Technical Report No.

56 – Processing promoters

Processing Agents in Black and Non-Black Compounds

Walter Schuette (Rhein Chemie Corp., USA) – June 1996

Paper presented at the ACS Meeting, October 17–20, 1995, Cleveland, USA (Literally)

„Rhein Chemie offers two lines of processing promot- The reason for these distinctions will become clear as
ers that can be described as soaps and blends. These we progress through this presentation. If we analyze the
rubber soluble soaps, known as the Aktiplast® products, composition of the Aktiplast types, we find that the
are the reaction products of saturated and unsaturated products consist of blends of saturated and unsaturated
C18 fatty acids with zinc oxide (Fig. 1).The blends, in fatty acids ranging from the highly saturated stearic
contrast to the soaps, are mainly rubber insoluble and acid to the high unsaturated linolenic acid (Fig. 3).
are blends of plasticizers from the families of fatty There is also a third series of processing promoters
acids, fatty acid esters, calcium salts of fatty acids, known as Rhenosin® (Fig. 4), which are thermoplastic
polyethylene, and high MW esters (Fig. 2). aromatic hydrocarbon resins. They function as homoge-
nizing agents, both discoloring and nondiscoloring.

Fig. 1: Processing Promoters from Rhein Chemie Fig. 3: Processing Aids fatty acid derivatives
The Aktiplast Series (Soaps)
Fatty Acids
Aktiplast T Molecular weight distribution
Zinc salts of mainly C-18 unsaturated fatty acids
Aktiplast PP
Zinc salts of mainly C-18 saturated fatty acids f.a. 10 12 14 16 18 20 22 C-No.
Aktiplast F 18’
Activated version of Aktiplast T 18’’
Aktiplast M Character e.g. for C=18
Activated version of Aktiplast PP unsaturated saturated
Aktiplast GT
Zinc salts of both high and low mainly saturated fatty
acids linolenic a. linolic a. oleic a. stearic a.
Aktiplast 8 18’’’ 18’’ 18’ 18
Activated mixture of fatty acids, soaps of fatty acids and
fatty alcohols Structure

Acid Soap Ester Alcohol Blend

Fig. 2: Processing Promoters from Rhein Chemie
The Aflux® Series (Blends)
Aflux 12
Fatty acid esters, water and hydrocarbons bound on
inert filler
Aflux 16
Calcium salts of natural fatty acids mixed with an amide
ester wax
Aflux 25
Blend of isoalkanes and fatty acids
Aflux 42
Blend of fatty acids, fatty acid ester and fatty alcohols
Aflux 54
Pentaerythrityltetrastearate

