- - "0

U . S. Department of Commerce Research Paper RPl850

National Burea u of Standards Volume 40, January 1948
Part of the Journal of Research of the National Bureau of Standards

Vulcanization of Synthetic Rubbers by the Peachey

Process 1
By Norman Bekkedahl, Fred A. Quinn, Jr., and Elmer W . Zimmerman
The Peachey process, whICh vulcanizes nat ural rubber by subjecting it alternately to
sulf ur dioxide and hydrogen s ulfide gases, has been found to vulcanize t he more common
svnthetic rubbers. The polvmcrs studicd were natural rubber, GR-S, GR- M, GR-I,
GR-A, Hycar OR- IS, Hyc~r OR- 25, Hycar OS-]O, Hycar OS- 20, and Hycar 08-30.
Good cures were obtained with all of t he polymers except GR- M. None of the synthetic
rubbers cured any faster than natural rubber. The nitrile a nd t,he styr ene copolymers of
butadiene cured at about the same rate or so mewha.t s lower. GR- I required roughly 50
times as long as natural rubber for an equivalent cu re, and GR M required even longer.

(' 1. Introduction time) were placed on a long piece of heavy-gage

The Peachcy process, which has been used to
vuleanize natural rubber by subjecting the rubber
alternately to sulfur dioxide and hydrogen sulfid e
.,
,\
gases [1, 2, 4, 6, 7],2 has now beeD applied to
synthetic rubbers. Thi communication describes
the results of an investigation initiated recently
by McPherson [5]. The polymers studied include
natural rubber, GR-8 (butadiene-sLyrene copoly-
mer) , GR- M (polyehloroprene rubber similar to
Neoprene- GN), GR- I (isobutene-isoprene copoly-
mer, or Butyl rubber), GR- A (butadiene-acry-
lonitrile copolymer, or nitrilc rubber), Hycar
OR- 15 (similar to GR- A) , Hycar OR- 25 (lower
acrylonitrile content than the OR- 15), Hycar
OS- 10 (butadiene-styrene copolymer having a
considerably higher styrcne content than GR-8) ,
Hycar OS- 20 and Hycar OS- 30 (both similar to
GR-S with the exception that the OS- 20 eon-
tains little or no fatty acid).
II. Experimental Procedure
The rubbers tested were sheeted as thinly as
practicable, usually from 0.5 to 1 mm, by means
of a laboratory rubber mill, and strips approxi-
mately 1.75 by 13 ern were cu t from the
sheets. Th ese strips (usually four to six at a
I Th is paper· was presented a t the 112th national meeting of the American
C hemica l Society held in New York City, September 15 to 19, 1947.
' Figures in brackets indicate the literature references at the cnd of this
paper.
galvanized wire scrcening that was inserted in a
25-mm diameter glass tube approximately 1 m
in length , each end being equipped with a ground-
glass joint. A triple inlet tube was connected to
one end so that the gases, sulfur dioxide, air, and
hydrogen sulfide, could be admitted separately .
A single outlet tube at the opposite end led the
unabsorbed gases first through a 20 percent solu-
tion of sodium hydroxide, then through a saturated
solu tion of bromine in water, and finally through
a dilu te solution of sodium hydroxide in order to
trap any of th e remaining gases, including bromine
vapors.
Except for the initial series of tests, which will
be discussed later, all of the test strips were exposed
to the vu lcanizing gases for 5-minute cycles, the
number of cycles being varied from one to as
many as 128 in an effort to determine the condi-
tions for optimum cure for each of the various
synthetics tested. A single cycle consisted of a
5-minute exposure to sulfur dioxide, a brisk
lO-seeond sweep of air to remove the sulfur dioxide
gas not absorbed by the samples, and a 5-minute
exposure to hydrogen sulfide, followed by another
brisk sweep of air.
In all of the experiments a separate· set of sam-
ples was used for each of the various numbers of
cycles indicated, i. c., one set of samples was in-
serted into the tubc, exposed for one cycle, and
removed; a different set was exposed for two cycles

Peac h ey Process on Synthetic Rubbers 1

 and removed, etc., until all of the desired numb er :I
~

----
-
of cycles were completed . The samples were then .... B
z
~ ../
placed in a vacuum oven at room temperature for
3 hours to remove all uncombined gases and also .....
~ 4
~
.-.I 0

