainly the dominion of tyres

Scraps have further been classified as uncured and cured items.

Compounds, partially mixed stocks and redundant or contaminated

 -* 2 |#

raw and synthetic lubber stock fall under the uncured class*
Cured scraps are the raw materials in the manufacture of today*s

reclaimed rubber*

1*3 Whole tyre, reclaim

The normal grades of reclaimed rubber are whole tyre

reclaim* peel (tread protion of a scrap tyre)* tube reclaim and

carcass so far a tyre is concerned; others are mechanical reclaim*

general purpose reclaim and low grade reclaim. The major part of

the reclaimed rubber used* particularly in tyres, is the whole

tyre reclaim that is.manufactured out of whole tyre stocks. Out

of the numerous types and grades of tyres ranging from very large
earth removing types to small scooter wheel tyres such stocks may
vary from new product scrap or reject tyres to well worn remoulded
tyres*. Except for special grades of tyre reclaim where certain

specific classes of tyres are used, stocks for general whole tyre

reclaim may comprise a blend of all types of tyres. But in order

to achieve uniformity in the finished product sorting of tyres

into general classes such as passenger* truck and bus* and

tractor is essential along with the maintanance of a reasonable

degree of uniformity of the styrene-butadiene rubber (SBR) content

of the. stocks. The latter is important from the viewpoint that

SBR, increasingly used in tyre components behaves quite differently

when heated.
 S 3 J-

1*4 Manufacture t Historic and Modern

Prior to proper reclamation the preparative steps include

separation of heads ("debeading"), separation of the tread (only
when it is thick) from the rest of the tyre ("splitting"), and
cutting the article into pieces first roughly and then finely
("grinding"). Removal of fibres is associated with a few processes
only that use fibre-free scraps. Other processes involve the
destruction of the fibres as the former step in the actual reclai­
ming operations. Destruction, removal and devulcanization respec­
tively of the fabric, free sulphur and the vulcanized rubber
compound, the three essential components of the vulcanized scrap
rubber, have been carried out as three separate and distinct
operations or more or less simultaneously. Historically several
agents have been used'*’ from time to time for such operations. In
removing the fabric (chiefly cotton in the earlier days) agents
used were lime water or alum or sulphuric acid (Hall, 1858) air
blast (Clapp, 1871) muriatic acid (Burghardt, Rowley and Salomoneon,
1878) fluoric acid (Mitchell, 1881), sulphuric acid (Hall, 18685
Mitchell, 1881, Bourn 1884), alkali, sal-ammoniac (McDermott) and
caustic soda (Marks), and boiling was the usual form of treatment
so far* Hse of zinc chloride in removing fabric (Cutler, 1913)
has also been noted. For removal of the free sulphur various
agents were used, Muriate of lime (Parkes, 1846), carbonated
alkali or lime (Christopher and Gidley, 1853), alkaline lye (Beer,
1855), muriatic acid (Heinzerling and Liepman), and caustic
soda all these were used essentially by boiling. In applying
 -* 4 i-

calcium sulphide (Mitchell, 1890) boiling method of treatment

followed at first was replaced by open steam under pressure*

Later on, eauBtie soda has also been used (Marks, 1899) Id
Jacketed digester* Devulcanization, although objected as per

implication of this term, involves chemical reactions caused

by 1iie application of heat and chemical agents on ground

material followed by intense mechanical working. Such agents

used to date include muriate of lime (Parkes, 1846), oil of

turpentine (1847), camphene (Gheever, 1864), coal tar or

naphtha (Penney, 1865), boiling water (Hall, 1858), superheated

steam (Hall, 1859), mixed petroleum (Henry, 1862j)steam under

pressure (Hall, 1858; Mitchell, 1889), calcium sulphide plus

petroleum (Mitchell, 1890) and caustic soda (Marks, 1899),

Most of the reclaiming agents (also called reclaiming

solvents and reclaiming oils) are composite byproducts usually

not well defined in their composition, They are oxygen acceptors

and carry olefinic or diolefinie type unsaturation. These

materials used in reclaiming processes act during the depolyme­

rization step (the step of heating). Swelling of the vulcanized

scrap is said to act as an aid in the process. Reclaiming

catalysts are also used in small amounts in the depolymerization

step. Out of the numerous materials combination of a few (‘’dope”)

of which are used in modern reclaiming processes, some chemical

groups have been found active in the reclaiming reaction,whereas

some only promote the breakdown of the polymer molecule, and
' 2
some preventing subsequent heat-hardening of the polymer »

Reclaiming oils have'been classified sometimes as devuleanislng

agents, softeners, tackifiers, extenders, solvents and/or

swelling agents. Ihe devuleanising agents generally used are

certain amines, aliphatic or aromatic mercaptane, aromatic di­

sulphides etc. Solvent types will probably be the aromatic type

naphthas, dipentene and related materials, whereas resinous oils,

paraffinic, naphthenic or aromatic oils may be collectively called

softeners.