Technical Application Service Rubber

 very little solubility in EPDM. According to our chart,
Fig. 4: Processing Promoters from Rhein Chemie
The Rhenosin Series
which give us a total solubility number of four, in NR,
the results look quite similar. The overall solubility is
Rhenosin 145A
Alkylated naphthenic/aromatic resins slightly better, with a solubility number of 7. Now,
Rhenosin 260 moving on to the more polar polymers, we see that the
Thermoplastic aromatic hydrocarbon resin alcohols show a decent solubility, the acids and even the
Rhenosin 300
Alkylated naphthenic-formaldehyde resin
esters exhibit an even better solubility. Thus, the blend
Rhenosin 300 M-10 definitely shows a much higher solubility number. It is
Alkylated naphthenic-formaldehyde resin and synthetic fair to say that Aflux 42 would generate very good
calcium silicate
Rhenosin 400 extrusion characteristics in EPDM and NR. Conversely,
Mixture of alkylated naphthenic/aromatic resins with zinc when used in CR and NBR, one would expect very
salts of mainly unsaturated fatty acids good carbon black dispersion.
Rhenosin 402
Mixture of alkylated naphthenic/aromatic resins with zinc
salts of mainly unsaturated fatty acids with a booster The Aflux 12, analyzed in the same polymers, shows a
Rhenosin 403
slightly different picture. Aflux 12 is composed of
Mixture of alkylated naphthenic/aromatic resins with zinc
salts of mainly saturated fatty acids with a booster esters that are slightly different from those used in the
Aflux 42. This product is a combination of wax, calci-
Rhenosin 300, a special alkylated naphthalene formal- um carbonate as a carrier and water. There is about 12%
dehyde resin, is particularly useful in very polar poly- water in the product. With that in mind, let us turn our
mers. The Rhenosin series also consists of blends of attention to the same matrix. We see that Aflux 12 is not
Rhenosin 145A with various zinc soaps, boosted and very soluble in EPDM. The wax is rated a five, so the
non boosted, referred to as 400, 402 and 403. total solubility is 5. The calcium carbonate is not
soluble since fillers are not soluble, and of course the
Now that we have an overview of the basic types of water is definitely not soluble. In NR, the esters and
available processing promoters, you will recognize that waxes have very poor solubility. Needless to say, the
all of them can be grouped into those products that are water is not soluble at all, so the total in NR for Aflux
largely polymer soluble and those that are largely poly- 12 is a very low number of 2. In CR, the picture is pret-
mer insoluble (Fig. 5). In practical terms, the differen- ty much the same; however, in NBR, the polar element
tiation between these classes is that the soluble ones has a slightly improved solubility for the esters, which
dissolve into the polymer, behave as internal lubricants, is probably the extent of solubility. To summarize,
swell the polymer chains, increase the surface area and Aflux 12 is a fantastic slipping and sliding agent in all
facilitate the dispersion of the materials to be mixed the polymers that we know and will be especially
into the polymer; whereas, those of the second group advantageous for injection molding and extrusion. This
are relatively insoluble in the polymer, behave as exter- is also true in carbon black compounds, due to the
nal lubricants, most likely migrate to the polymer sur- water in the Aflux 12 and the hydrophobic nature of the
face of the stock where they improve injection molding black combine to produce good extrusion rates. For
characteristics and suppress die swell. those people who say that the water is probably being
lost during the mixing, we would have to say that this is
logically true; however, as you store the mixed com-
Fig. 5: Processing effects are function of solubility pound, the Aflux 12 in the mix will absorb water from
Polymer Known as Swell and Facilitates the environment.
soluble = Internal = lubricate = dispersion
processing lubricants polymer of ingredients
promoters chains
Fig. 6: The function of a processing promoter in any
Polymer Known as Migrate to Facilitates
given polymer is determined by its solubility in
that polymer
insoluble = External = polymer = extrusion and
processing lubricants surfaces injection molding
Aflux 42 EPDM NR CR NBR
promoters characteristics
Alcohols 0 1 7 7
supresses die
Fatty Acids 2 3 5 8
swell
Esters* 2 3 5 8
Total 4 7 17 23