~y V-
IL
the water vapor that is formed in the vulcanizing ....
x 3
reaction, and were th en weighed to determine th e
weight increase, which was assumed to be caused
by th e added sulfur.
The extent of cure of each strip was qualitatively
"...
~

!
... 2 iL
V
/
evaluated by h and-stretching. Som e of th e sam- ...'"c
.. I) .;
I)

ples from each run were then quantitatively z

analyzed to determine how much sulfur had ac-
tually combined with the polymer. The difference
between the percentage incr ease in weight and th e
o V
o 5 10
T IM E OF EXPOSURE. MINUTES
15 20

combined sulfur was assumed to be free sulfur.

FIGURE l. In crease in weight of samples of compounded
<:
Chemical analyses on a number of th e samples for natural rubber plotted as a function of the time of ex-
free sulfur indicated this assumption to be correct. posure to sulfur diox1'de and to hydrogen sulfide for one
cycle of operation.
III. Results of Experiments The let ters representing the curves refer to the com pounrl ing formll ias
given in ta ble 1. Data from which these curves were prepared a re give n in
ta ble 2.
Before beginning the actual v ulcanization
studies, strips of each of the rubbers to be tested
values for these tests are given in table 2. It will
were submitted to a 16-hour exposure to sulfur
be noted t hat compounds B , C, and D effe cted a
dioxide gas; another set of samples was similarly
significantly greater absorption of sulfur t han A
exposed to hydrogen sulfide gas for the sam e
(rubber alonE), but that C and D produced no
length of time. The average increase in weight
noticeable advantage over B. From the results
during this treatm ent was 0.2 percent, indicating
of a r epetition of th is test, in which the sampl es
that there was very little, if any, ch emical addi-
were placed in reverse order: in th e tube, changing
tion of the gases to the rubber.
in effect t he direction of fiow of th e gases with
An initial series of tests was m ade to determine
respect to the samples, it has been shown that th e
th e most practical period of exposure of the rubber
to each of th e two gases. Natural rubber was TABLE 1. Compounding J01'mulas
used for this determination. In add ition to the
pure ribbed smoked sh eet, three batch es of
smoked sh eet containing various combinations of -------------
Ingred ients I ~l I~J __c_I __~_
fillers and accelerators (see table 1) were exposed Ribbed smoked sheeL ______ _____________ 100. a 100. a 100. a 100. a
Zincoxidc _______________________________ ________ 6.0 6.0 6.0
to determine wheth er or not these combinations Stearic acid _______________________ ______ _ ________ 0.5 0.5 0.5
would cause a change in the rate of vulcanization. M crcaptobenzothiazolc ______ ____________ ________ ________ .5 .5
Zin c dimeth y ldith iocarba mate ___________ ________ ________ ________ . 05
Single cycles of 1.25, 2.5, 5, 10, and 20 minutes,
respectively, were run. A study of the curve of
th e percent increase in weigh t plotted against th e TABL lc 2. T'ulcanizalion for one cycle
duration of th e cycle (fig. 1) shows that the longer
times of exposur e to t he gases in a given cycle ,\'ei ght in creases
Type of polymer Duration of cycle - - - - - - - - - - - - -
vulcanize a sample of rubber in a small er number of A.I
cycles, but that th e sulfur can be added in less total --------1---------- - - - ---- - - - ----
time using shorter cycles . Extremely short cycles, min Percent Percent P ercent P ercent
1.25- -- ------------ O. 90 I. 10 I. 10 1. 14
however, waste vulcanizing gases and also do no t 2.5 _______________ _ 1.47 1.76 1.88 1.97
give time for the gases to penetrate into the in- 1
NaturaL ____ ___ _____ 5 _________ __ ___ ___ _
10 _______ _________ _
2.44 3.02 3. 14
3.344. 0 2 4 . 13
3.15
4. 10
terior of the r ubb er samples. As a compromise it 20 ________________ _ 3.99 4.66 4.82 4. 75
was decided to usc 5-minute cycles for th e E'X-
periments to be described here. The numerical 1 For compowld i_og formu las, see tab le 1.