Vulcanized polychioroprene and mixed vulcanizates contai­

ning it may be reclaimed in the presence of alkyl or arylamines,

ammonia, or ammonium salts3?4’5. Hydrolytic decomposition products

of cellulose have been reported to assist in plasticizing neoprene

6
vulcanizates . Activator along with softener has also been used
7
in reclaiming neoprene. Use of an accelerator (mereaptobenzothia-
zole), the decomposition of which into free radicals is said to

initiate the depolymerization, is indicated in the reclamation of

neoprene or nitrile rubber. Nitrile rubbers have also been

8
reclaimed in the presence of acrylic esters , pentachlorothio-
0
phenol Zn salt and thermomechanically by using a colophony
10
plasticizer and as activators Neozone and Renacit IV • Reclaiming
13 -
agents in presence, of a small amount of oxygen*^* were used in the

reclamation of butyl rubber. Under the influence of ionizing

radiation*1,3 at 50 mierorad, butyl rubber has been reclaimed. Only
 6

small amount of reclaiming additives was necessary in the produe-

3.3
tion of reclaim from resin-cured butyl rubber . Use of hydrogen
sulphide1^ is also noted in the reclamation of butyl rubber*

Recovery of polyurethane from scraps has been indicated. Re-

16
clamation of silicone elastomers by using a dimethyl dihalosilane

was also reported* There are evidences of reclamation xfxihflx or

17 IS
other elastic copolymers 9 , In synthetic rubber reclamation
19 20
use of antioxidants and plasticizers has also been noted*

Heating the vulcanizate of smoked natural rubber with

antioxidants2X (at 140-175°) causeB a more rapid devulcanization

(reversion) than without them* As a result use of these antioxi­

dants in the devulcanization led to a good quality reclaimed

rubber mix of low viscosity. Folyalky-lated benzene by-product

fractions (from isopropylbenzene manufacture) along with water
22
and a peptizer have been used in the regeneration of vulcanized

rubber from tyre rubber waste* Rubber was reclaimed by dissolving

or suspending old tyre rubber in an aromatic hydrocarbon by means of
23
ultrasonic energy * Peptizing agent like pentachlorothiophenol >Zn

salt has been used in the reclamation of natural rubber and styrene-
9
butadiene rubber (SBR) * Zinc pentachlorothiophenolate (Renacit VII)
24
has also been used for butadiene rubber reclamation. When this
material is used in SBR, the amount required %*as highest, whereas

the lowest amount is needed in natural rubber reclamation. Benzyl-

pC
isothiouronium chloride is used as an activator with alkalis in
 *•7 !*

reclamation of natural rubber. Some workers found sulphur mono-

26
ehloride-3-pentadeeylophenol condensate metal salt to give the
best result out of five different reclaiming agents used in SBR
27
reclamation. Amino compounds have been said to be useful in the
reclamation of SBR as well as mixtures of SBR and natural rubber*
natural rubber and SBR have also been reclaimed using rosin and
28
mixed dixylyl disulphides whereas polyisoprene, stereoregular

polybutadiene> butyl and other rubbers were reclaimed using softe-

29
ners in the presence of a depolymerization catalyst . Reclaimining
30
oil containing unsaturated polymer was used in the reclamation of

stereospecific butadiene rubber*

A number of processes has been followed uptil now for the

reclamation of rubber —

i
(i) Solvent process (MacCartney, 1870) — Ground scrap rubber
was treated td.th solvents for raw rubber at 265-S00°F, until so-

called solution occurred,

(ii) Dry distillation process (Danckwerth and Kohler9187S)i — On

a small scale attempts have been made on dry distillation of

vulcanized scrap rubber,

1
(iii) Plasticization process (Penther9 1914) —— The vulcanized

scrap has been milled with or without oil or chemical agent,

(Iv) Thermal process (Varenhorst and Folj Dunlop and Twiss,

1918)
1 large pieces of vulcanized scrap rubber containing fabric

were heated in an autoclave in superheated steam or other inert gas

 8 ;■*

at 60 psi and 428 - 482°Fj the fabric carbonized and remained in

the reclaim produced.

Glazunoff solution process (Glazunoff, 1936) •— Scraps

are ground and heated with a solvents the solution filtered and

the rubber reclaimed by evaporation* presence of peptizing agent

accelerates the process of reclamation.

(v) Hot water process (Cole, 1937) —« Scrap tyres were

chopped, placed in a wire basket, and heated in water in an

autoclave under pressure at 4820jfr (250°C) • The fibres charred and

remained in the finished reclaim*

gg
(vi) Bemelmans process (Bemelmans, 1938) —— Vulcanized

scraps were heated in presence of an inert gas in a closed vessel

at atmospheric pressure at 450-480°F» Plasticization of the rubber

is accompanied by simultaneous destruction of cellulose by carboni­

zation.

(vii) Nervastral process (Ghez, 1940)

1 —— Scraps were placed in

a wire basket and heated at atmospheric pressure in motten asphalt,

whereby the fibres carbonize.

33
(viii) Thermodynamic process {Cotton) —— Ground scraps were

preheated in open steam, the hot rubber vigorously masticated in

an internal mixer with the addition of fillers and if necessary*

of a chemical plasticizer, then worked at 22Q°C for about 20-30

minutes.
 -5 9 *-

Besides these historical processes there are a few proee-

sses falling under the class of modern methods of reclamation.