In the first example (Fig. 6), we compared two blends; Aflux 12 EPDM NR CR NBR
Aflux® 42 and Aflux 12. We will discuss the solubilities Esters** 0 1 2 5
Wax 5 1 0 0
of the many components of these blends in the various CaCO3 0 0 0 0
polymers and describe how they function in these same Water 0 0 0 0
polymers to show you the correlation between polymer Total 5 2 2 5
solubility and the effect of these processing aids in a
The ratings are from 0 to 10 where 0 means total
rubber compound. insolubility and 10 means total solubility
Starting with Aflux 42, we begin our study by identify-
*Esters of fatty alcohols and fatty acids
ing the exact components of the process aid. The Aflux **Pentaerythrityltetrastearate
42 is a blend of fatty alcohols, acids and esters. In ana-
lyzing the behavior of these individual chemicals in
EPDM, we see that the alcohols have no solubility in Let us examine a couple more examples. For easy ref-
EPDM. The fatty acids, and similarly the esters, show erence, I have copied the solubility chart of Aflux 42 on
the bottom of Figure 7. The first example is showing
Fig. 8: Aflux 12 in a white NR/BR compound
the performance of Aflux 42 in a CR stock, where it is Tennis Shoe Sole
relatively soluble. Due to this solubility, it behaves as a
Recipe (phr): A B
dispersing aid, allowing for dramatically lower mix
temperatures and thus longer scorch times. As the Aflux SMR 20 70 70
Cis-BR 30 30
42 is increased from zero phr in the control to 6 phr in HiSil 233 55 55
increments of 2 phr, the Mooney scorch increases from Zinc oxide 4 4
7.5 minutes to 11.6 minutes. The Mooney scorch is Flexon 845 4 4
Diethylene glycol 3.5 3.5
increased about 50% by the time four parts of Aflux 42 Ti-Pure R101 10 10
are added to the compound. Antilux® 654 0.6 0.6
Vulkanox KB 1.5 1.5
Stearic acid 1.5 1.5
Fig. 7: Aflux 42 in a white Polychloroprene compound TMTM 0.3 0.3
MBTS 1.0 1.0
Recipes (phr) A B C D MBT 0.5 0.5
Baypren® 210 50 Sulfur 1.5 1.5
Baypren® 215 50 Aflux 12 – 2.5
Vulkanox® AFC 1
Vulkanox KB 1 ML(1+4)100C: 68 57
Stearic acid 1 Extrusion rate (cm/min.): 69 91
OSW 110 3
Vulkasil® S 50
TiO2 (Anatase) 2 therefore, it behaves as an external lubricant, resulting
Disflamoll® DPK 13 in very good flow properties.
Rhenomag® P2 4
Zinc oxide 5
Rhenogran® ETU-75 0.7 The next example (Fig. 9) is a comparison between
Aflux 42 – 2 4 6 Aflux 12, which has very limited solubility in NBR,
Mooney Scorch at 120°C: and Aktiplast T, a soap, which is totally soluble in NBR.
t5 (min.): 7.5 8.7 10.7 11.6 Referring again to the solubility matrix, we can defi-
t35 (min.): 14.5 18.5 21.2 23.0
nitely see that Aflux 12 generates an incredible surface
Extrusion at 180°C: lubrication resulting in greatly increased injection
speed (cm/min.): 97 99 93 101
output (g/min.): 135 140 133 142 molding speed and a much higher loading of the injec-
tion spider mold. These properties are somewhat
Physical properties (cured 30 minutes at 150°C):
improved over the control with the use of Aktiplast T,
Hardness (Shore A): 65 62 64 63 which is totally soluble in NBR.
Elasticity (%): 35 34 32 32
Modulus 100% (MPa): 2.1 1.9 1.7 1.7
Modulus 300% (MPa): 5.2 5.1 4.4 4.2
Modulus 500% (MPa): 8.7 8.9 7.6 7.3 Fig. 9: Internal versus External Lubricants in NBR
Tensile strength (MPa): 14.2 15.0 15.0 15.1 Recipes (phr):
Elongation at break (%): 690 710 770 690
Tear (Die C) (N/mm): 26.1 23.7 29.1 27.1 Perbunan® N 3307 100 100 100
Carbon Black N-550 65 65 65
Vulkanol® 85 10 10 10
Stearic Acid 0.5 0.5 0.5
It simply shows that Aflux 42 in polar polymers has a Vulkanox HS 1.5 1.5 1.5
Vulkanox MB 2 1.5 1.5 1.5
decent solubility. This solubility improves filler disper- Zinkoxyd Aktiv 5 5 5
sion, and because of enhanced filler dispersion, physi- Sulfur 0.4 0.4 0.4
TMTD 2.5 2.5 2.5
cal properties are improved. However, you do not see Aktiplast T – 3 –
the dramatic improvement in extrusion rates that you Aflux 12 – – 3
would have obtained with Aflux 12. What is important Mooney viscosity
to note is that even with the increases in Aflux 42 con- ML(1+4) 100°C 85 80 70
centration, which is essentially adding more plasticizer Physical properties (cured 10’ @ 160°C):
to the compound, physical properties are maintained. Hardness (Shore A) 73 70 70
Elasticity (%) 31 30 30
Tear strength (N/mm) 24.4 22.9 27.2
The next example is Aflux 12 in a typical tennis shoe 100% Modulus (MPa) 4.9 4.1 4.3
sole (Fig. 8). Again, I refer to the bottom of the page to 300% Modulus (MPa) 16.3 13.6 13.8
Tensile strength (MPa) 19.8 20.1 19.1
review the solubility of Aflux 12 in NR. The recipe is a Elongation at break (%) 400 500 435
simple NR/BR blend, loaded with HiSil, and the normal
Extrusion speed (cm/min.) 118 140 144
standard thiazole cure system. The control stock does Extrusion output (g/min.) 100 125 140
not contain Aflux 12. The most obvious differences be- Rheovulkameter (180°C/50s/80 bar)
tween the two stocks are that in the Aflux 12 containing IM volume (mm3) 305 580 863
stock, the ML(1+4) is greatly reduced and the extrusion IM speed (mm3/s) 11.3 16.5 24.5
rate is greatly increased.