2 Journal of Research '=

1
\_-- I
I,
f

"!
(' pos ition of the sample in th e reaetion tub e does no t Figures 2 and 3 show in graphi C's l form th e data
anect th e perce ntage weigh t incr ease. obtain ed from the butadi ene-ty pe polym er . All
In table 3 ar e summariz ed the data obtained of th ese rubbers were run simul Lanrously. Th e
from all of the synth etic rubb er s and natural solid lines indicate th e amoun t of combined S UlJl I r,
rubber studi ed . The increase in weight is based on and the broken lines r epre ent the total uUm.
th r wrig ht of th e original sample. The combined Figure 4 shows similar r es ults for GR- I and GR- i\ f
.' s ulfur is also compu Led on this basis and therefore syn th etic rubb ers. Th ese poly mers were n Ul
r ep resent th e parts of combin ed sulfur p er separately from the others b ecause of th eir
hundred par ts of original polymer . The extent of extr emely low ra te of cure. The results obtained
curr was estimated by hand-stretching the individ- from vulcanizin g natural r ubb er ar e shown on this
li al spec im ens and observing th e r ate and degr ee of same graph for comparison.
rrco vrry. It is believed that t h e op timum elll'e, as
". indicate d for each type of rubber , rcpresents tb e 28
-, .... '

-- -
vll ica nizate tbat bas th e high es t tensile strength . ,
24
,~
24
--- -- - c,!,'"

.... 20
~~_s ~ 20
....
<.>

-
, --
...z<>
-
~
::; 16
. ",'"
...'" '"
Q.
.- l--"
---
16 /

~
", - -41 /
12
Q.
/)
~
------
... /~
f~p.1~/
p.\..
,/

P
r, --- ---
",' ...J
\ 12 :::>
...
~ ---
:::> / 8
( C/I
,-
...J /
H"'C~.2~!5 ,,
--- -
:::>
C/I 8
- ---- - ---
//- ~-
// GR :.'_
- --- ---
- -- - ---------
4
<LR..:~---
4

~:;
~ ,:::..
-;;'(CI>.R

HYCI>.R OR-15
OR-15
H'(CI>.R OR - 25

GR -I>.
o
o
-' ~~
16 32 48 64 80
GR-I

96 112 128
o NUMBER OF 5-MINUTE CYCLES
o 4 8 12 16 20 24 28 32
NUMBER OF 5-MINUTE CYCLES
FW U R E 4. Percentage oj w lJur added to OR- lI ! , OR - I , an d
F r GU R E 2. Percenta ge of sulfw' added to OR - S, OR- A, natural Tubber samples plotted as a f unction oj the nwn-
JI yCC!1' OR- 15, a nd H ycar OR- 25 n .bbel' sample:; l)lotted bel' of 5-minule cycles of ex pOWl'e to the gases of th e
as a func tion of the number of 5-minute cycles of exposure P eachey process .
to the gases of the P each ey process. TIlle solid li nes indicate combi ned sulfur as determi ned by chemi cal ana ]"
'T he solid lines indi cate combi ne d sul fur as d ete rmin ed h y che m ical a na l- ysis, and t he broken l ines indicate t he total sulfu r , as determ ined by wr igh t
ysis, a nd th e. bl'ok en lines ind icalC th e to ta l s u iru r as d rtC'l'lllineci b y we ig ilt i llcrease of t he sa m p le.
increase of t h e sample.

24
A confirmatory experim en t was p erformed in
which natural rubber and all of th e syn th etic
~
...<> 20 c:,_2 01 -.....-,..- -
f-'-
- polym ers, v~'i th th e excep tion of GR- I and GR- M ,
were vulcan ized simultaneously for 4, 8, 16, and
...'" 16 ~'(~! ~o
0....-:,.
32 cycles, r espectively. Th e increases in weight
Q.