1
(i) Heater or Pan process (Hall* 1868) — Fibre-free scraps,

ground to a fine mesh, and mixed with reclaiming oils and alkali-
nizing agents, are loaded in pans and placed in autoclave where they

ar©' heated by open steam for a controlled time and temperature

(ranging between 338°F (100 psi) and 407°F (260 psi),

1
(ii) The Acid process (Mitchell) Which is now only of

historical importance, is similar to the Pan process, except that

thjs fibre is removed by acid. Here, rubber scraps are heated with
8-10$ sulphuric acid solution in large acid-resistant vats at

175°F fop £0 2 hours, washed and heated in the presence of a

plasticizer*

1
(iii) Digester process (Marks, 1899) <— Scrap rubber, (with

or without fibre) cracked to the required size is treated with a

4-10$ solution of caustic soda in an autoclave at a temperature
between 345°C (for about 24 hours) and 390°F (for about 3 hours).

A neutral digester process has also been attempted earlier.

Here scraps were treated xvith 1-3$ solution of metal chloride

(calcium or zinc chloride)♦

(iv) High pressure steam process (Gross, 1934)34 —— Scraps free

fibre are coarsely ground, mixed with reclaiming agents and heated
with steam in a high-pressure autoclave at 800-1000 psi (520-550°C

for 1 to 10 minutes).
 s 10

(v) Engelke process (Meyer, 1937)1 —« Scraps containing

fibres are cracked, mixed, if necessary, with plasticizing oils
and peptisers and heated at a very high temperature In a high-
pressure autoclave for a short period*

(vi) Lancaster-Banbury process (Banbury, Comes and Schnuck,

1946)**® —— Scraps, freed from fibres, tha are coarsely ground,
mixed with reclaiming agents and loaded into an internal mixer
whereby the mechanical work raises the temperature upto
390 -550°F,

(vii) Reelaimator process (Elgin and Sverdrup, 1953) 36 —■ Cracked

scraps freed from fibres are finely ground and treated with reclai­
ming oils and devulcanizing agents in a screw-type extrusion machine
(at a temperature around 390°F) for 3-5 minutes*

(viii) Lurgi-Ficker process (Ficker, 1972)°' Scraps, after

crushing and grinding are fed into a continuous mixer moistened
with softener and reclaiming fluid and heated at about 200°C, the'
heat medium being a high-temperature oil*

In general, all the processes, have similar finishing

steps, Usually, the reclaim is further compounded, refined on
tight mills, and strained to remove forei|!g*» solids.

Out of the various processes both historical and modern,as

mentioned above, some gave rise to good quality reclaims, whereas
others did not. On the other hand, merits as well as demerits
 *» * 11 J«»

varied In their potentialities from one process to another.

Quality of reclaim as produced by the solution process of

MacCartney was relatively poor, although a low mineral filler

content was possible besides the recovery of the fabric along

with the rubber. The distillates resulting in the dry distilla­

tion process had too frightful odour to bring this process to a

commercial stage. The plasticization process could not provide

the rubber sufficient heat to bring about the required chemical

action. Crlazunoff solution process gives reclaim of somewhat
inferior properties. The disadvantage in the Bemelman's process

is the difficulty in achieving uniform heat distribution in gases

of low heat conductivity, such as nitrogen. The pan process may
provide specialized reclaim as it is not limited by problems of

fibre destruction and washing. The acid process has the advantage

of destroying not only cellulose, but also the filler and the

whiting frequently present in the product. In case tyres contai­

ning synthetic rubber were treated by the alkali digester process,

the alkali caused the synthetic rubber to harden during the

digesting process* Because of this and also the reduction in the

proportions of curatives (such as sulphur the excess of which was

removed by caustic soda) by the introduction of organic accelera­

tors in rubber compounding the alkali digester process was replaced

by the neutral one. In the neutral digester process, however, use

of water alone (instead of metal chlorides) built up excess
pressures in the digesters. Besides one more disadvantage of the
 m 3 12

digester process is the requirement of a washing procedure

followed by drying so as to remove the excess of defibering

agent and the salts formed as reaction products with the

fibres* Reclaim obtained by the steam processes is, in general,

more plasticj also such processes consume much less energy than
other methods* The type of plant used in the Engelke method may

deal with some types of synthetic rubber* Laneaster-Banbury

process is a very rapid one* The Reclaimator process is, however,

based upon its ability in arresting the softening process at the
first point of maximum softness. Heating is so uniform throughout

in the Lurgi-Fieker process that practically each particle reaches

the same temperature at the same time*

•

Among the several processes outlined above three principal

processes commercially used at present are ——

(a) Digester process

(b) Pan process

and (c) Reclaimator process

and hence it will be worth projecting here the flow-chart of

these processes.
 13 :

(a) Digester Process !-

Reception of Scrap tyres — Testing for styrene-butadiene

rubber (SBR)
4
Sorting of tyres according to
service) type* etc.

Entry, into Cracker I followed by

i
coarse screening-removal of bead
wires - cracking of tyres to rough
size and their screening
4
N -

Entry into Cracker II-grinding of

scrap to the requisite degree-remova]
of ferrous metal and fine rubber.
I
Conveying cracked stock to storage-
hoppers |

Loading of cracked stock into

agitated digesters - treating them
with plasticizers as per requirement

Setting the wash liquors Boiling the stock from digesters -

with fine rubber or their washing and drying
screening them so as to
separate the dischargable
V ■
effluents
Conveying aired rubber to mill
room - massing) the stock by suitable
form of milling followed by straining
and removal of metal and other
extraneous matter — refining the
strained stock on refining mill to
fine gauge.