As we all know, NR/BR extrusion compounds can be as

hard as wood and the extrusion rate or flow rate, espe-
cially across the mold, is important. In this case, the Without 3 phr Aktiplast T 3 phr Aflux 12
Processing Promoter
Aflux 12 has very little solubility in the NR matrix;
In this case, the slight improvement in molding num-
Fig. 11: Blooming of Aflux 16 and Aflux 42
bers is due to some of the Aktiplast T ingredients being
on the surface. On account of its greater solubility in
the rubber matrix, it cannot perform like the Aflux 12.

Unfortunately, we did not see an increase in tear

strength that would be associated with better carbon
black dispersion; however, I would like to point out that
tear strength values can be rather erratic at times.
Same compound; Angled photographs
One point worth mentioning, is that the tensile strength
values have been maintained throughout the entire
gamut of the test series and percent elongation at break
values have only slightly changed with the increased
levels of plasticizer. If these changes are unsatisfactory,
removing some of the plasticizer will restore them to
the original values.

In Figure 10, I would like to show the effects of an

Aflux 16 and Aflux 42 comparison in an EPDM mold-
ed compound. Thinking back to the beginning of this
presentation, you will remember that the Aflux 42 is Fig. 12: Mechanical Mastication
virtually not soluble in EPDM; whereas, Aflux 16 is
Advantages:
chemically a calcium soap and much more soluble in
EPDM. The important point to be demonstrated here is a) Homogeneous mastication of rubber providing
smooth compound with good flow properties.
mold fouling. In these comparison stocks, both the b) Vulcanizate has good physical properties.
Aflux 42 and the Aflux 16 are used at the 3 phr level.
Disadvantages:
Basically, all of the physicals are pretty much the same.
The big difference can be seen when you look at the a) Takes a long time
b) Energy intensive
mold and slabs. Since Aflux 16 is totally soluble in the
polymer, it does not bloom to the surface and thus does
not cause mold fouling (Fig. 11). Chemical Mastication