,; ,,- ..... :.,,' o~ .. ~ agreed so closely wi th those ob tained in the pre-

...
:::> 12
," %1- 5- 20

" " '" ...... ~ ~

",'
...J
:::>
v iou s runs tha t i t was tll ought unnecessary to run
'" " ---
~ -::::-- ---- -- --- -
C/I 8
., ch emical analyses for th e amount of combin ed

--
os-~~
\ ",'" '" ,) ... sulfur or to tabulate the addi tion al data .
4

o
...~ ~ --- -- 05- 10
As a ma t ter of interest, th e v ulcanized pure
ribbed smoked sh ee t specimens describ ed in table
o 4 8 12 16 20 24 28 32
NUMBER OF 5-MINUTE CYCLES 2 were subj ected to two physical tests, n amely ,
F IG U RE 3. P ercentage of w lf u r added to JJ yCC!1' OS- 10, stress at 15 kg/cm 2 (21 3 psi) and permanen t set.
flycar 0 3 - 20, and H ycar OS - 30 Tu bber samples plotted Each group of similar degrees of vulcaniz ation
as a function of the numbeT of 5-minule cycles of eXpOSltTe (1.25, 2.5, 5, 10, and 20 minutes) contained four
to the ga ses of the P eachey process. strips, two of which had b een cut longitudinal to
'rhe solid lioes in d icate combiued surful' as deter m ined by chem ica'i an al- th e direction of passage of the rubber b etween th e
ys is, and th e broken lines indicate the total s ulfnr as de termined b y weigh t
increase of t he sam pIe. mixing roll s of th e mill and two of which wer e cut

( Peachey Process on Synthetic Rubbers 3

_-.J
 cp.

TABLE 3. Vulcanizations for various numbers of cycles TABLE 3. Vulcani zutions for various numbers of cycles-
Continued
N um- Weigbt Com-
Type of polymer ber of in- bined Extent of cure 2 Num- Weight Com·
cycles Crease sulfur I 'l'ype of polymer ber of in- bined E xten t of cure 2
cycles crease sulfur I
- -- - - - - - 1 - - - - - - - - - --------- - - - - -
P er- P er-
cent
cent o o
J
None.
o 0. 11 None. 0. 13 No noticeable cure.
. 56 E xtremely sligbt cure . . 24 Do. \
I. 43 · 68 Sligh t cure. 4 . 39 0. 10 Do.
GR-8 ____________ __ 4 1. 57 . 99 U ndercure.

I<
9 .55 Do.
8 4.30 3. 08 Good cure (optimum). GR-I. ____________ _ 12 1. 19 Sligh t cure.
16 14.47 8. 83 Ovm·cure. 16 1. 23 0. 12 Do.
32 22.77 14.77 " Leathery" cure. 24 1. 77 U ndercure.
32 2. 13 0.22 Do.
o None. 64 2.45 .51 Sligbt undercure.
. 71 Slight cure . 128 5.30 1.12 Good cure (o p t imum).
. 99 · 79 U ndereure .
GR-A ____________ _ 4 1. 22 1. 10 F airl y good cure. o o Noue.
8 2.65 1.14 "T igh t" cure (optimum). 1. 22 0.64 Appreciable cllre.
16 4.27 Overcul'c . 2 3.52 2.31 Good cure (optimum).
32 6.05 2.84 "Leathery" cure. 3 6.60 4.55 Sligbt overcure.
Natural ____ ______ __
o 0 o No ne. 4 6.95 4.78 Overcure.
4 1.30 .84 F airly good cure. 6 9.98 7.20 Greatly overcurcd .
8 2.52 1. 37 "Tight" cure (optimum). 12 11 . 79 7.76 HLeathery" cure.
16 4.50 24 12.98 S. 83 Do.
32 6.03 2.05 "Leathcryll cure.

o None. I Based on parts per hundred parts of polymer.