Quick cooling of the reclaim -

passing it to storage bins
 14 :-

(b) Pan process *-

Reception of scrap tyres —^ Removal of fibres

Grinding of cracking to desired

level

Mixing the ground stock with

plasticizers in a mixer

*Y
Loading into suitable containers
(pans and boats) and charging into
autoclave - application of steam
under pressure for a fixed period

4
Blowing m the steam off -removal
of stock followed by its unloading
into breaker and cooler

Refining on mills

Passage to stock warehouse

(e) Reeiaimator process*.

Reception of scrap tyres *—^ Removal of coarse cracked beads

4
Complete removal of fibres by
mechanical treatment
A
Baling of separated
fibres
'M/
Grinding of separated fibre-free
rubber-sifting to suitable mesh size

Mixing the ground rubber with

requisite plasticizing oils
•v
Passage through an extrusion tgape
machine provided vrith the control of
zone temperature (Reeiaimator)
~Y
Refining on mills
 S 15

1*5 Performance of reclaim

Property of reclaimed rubber, evaluated by both chemical

and physical tests, depends on the state and type raw material

(scrap) from which it was manufactured a© well as the process

followed in its manufacture* Although reclaim is used with new

rubbers in varying proportions in many compounds, there are many

products where reclaim is the only source of rubber hydrocarbon

(for example, mechanical goods, hard rubber batten boxes, semi-

pneumatic tyre and so on). A figure of 50# is usually taken as

the polymer content of a whole tyre reclaim. Resilience and

fatigue properties of reclaim are influenced by the composition

of the original rubber compounds* Its use brings about a decrease

in tensile strength, but gives rise to an increase in the rate of

cure as well as in cured hardness* Reclaim is also regarded as a

high grade compounding ingredient and displays its importance as

the right plasticizer, or accelerator or reinforcing ingredient*

1*6 Choice of ingredients

Most of the reclaims are compatible with new rubbers

except in the ease of butyl rubber, with which butyl reclaim hi one

is compatible* Reclaim admixed with virgin elastomers like natural

rubber does not form a continuous phase, but tends to stand out as
small discrete particles^®* Dispersion of reinforcing blacks in

natural rubber and reclaim may not be equal, the latter absorbing

little or no black during the conventional addition of the black

 QQ
In mixtures of these rubbers' * Prior addition of reinforcing

pigments to reclaims may, therefore, be advantageous* Apart from

that the reinforcing effect of fillers in reclaim puts them in the

order same as that In a virgin rubber* Thus carbon black reinforces

more than clay and whiting usually introducess no reinforcement at

all. There are all-reclaim recipes where china clay Is used as the

principal filler. As a means of heat dissipation within the compound,

it helps in attaining a fast high temperature cure without blowing

by minimizing the effects.of the, exothermic reaction* Glass of

softener to. be used in reclaim is the same as with new rubber and in

case of blend with natural or synthetic rubber, the selected softener

is likely to be that commonly employed with the type of the rubber

used. The level of tackifying plasticisers may be required to be

reduced with the gradual Introduction of reclaim in compounds of new

rubber.

Although some proportion of zinc oxide Is customorlly added

in reclaim compounds, the reclaim Itself contains some proportion of

this activator originally present in the scrap from which it was

prepared. In passing from an alkaline reclaim to a neutral one, the

latter curing a little more slowly than the former, an alkaline

activator such as lime or triethanolamine may be required for compen­

sation to be appropriately added in proportion depending on the type

of accelerator Used. Accelerators and vulcanizing agents used in

reclaim are the same as, in new rubber. Curing of reclaim is faster
 -* 1? :-

than that of styrene-butadiene rubber and hence even a small

proportion of reclaim materially speeds the cure of the syn­

thetic rubber* This increase in the rate of combination of

sulphur in reclaim is caused by the presence of combined sulphur,

as concluded from experiments made with smoked sheet* Sulphur is

probably more soluble in reclaim than in new rubber and thus the

use of reclaim does help to reduce the degree of bloom.

Vulcranizates containing. reclaim exhibit enhanced stability

to thermooxidative degradation* This may be due to the dilution

with the more stable reclaim which otherwise functions as an anti-

40
oxidant . In fact use of reclaim is said to permit a significant
reduction in antioxidant1. Two hundred parts by weight of a first-

quality whole tyre reclaim contain about 100 parts of rubber

hydrocarbon, 35-40 parts of carbon black, 30-40 parts of plasticizer

41
20-30 parts of mineral filler including zinc oxide . This carbon

black, reclaiming agent and the accelerator that could be present

in conventional reclaimed rubber - all have stabilization activity.

On evaluation of selected fractions of depolymerized scrap rubber

as polymer stabilizers it was found that a significant portion of

the stabilization activity is due to the elastomer content of scrap

rubber and presumably because of a change in microstructure of the

elastomer Itself during depolymerization.

 -s 18 U

Adhesives based on reclaim exhibit good adhesion to a great

variety of surfaces* This may be due to the more polar groups

introduced by vulcanization followed by curing* These together with

the highly branched structures produced also account for the solution
1
properties and thixotropy of the adhesives prepared from reclaim .

1.7 Advantages

The advantage of reclaimed rubber came out first so as to

supplement the .import of raw rubber and thus lower the consumption

of the latter resulting in a price control. Reclaim is still the

cheapest source of rubber hydrocarbon. Its use gradually gained,

increasing Importance due to the several advantages it provides.