1. 15 Slight cure. 2 Estimated by ha nd-stretching.
1. 48 · 86 U ndercure.
H ycar OR-25 _____ _ 4 1. 90 1. 28 Fai.rly good curc.
8 3. 58 2.55 "T ight" cure (optim u m). transverse to the direction of milling. After de-
16 6.39 Ovcrcure.
32 8.98 5.34 "Leathery" cure. termining the cross-sectional area of each strip]
o 0 0.20 None.
the proper-sized dead weight was hung on the
0.38 · 26 Sligh t cure. strip and th e elongation between two gage marks
. 64 .54 U ndercure. was measured at the end of 1 minute. The weight
H ycar 08-10 ______ _ 4 .96 I. 24 F airl y good cure.
8 1.93 "Tigh t" cure (optimum). was then allowed to continue h anging on the
16 4.52 5. 19 Overcure. sample for an additional 4 minutes] after which
32 7.55 "Leathery" cure.
time it was r emoved and the sample allowed to
0.30 Non e. relax for 1 minute. The distance between the
1 I. 09 Slight cure.
2 2. 14 1. 21 Good cure (optimum). gage marks was again m easured] and from this
Hycar 08-20 ___ ___ _ 3.49 2.29 Slightly overcured.
7.73 5.32 OVCI·cu re.
figure the permanent set was calculated . The
16 13.61 8.85 " Leathery" cure. results of these physical tests are summariz ed in
32 20.32 ]2.81 Do. table 5 and shown graphically in figure 5.
o 0.10 N on e. Another interesting conclusion may be drawn
0.69 Slight cure. from the results. The amount of combined sulfur
1. 29 O. 66 U ndercured.
Hycor 08-30 ______ _ 4 1. 73 1. 17 Good cure (optimum). in th e optimum cures for natural rubb er and for
8 5.21 3.58 Overcure. all of the synthetics] with th e exception of GR- M]
16 11. 74 " Leathery " em'c.
32 21. 29 13. 45 Do. is b etween 1 and 3 p ercen t (see tahle 4) . This
agrees very well with P eachey ]s co nclusion that an
0.46 :-<ol]e.
0.31 No noticeable cure. optimum cure is attained in natmal rubb er by his
2 . 75 Do. process when a coefficient of v ulcanization of 2.0
4 1.41 Do.
8 2.65 Do. to 2.5 is attained [6] 7] . The n atural rubber and
GR-M ________ __ __ _
12 3. 97 Do. all of the synthetic rubbers investigated] with the
16 5. 17 0.12 Do.
24 7.69 Do. exception of GR- I and GR- M] were also vul-
32 10.44 3.57 Do. canized to a " leath ery" state] and to vulcanizing
64 14.63 7. 18 Some cure noticeable.
128 27.55 15.64 Slight undercure. coefficients as high as 3 to 15 . At these higher

4 Journal of Research

L
 cq.

;,.

'> 220 independently of the other to cau e any significan t

200
0 increase in weight in the rubber. Thel'cCo l"e it i
~
z
w 180
\ J>easonably certain that any appreciable increase in
weight on the dry basis is caused by a combination
u
II:
w
Go 160
z·
\ of the nascent sulfur, which is r eleased by th e in ter-
action of the two gases within the specimen, wi th
0
~ 140
1\ the unsaturated bonds of the rubb er , plus any
~
c
free sulfur that the sample is able to hold in
'"0z ~
t ..J
w
120

100
~ ~
.........
I---, ) -
I---, f - -
~O
0 5 10
TIME OF EXPOSURE. MINUTES
> FIGURE 5. Elongation at stress of 15 kg/cm2 (213 psi) for
natural rubber samples under different degrees of cure.
For some of the samples t he stresses were m easured
01hoI's transver sely to t he d irection o f p assage between the mixin g ro lls.
degrees of vulcanization there was quito a large
amount of free sulfur deposited on tho surface of
th e rubber. No attempt was made to continue
toward a higher degr ee of vulcanization. St.
R einer [8J, however, did continue the reaction
fur th er and claims that h ard rubb er can b e pro-
duced from natural rubber by this process.
T A BLE 4. Optimu ?n cu res fr o?n table 3
Cyr-Ics fo r
T y pe of polymer optimum
cure
Nat ural. ............................... .
O R - A __ ._ .. _. __ ....... _... _.. _..... _.. .
IT year OR- i 5_....... __ ._ ... _. _.. _. ___ .. .
IT year OH- 25_.. ___ ......... _._ .. _. ____ . _
n year OS-1O _.. _._ ..... _... _. __ ........ .
n year OS-20 _.... . .. _... . . .........•....
n year OS-30 _............ _............. .
O R -S .... _..... ...... ................ . . .
a R- L ................ . ................ . .
O R- M ..... _......... . .. _. ... .......... .
1 Based 011 pa rts per hlllldred parts of polymer.
IV. Discussion of Results
As only about 0.2 percent weight incr ease was
effected by either of the P eachey process gases
alone, it is clearly indicated that there are no ap-
preciable side reactions whereby one gas might act
TRANSVERSE -
solu tion or as a deposit on the surface _ Thi s
reaction of th e gases within the rubber sample, in
addition to forming nascent sulfur, also produces
LONGITUiOINAL water_ Although it is quite possible that t he
15 2
quantity of moisture present in the samples or in
th e gases may have an effect on the rate of the
vulcanizing reaction [3J no attempt was m ade to
measure this amount because all of th e sa mples
lon ~ i tudinally a nd
were subjected to th e sam e general condi tions that
should produce comparative resul ts_
It is interesting to note th at in the init ial series
of tests on naturai rubber, as can be see n in fi gul'e
1, a greater quantity of sulfur was taken up when
the rubb er had been compounded with zinc ox ide
and stearic aGid, but that no furLher sign ifLcant
addit ion of sulfur was noted when an accelerator
(m ercap tobenzo thiazole) and an ultra accelerator
(zinc dimcthylclithiocarbamate) were added _ Sev-
eral possible explanations may be suggested _ The
z inc oxide and t he stearic acid may suppl y an ac-
" ' eigh t Com b ined
celerating efl'ect th at causes more sulfur to com-
illcrcases sulfur 1 bine with the rubber in a given length of time, in
---- effeet speeding up t he r ate of cure. It may also
P ercent Percent
2 3.52 2.31
b e tha t the sulfur is merely displacing the oxygell
8 2. 65 1.14 of the zinc oxide to form zinc sulfide, which could
8 2.52 1. 37
8 3.58 2.55
readily account for th e additional increase in
8 1.93 1.24 weight_ S_ J _ Peach ey [6J believes that com-
2. 14 1. 21
4 1. 73 1.17
pounded rubber absorbs the gases more readily
8 4. 30 3. 08 than pure rubber. As this phase was not of pri-
128 5. 30 1.12
mary intercst to t his investigation, thi s problem
> 128 > 27. 55 > 15.64
was not probed deeply enou gh to ascer tain the
correct explanation_ However , it is felt th at
these particular accelerators apparently h ad little
or no influen ce on the amount of the sulfur added.
St_ Reiner [8], on the other hand, claims that
certain organic accelerators speed up the reaetion_
vYhether or not h e too used a metallic oxide alon g
with t he accelerator , as is customary for ho t
curing, and mistakenly attribu ted the increase in

Peachey Process on Synthetic Rubbers 5

r ate of th e sulfur adcli tion solely to th(' presence of
t h e acceler ator is no t knowll.
In some of the preliminary run s, it wa s noticed
th at th ere wer e vari ations in th e amoun ts of sulfur
tak en up by th c same polym er for a similar num-
ber of cycles in differen t series of runs. In th ese
early runs th e polymcrs may not h ave been sh eeted
as uniformly in t hickness as in th e later run s. As
h as already been mentioned, th e amount of mois-
t ure presen t in the polym er may also h ave affected
th e rate of cure . H owever , this phase of th e
problem was no t studied fur ther , as th e sole pur-
pose of this investigation was m er ely to learn
wh ether or no t syn th etic rubb ers could b e vul-
cani zed by t his m ethod.
It sh ould b e pointed ou t th at H ycar OS- 20 and
Hycar OS- 30 cured at approximately the sam e
rate, showing t hat th e presence or absence of fat ty
acids in th e butadi ene-styr ene type polymers is
imma t erial as far as th c vulcani zing process is
v ulcaniza te. T able 5 and fi gure 5 show that all
of th e sp ecimens cu t transverse to the direction
of passage of the rubber between th e mill rolls
h ave a substan tially high er degr ee of elongation
and permanen t set t ha n those cut longitudinal to
the direction of millin g wh en subj ected to th e same
relative stress. The sh earing action produ ced by
the differ ence in sp eeds of the two r olls of the mill
par tially stretch es and aligns th e molecules of th e
rubber. The sp ecimens t hat are cu t and vulcan-
ized in th e same direction as th e partially elongated
ch ains n atur ally will no t str etch as much as those
cut at righ t angles to th e already str etched con-
figura tions under the same force .
T ABLE 5. Bffect of direction 0/ millmg on stress and set
:Elongation Permanent set
Len gi h W eight - - - - - - -- - -
Type of polymer of in-
cycles crease Long:i·
Lu di·
Trao!;j- Longi- rrrHn~ -
iudi·
n al verse n al Y el'SC

co ncern ed (see fi g. 3) . Th e H ycar OS- JO , having ------------ - - - - - - - - - - - - - -

a high er s tyr ene conten t th an th e H ycar OS- 20, ndn. Perce nt P ercen t Perc ent Perce nt P er ('en!.