It is used as a processing aid, often disproves the dispersion of the

compounding Ingredients, facilitates mastication and shows beneficial

effects (of which dimensional stability is an important one) in

calendering and extrusion. The qualities that have made it use so

significant are uniformity, low thermoplasticity, fast processing

and short mixing time, low swelling and shrinkage. Other properties

contributed with pride by reclaimed rubber are low heat development,

minimum reversion high rate of cure, good ageing and so on*

Replacement of natural rubber or SBR by reclaim, however, gives rise

to an increase in the thermoplastielty and tack of the uncured stock.

 -S 19 j-

Beside its cheapness reclaim possesses a number of desirable

properties* In reclaim* combined sulphur content that cannot be

removed in commercial practice is said to be responsible for the

high rate of cure, which may be used as an asset by controlling

it by proper compounding* Antioxidant can be significantly reduced

in compounds of low cost specifications by use of reclaim* Presence

ofl zinc oxide in reclaim, on the other hand, is a helping hand in

bringing flown the proportion of zinc oxide in compounds.

Thermal or neutral whole tyre reclaim is.used in hard rubber

formulations (e.g. in battery boxes) either alone or in combination

with natural rubber or SBR, In rubber to-metal compound for high

temperature applications use of reclaim with new rubber is expected

to be beneficial In respect of heat resistance than

that of the new rubber (e*g* HR) alone, because of the considerable

weakening followed by ultimate destruction of the bond by high

temperature in normal cases. Also unlike the natural rubber

vulcanizates, the reclaim stocks show no tendency to reversion,

thus eliminating this tendency by taking part in natural rubber

mixes.

1.8 Shortcomings

Demerits on the use of reclaim are limited. In cases where

high mechanical properties namely tensile strength, tear- and

abrasion resistance are expected, reclaims are not preferred,

although for resistance to cut-growth, in particular- mixtures of

 -5 20 i~

whole tyre reclaim and neoprene have been found to be good* Again

for compounds where high resistance to water absorption is essen­

tial a stock free from reclaim is said to be the best* Selecting

a grade of reclaim and adjustment of new rubber to reclaim in a

compound are dependent on the end-use and hence the physical pro­

perties the finished product is desired to be provided with under

the service conditions. Although in many products reclaim is the

sole elastomer and the only source of rubber hydrocarbon normally

in the mix recipe some new rubbers are introduced in proportions

depending on the .importance, on tensile property development. Cured

hardness, however, increases on gradual replacement of new rubber

by reclaim in a stock.

1.9 Analysis

Reclaimed rubber, as manufactured by any of the processes

mentioned before and graded on the basis of the raw material used

in such processes, is subjected to examination - chemical tests

for composition and physical tests for performance# Such examination

generally follows some standard methods and thus help to maintain a

product of known composition and reproducible quality, to control

effectively the process of manufacture and, above all to produce a

more homogeneous material by more efficient methods.

 i 21

Chemical test S-
(a) Ash content t This determination serves as a measure of

uniformity of composition and as a first step in the determination

of trace metals. The ash may be due to zinc oxide and/or silaceous

filler and sometimes lime obtained from the original whiting.

(b) Acetone extract i This may be considered as determining the non­

volatile oils, etc. present in the waste of origin, together with any
non-volatile plasticisers used in the reclaiming operation. The
acetone extract also usually contains a little, depolymerized rubber,

accelerator and antioxidant residues, processing oils pitch etc.and

in the case of SBR oils used in extending the synthetic hydrocarbon •

This extract determination is necessary for an estimation of rubber

by difference.

(e) Chloroform extract t Prolonged extraction on the uncured stock

removes the so-called soluble fraction of the reclaim hydrocarbon,

i.e. low molecular weight highly branched structures containing very

few crosslinks. The extract has also been accepted as a criterion of

the efficiency of the reclaiming process — with progress of depoly­

merization there is an increase in the chloroform-soluble fraction

42
(low molecular weight scission products) . With shelf ageing the

ratio of the soluble to insoluble RHC gradually diminishes and the

soluble rubber is said to become attached to the main network by weak

43
links which are readily broken on milling . On standing a reclaim

containing substantial proportions of SBR tends to decrease in plasti­

city, this decrease being generally accompanied by a decrease in

 -8 22 8-

chloroform extract and on re-milling, both the chloroform extract

and the plasticity can be restored. In ease chloroform extraction
is carried out after acetone extraction, the former represents the
soluble portion consisting of highly branched low molecular weight
rubber with attached sulphur residues* This on drying down readily
crosslinks and becomes insoluble as expected from statistical
considerations of the high degree of branching and the random
distribution of the sulphur atoms which can enter Into cross-linking
reactions. A comparatively few crosslinks will insolubilize a
highly branched structure.

(d) Acidity/Alkalinity 8 The rate of vulcanization (retardation

or acceleration) Is.affected by the presence of residual acid or
alkali.in a reclaim. The alkali reclaims are faster curing with
acid accelerators such as MBT, the acid reclaims slow curing while
' 44
the neutral ones are intermediate • The determination may be
carried out by a process involving extraction with hot distilled
water followed by determination of pH of the extract in a pH meter,
calibrated against an (aqueous) solution of known pH.

1.10 Theory

Virtually all commercial reclaiming processes ire fundamen­

tally based on thermal treatment followed by mechanical working.
Heating in steam has been the economical mode of applying this
energy that is employed electrically in present continuous processes
to supply the heat and working necessary for the breakdown of the
 23 S-

vulcanized scrap* Suitable swelling solvents, plasticisers, re­

claiming agents, etc* are used to facilitate the degree of plas­
ticity, inhibit unfavourable side reactions like reaggregation
and suitably lubricate the ultimate reclaim45 . Prior heat
treatment is necessary to condition the scrap, so that by milling
the reclaiming process may be completed. In addition to elimination
of inadequately plasticised particles the refining step also serves
to further reduce the molecular weight. In the efficiency of such
breakdown roller temperatures, were reported to play a significant
role46. Thud a roller temperature at 50° to 80°C gave a much more
effective breakdown than at 120° to 140°C. The main process in the
cooler milling is,' therefore, said to be the mechanical breakdown
of unstable intermolecular bonds, as well as some of the stronger
bonds In the main chains* The degree of prior thermal breakdown Is
critical as the rate of this mechanical breakdown is related to the
initial molecular weight. Moreover, the degree of cure of the scrap
is the factor determining the conmercial success of any process
based solely on mechanical working.

The fundamental properties of the reclaim —— Its general

reactivity in regard to both physical behaviour and chemical reacti­
vity are determined by the type of polymer present in it and hence
by the properties of the unvulcanised polymer. Vulcanised scrap is
known to be collected mainly from tyres in the present - day
production of which styrene-butadiene rubber (SBR) is used in
combination vlth natural rubber. The giant and heavy-duty tyres may
 it 24 i

contain an all-natural tread and a high-SBR sidewall# On the other

hand| there are many tyres that have some straight SBR components
together with components made of a blend of natural rubber with
SBR* Heat-resistance of SBR is more than that of natural rubber and
unlike the latter that undergoes a positive orderly breakdown
(depolymerization) the former is much more difficult to depolymerize,
when heat is applied* On application of heat natural rubber only
softenes whereas SBR has a strong tendency to harden irreversibly
(most probably synonymous to crosslinking) after a short time of
softening* After an original sharp and quite short-lived.decrease in
the viscosity SBR hardens very fast* The decrease in viscosity was
much less pronounced at lower temperatures. The rate of hardening
that depends on the temperature of heating is also greater at higher
temperatures than at lower ones. But the drop in viscosity was not
large enough to make it of commercial use despite the preference of
lower temperatures* A second factor determining the rate of heat
hardening of SBR is its immediate environment. Metal (zinc or calcium]
chloride replaced caustic as a defibering agent, as the heat hardeninf
of SBH was galloping in caustic solution, whereas those in dilute
zinc chloride solution and steam (or water) were similar.

In order that the heat hardening process is retarded and the

heat softening reaction is promoted and maintained In SBR to the same
extent as in natural rubber, reclaiming chemicals and oils are used.
In case of reclamation of synthetic rubbers the reclaiming agents may
be said to function almost as the exact counterpart of organic
 25 I-

aeeelerators In vulcanization. Use of these agents has largely

overcome the complications arising from the presence in SBR of
the fcdcghax highly reactive vinyl groups that admit of a variety
of reactions, most of which amplify the net-like structure4*^*48.
Although a product today of considerable refinement and control
in regard to configuration, molecular weight and branching, etc.
as compared to its production in early stage, SBR has the possi*
bility of forming a number of different repetitive units, seme of
which can carry highly reactive short branches. In reactivity it is
thus different from natural rubber predominantly composed of
cis-1,4 addition units carrying ^ -methylenic carbon atoms. A
wide, divergence was observed also between natural rubber and SBR
(scraps and hence vulcanized) in their rate of absorption of the
reclaiming agents, the latter having a slower rate than the former-,
An additional and excessive depolymerization is, therefore, caused
in natural rubber by the larger portion of the additives, when they
are added to a mixture of the two scrap components, SBR portion
thus again remains much harder than the natural rubber portion and
such mixtures,will, therefore, give rise to a very inhomogeneous
reclaim. The depolymerized vulcanizate was provided with more
uniform consistency when use of some chemicals (certain diterpenic
acids) retarded generally the oil absorption of vulcanized natural
rubber scrap thereby permitting more uniform distribution of the
reclaiming oils in the vulcanized scrap particles of the two polymers
 * 26

The presence of oxygen was also as important as the use of

reclaiming agent but the activity of one in absence of the other

was much less compared to their effect in combination. Prior to

reclamation of the vulcanized scrap, measurement of its physical

properties, that depend on its age and prior usage, reveals that

the scrap has already undergone certain changes in regard to possible

oxidation and breakdown during the life of its usage where the vul­

canized rubber has been subjected to heat and oxygen. Also grinding,

an important step prior to heating in reclamation and particularly

essential in case of synthetic rubber for the absorption of reclai­

ming agents, causes an increase in temperature and the exposure of

the scrap to air increases tremendously as its vulnerable surface

area increases with decrease in partiele size. During the use of

the vulcanized rubber as well as in the grinding of the scrap or

during the initial heating some hydroperoxi.de (or peroxide structures

are formed (expected at different rates in case of natural rubber and

SBB since -methylenie C-atom is the most likely point of attack in

the isoprene chain and also in the C-atoms at the double bonds SBR

does not have any substitutional groups), the decomposite of which

causes the high rate of molecular breakdown during the early stages

of the reclaiming process. Faster rate of such decompositions is the

reason behind the greater rate of molecular breakdown in the alkaline

compared to neutral solutions, as measured by the amount of soluble

fraction obtained* Such breakdown in a metal chloride solution

appeared to be comparable with that in water. Possible presence of

/
 27 *

greater concentration of oxygen yields, in parallel, more

oxidation product and hence causes the faster rate of reclaim

production in the heater (open steam heating) compared to the

digester (water) process* This may he supported by the greater

production of soluble rubber in the heater process compared to

the digester at a given time and temperature as detected in

systematic laboratory experiment on natural rubber. Vulcanized

scrap with an antioxidant, as added prior to the depolymerization
step, also produced a smaller amount of soluble matter than that
without antioxidant* It is not possible to consider the completion
of any type of reclaiming under conditions free from oxygen* That
new tyres (factory rejects) do not reclaim very well and perhaps