Hycar OS- 30, or the GR- S, mu st h ave fewer 1, ~,

2.5
1. 16
1. 97
135
122
203
15 l
4.8
3.2
8. 8
5. 6
double bond s, and consequen tly vulcanizes a t a Nat ural .... ............ 5 3. 18 98 12 1 1.6 4. 8
.10 3.86 88 104 1.6 4.
slower rate. GR- A and H ycar OR- I 5 wer e so 2~ 4. 29 80 96 1.6 4.
similar in th eir rates of cUre that th e da ta h ad to b e
plo tte d as one and the sam e curve (sec fi g. 2) .
H ycar OR- 25 has a lower acryloni trile conten t These sam e conclusions are drawn from some
than t he H ycar OR- I 5 and t he GR- A, and ther e- unpu blished experiments performed several years
for e, b ecause of t h e larger number of double bonds, ago by W . H . Smi th and F . L. Ro th of th e Na tional
vulcani zes at a greater r ate. Bureau of S tandards. They stretch ed a wide
After a large numb er of cycles GR- I h ad t aken flat strip of raw rubb er and vulcanized i t while in
up very li ttle combined sulfur, probably b ecause the elongated sta te by th e sulfur chloride method.
of th e presence of r elatively few double bond s in Dumbbell sp ecimens wer e cut from thi s vulcanized
thi s polym er . This may explain why so mu ch strip bo th in th e direc tion of str etch and also at
time is r equired for a good cure. The vulcaniz a- righ t angles to it . The specimens that were cu t
tion of GR- M , which normally is vulcanized by transverse to th e direc tion of original stretch were
th e use of m etallic oxid es rath er than of sulfur , softer and showed considerably greater valu es of
also b eh aves differen tly in the P each ey process. ultimate elongation and tensile strength .
1
).Iuch sulfur was t aken up by the GR- M:, and even
combined ch emically with i t, bu t an undercure
,,·as still ob tained when over 15 percen t of sulfur The au thors are indeb ted to Eleanor F. P ang-
had combined . born for making th e many sulfur determinations
By vul canizin g strips of rubber by th e P each ey necessary for th e preparation of th e tables given
process, it was possible to show a very striking in this pap er . The investigat ion r esulted from
illustr a tion of th e influence th at th e direction of an original s uggestion by H arry L. F ish er, Office
milling h as on cer tain physical proper ties of th e of Rubb er R eserve.

6 Jo urnal o f Researc h
 v. References 15J A. T. M cPherson, Vulcan iza tion o f GR- S byI the
P eachey process, Rubber Age 59, 323 (1946) .
::: I] J P oss ibilil ie
of the Pcach ey process, India Rubber [6] S, J. P eachey, Lecture on cold vu lcan izat ion, India
Worlel 62, 787 (1920) . Rubber J. 63, 427 (1922).
12J Thc pcrfccted P eachey process, Rubber Age 19, 195 [7 J S. J. P eachey and A. k ip scy, Ncw proccss for t he
(1926) . v ulcanization of rubber, J . Soc. Chem. I nd. Trans.
40, 5( 1921),
131 L. H oeh and H. Schmidt, The format ion of s ulfur from
18J St. R einer , Obs') rvations on the fo r mation of s ulfur
;> hydrogcn s ulfidc and sulfur di ox ide, E a utschuk 10,
from hydrogen sulfid e and s ulfur dioxide, Kautschuk
82 ( 1034 ) .
10, 128 (1934),
>- 14J F . Jaco bs, The Peache~' process, Caoutchouc and
Glltla-PCJ'clla 2(; ,14506 (1929) . W AS HINGTON, Sep tember 5, 1947,

I
I
/.
Peachey Process on Synthetic Rubbers 7