also that synthetic elastomers that are resistant to oxygen are

difficult to reclaim reveal once more that depolymerization occurs

by chain scission Involving oxygen probably in the form of

peroxides * The oxidative reaction is not of permanent nature

and oxygen thus although functions as a promoter of reclaiming

breakdown but under ideal conditions of reclaiming the amounts of

oxygen necessary are small* Regardless of whether the depolymeri­

zation step (the second step of heating) is carried out in an

autoclave under water or steam conditions or in a screw type

SO
machine such as the Reclaimator , it Is desirable to limit the

amount of oxygen at least during this step* The manufacture of

thermal reclaim consists of heating to 200-300°C In absence of

air, thereby involving thermal rather than oxidative breakdown of

the rubbei^.
 -8 28 8-

Presence of oxygen in a reclaim molecule was not,however,

indicated when infrared spectroscopic analysis was carried out

on the- reclaim obtained by subjecting the natural rubber scrap

(prepated in the laboratory under controlled conditions) to the

depolymerization step without the addition of reclaiming oils or

catalysts. On the other hand, while using some reclaiming agents

and catalysts such as phenol alkyl sulphides and disulphides even

though only insignificant increases in the combined oxygen content

could be found in the insoluble portion of the polymers exceptio­

nal activity of these agents on sulphur cured SBR vulcanlzates was

noted in the presence of oxygen promoting the production of low

molecular weight polymer fragments even under milder conditions.

The extreme effectivity of these agents in general and their

greater effectiveness on sulphur cured vulcanlzates than on non­

sulphur cured scrap as evident experimentally are also expected

from the fact that despite their inability in removing sulphur

from the vulcanizate they may simultaneously catalyse the oxida­

tive breakdowns of the polymer chain and bring about oxidative

disruption of the sulphur crosslinks, thus restoring the vulca-

hized polymer to a more two dimensional state. Besidesthe agents

of the disulphide type those of the mercaptan class may also

function by an oxidative scission of the sulphur crosslinks, as

wel& as by suppressing reaggregation by reaction with the fragmen­

tary molecules resulting from the thermal degradation of the
rubber52 953,54^ -gse 0£ certain acid anhydrides such as maleic
55
anhydride as promoters of thermal decomposition has been referred.
 —s 29

It has been pointed out that by a combination with the hydroxyl (OH)
groups normally present in the waste» the thermal oxidative struc­
ture is reduced and so reclaiming is accelerated.

In view of the generally accepted theories supporting the

recovery of plastic state in reclaimed rubber, there is a scission
of the tri-dimensional network responsible for the vulcanized state
or rearrangement of the sulphur links. That some of the crosslinks
are removed and random chain scission takes place leading to the
break-up of the three dimensional network, whenvrubber scrap is
heated has also been reported by Ceresa56 . Normally this heat is
applied in presence of swelling solvents, plasticizer and/or reclai­
ming agents and as the lubber swells, reaggregation of chain frag­
ments is.suppressed in the swollen condition. The swelling pressure,
on the other hand, also aids to facilitate chain scission by weake­
ning Van der Waal*s force between bonds®^. Beside the use of these
auxiliary substances in addition to mechanical working heat is a
factor common to all reclaiming processes. As a result reclaimed
rubber contains more combined sulphur than the original vulcanized
rubber rubber which contains free sulphur in addition to its combined
sulphur and as is already known the effect of heat on vulcanized
rubber is largely dependent on the amount of sulphur present* If the
vulcanised rubber contains much free sulphur, then the action of
heat at first causes a hardening and when almost all the sulphur has
combined, further heating gives rise to a reclaiming action. Reac­
tions that are competent (proceeding with their own reaction rates
under any given set of conditions) in softening the rubber may be
 30 t-

classified as chain scission, depolymerization and chain termination,

whereas those tending to harden it may he polymerization and cross-
linking. In natural ruhher the energy level necessary for chain
scission is lower at a given location within the chain. It is also
lower than that necessary for breaking the sulphur link. This is due
to the possibility of formation of allylic fragments as a result of
which chain scission should predominate. Depolymerization, on the
other hand can occur either by breaking the existing crosslinks in
the vulcanized polymer or by promoting scission of the main chain of
the polymer or both. Theoretically otherwise depolymerization can be
considered the reverse of polymerization and therefore reactions
occurring during depolymerization should be well assessable by
following the reaction backwards?. Depolymerization in case of vinyl
type polymers has been found to proceed mostly by free radical chain
mechanism initiated by chain scissionss , During reclaiming various
physical confoimatione of chain fragments can be produced. These
chain fragments can be expected to be more or less typical for each
polymer. The reactivity of these chain fragments will depend on their
chemical composition. In case of s SBR, crosslinking as considered
to occur, is probably hastened considerably by the type of chain
fragments that can be produced from such a diverse structure of
polymer and amplified by the highly reactive vinyl branches which the
polymer contains47• It is impossible, in general, to describe the
exact nature of these fragments other than to state that it is
doubtful that all the crosslinks in the original vulcanizate have
 « 31 t*

been broekn. Hence, the reclaim is expected to contain a more

three-dimensional structure, a polymer with some crosslinks built

into the molecules and having on an average shorter polymer chains,

as compared to the parent raw polymer# It has also been shown that

the main reclaiming process attacks the carbon carbon bonds of the

vulcanized polymer chains to a greater extent than the carbon-

sulphur bonds of the crosslinks formed during vulcanization* If a

sulphur cure and a non-sulphur cure such as p-dinitrosobenzene

cure (GMF cure) have the following structural units respectively,

it becomes evident that reduction in molecular size and hence

plasticization of the elastomer could be brought about in either case

QMf

by scission of carbon to -carbon bonds in the original hydrocarbon

chain69?60. In case of the sulphur cure the network could be opened

up and a two-dimensional state restored by scission of the sulphur

bridge, removal of the sulphur by combination with the reclaiming
 * 32

agent* or any, reaction required to break whatever bonds the

sulphur may form in holding together.the hydrocarbon chains in

the vulcanized state. If the reclaiming agent has a specific

reactivity toward sulphur it would not attack the crosslinks in

the non-sulphur cure and hence would be less effective than in a

vulcanizate crosslinked by means of sulphur. Peptizers serve to

61 ,
amplify rather than change the pattern of breakdown , Whereas a
substantial proportion of the sulphur of the disulphides used as
reclaiming agent is converted into zinc sulphide during the thermal
(SO
treatment , which of itself may assist reversion. As indicated

by the chemical behaviour of the various types of synthetic rubber

vulcanizates toward different reclaiming agents, what, above all,

is important is the nature of the chemical bonds of the cross-links

whereby fundamental differences exist* Again, under identical

reclaiming conditions synthetic rubber scrap breaks down to a

63
lesser degree than natural rubber . In order to throw light on the

bonding of sulphur to natural and butyl rubber and on the thermal

stability of crosslinks before and after reclamation long continued

extractions were carried out with acetone and sodium thiosulphate

solutions * Reclaiming, therefore, is said to destroy polysulphide

linkages, resulting in increases in zinc sulphide content, the
effect being rapid at 191° and present on long continued heating at
100° . Sulphurless vulcanization with tetramethylthiuram disulphide

does not produce polysulphides. To ensure an adequately plasticized

 S3 S«

reclaim a proportion of the soluble rubber, as indicated by the

chloroform extract, appears to be essential. Besides the solubi­

lization of this relatively small proportion of the elastomer,

the bulk remains as an insoluble get to which the carbon black

is normally bound either chemically or physically.

Devulcanization of a network, as said to be brought about

mechanically or chemically, theoretically involves scission that
can be classified as (a) scission of all the crosslinks, (b)

scission of a fraction of the original rubber chains at points

between crosslinks, (c) scission of some of She crosslinks, and

1
some of the chains between crosslinks • As shown in the schematic
representation of the Figure-l*X (a), (b) and (c) the network

degradation occurring during reclaiming is fairly represented by

(c), hypothetical representations being (a) and (b) respectively.

As mentioned above, the proportion of rubber chains are chemically

and physically anchored to the carbon black particles, such

consideration being schematically pictured in Figure-» based

on which continual reclamation of the same stock leads to a highly

branched material. So far as the prehistory of reclaim is concerned,

chemical bonds are formed, during mastication with carbon black
particles and further linkages are introduced thermally during
vulcanization. Reaction of the rubber maeroradic&ls with carbon
black may be represented as a
 t 34 8

Daring vulcanization, particularly with long cure times or at

high vulcanization temperatures,thermal degradation of rubber
chains may be appreciable and with certain vulcanization

systems may be accelerated. As during mastication any mechani­

cal treatment of vulcanized rubbers leads to degradation -

scission of crosslinks or of polymer chains between crosslinks -

via free radical processes. Extraction with solvents of vulca-

nizateB also causes thermal degradation that covers scission of

rubber- filler interaction sites (rubber-black bonds) in addition

to the scissions of crosslinks and of rubber chains. Except in

cases, where'formation of new crosslinks and degradation of

existing crosslinks occur concurrently, the ease of network

degradation is not generally affected by the nature of the cross­

link*

1.11 Object and Scope

Normally BTA/TGA studies indicate the effects of compounding

ingredients in elastomer systems. Various parameters can be set for

DTA/TGA studies relating to the identification of specific effects.

Reclaimed rubber (having significant properties including

thermal characteristics) is used extensively in rubber compounds.

The effects of such reclaimed rubber-based compounds have so far

been studied for certain properties by standard experimental tools.

*
 s 35 s

In order to have Improved views on the known properties

of reclaim along with unveiling of new informations DTA-TGA. of
reclaimed rubber under different perspectives were undertaken
in the present work* Such studies covering some, if not all,
of the common spheres of reclaim will certainly help in evolving
new ideas about its thermal performance from its past history
to processing prior to the stage of the finished product
involving it*

4
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