Advantages:
Fig. 10: Aflux 16 versus Aflux 42 in an EPDM Injection a) Fast mastication process
Molding Compound
Disadvantages:
Recipes (phr): A B
a) Dispersion problems with small amounts of peptizer
EPDM 100 100
b) Masterbatch is not homogeneous
Carbon black N-550 85 85
c) Masterbatch stickier and not easy to process
Rhenopren® EPS 5 5
d) SBR and NR/SBR blends tend to form gel
Paraffinic oil 85 85
Rhenogran ZNO-85 3.6 3.6
Stearic acid 1 1
Rhenosorb® C/GW 5 5 compound with very good flow properties. Since mini-
Vulkanox OCD 1.3 1.3 mum damage was done to the molecular weight, the
DPTT 0.5 0.5 vulcanizate has very good physical properties. The
ZDBC 2 2
TDEC 0.3 0.3
disadvantage of the procedure is that is is very time
TMTD 0.3 0.3 consuming and requires a lot of energy.
MBTS 1 1
Sulfur 1.5 1.5 On the other hand, the outstanding advantage of chemi-
Aflux 16 – 3
Aflux 42 3 – cal mastication is the fast rate of mastication. The main
disadvantage is the inherent dispersion problem caused
Mooney Scorch at 270°F (min.): 10.0 9.3
by trying to disperse small amounts of peptizer homo-
Physical properties (cured 10 minutes at 350°F):
geneously throughout the bulk of the rubber, because
Hardness (Shore A): 50 50 most chemical peptizers are used at 0.2 to 0.3 phr
100% Modulus (Mpa): 1.9 2.0
200% Modulus (Mpa): 4.1 4.2
levels. From this information it is not too difficult to
300% Modulus (Mpa): 5.9 6.1 realize that the batch has to be very unevenly peptized.
Tensile strength (Mpa): 12.1 12.5 Masterbatches masticated with chemical peptizers are
Elongation at break (%): 540 520
generally stickier and difficult to process. In addition,
NR and NR/SBR blends tend to form a gel pretty
Another topic of discussion, of particular interest to the quickly. If we compare this with the diluted activated
tire industry, concerns the differences between me- zinc soaps that RCC offers as diluted chemical pepti-
chanical and chemical mastication (Fig. 12). The zers, one will see that the activated or boasted zinc
advantage of mechanical mastication, is a homo- soaps show extremely high efficiency even at low
geneous mastication of the rubber resulting in a smooth temperatures.
Other advantages include greatly reduced mixing times The reason for combining a highly viscous material
with faster and more homogeneous dispersion of the with activated zinc soaps was to avoid slippage in the
active chemicals and carbon black (Fig. 13). You will mixer before the chemicals could dissolve in the poly-
surely avoid the “hot spots” because the carrier will dis- mer matrix and begin breaking down the polymer
solve first into the rubber matrix to release the small chains.
amount of oxidizing agent. Consequently, there is less
surface tackiness, less mold fouling in injection mold- In this next example (Fig. 15) you will see a direct com-
ing, and better processibility overall. Due to the solubi- parison of Aktiplast M against Renacit® 7. The test was
lity of the carrier, you have very good filler or carbon designed to use a 40% fill factor in a normal Farrell lab
black dispersion. Also zinc soaps protect, e.g. the aspi- Banbury featuring a 60 second mix time at a defined
rin, for preventing cyclization for NR and NR/SBR rotor speed. In each case, the NR was either mixed with
blends. And finally, the polymer matrix will retain a 0.3 phr Renacit 7 or with 2 phr Aktiplast M. You may
much higher MW that will enable the compound to recall that Aktiplast M is 99% a process aid with only a
have much better overall physical properties. minute amount of a chemical oxidizing agent. There-
fore, the comparison of 0.3 phr against 2.0 phr is com-
pletely realistic.
Fig. 13: Aktiplast M & Aktiplast F
Advantages of Using Diluted Chemical Peptizers
Efficient peptizers even at mill temperatures as low as Fig. 15: Peptizing Effect
60°C Aktiplast M – vs – Renacit 7
Reduce mixing time The conditions were as follows:
Facilitate more homogeneous distribution of the active
chemical 1. Farrel BR laboratory banbury
2. 40% fill factor
● No ”hot spots” 3. 60 second mix time
● Less surface tackiness 4. Rotor speed: 60 RPM
● Less mold fouling in injection molding
Ingredients:
Improve overall flow characteristics of uncured stocks
1. SIR 20 Natural Rubber
Facilitate more homogeneous dispersion of fillers/cura- 2. 0.3 phr Renacit 7
tives
3. 2.0 phr Aktiplast M
Eliminate tendency toward cyclization in NR/SBR blends
Test Procedure:
Polymer retains overall higher average molecular weight
1. Each batch passed once through a 1/4’’ open mill
● Better carbon black dispersion due to higher shear 2. Each batch cut into 16 pieces
● Overall improvement in physical properties
3. Mooney Viscosity at 100°C determined on all pieces
from center and edges of ”sheeted” batch

The entire product line of processing promoters that we Test Results (Mooney Viscosity at 100°C):
offer with chemical peptizers is composed of four spe- Renacit 7 Aktiplast M Renacit 7 Aktiplast M
cial products: (1) Aktiplast T, which is a boosted un- 61.3 54.2 63.4 53.4
68.3 55.5 63.6 54.1
saturated C zinc soap; (2) Aktiplast M, which is a
18
70.9 58.0 67.0 55.8
boosted basically saturated C zinc soap; (3) Rhenosin
18 Mixed 60 sec. at 60 RPM Mixed 60 sec at 80 RPM
402, which is a blend of Rhenosin 145 plus Aktiplast F;
and (4) Rhenosin 403, which is a blend of the Rhenosin
145 with Aktiplast M (Fig. 14). After mixing in the Banbury, each batch was passed
once through a 1/4” open mill to sheet it out. Each sheet
was cut into pieces and the viscosity of each of these
Fig. 14: Processing Promoters of Rhein Chemie
pieces was determined at 100°C. Samples were taken
Containing Chemical Peptizers
from the center and edges of the sheeted batch. It is
The Aktiplast types listed below function as peptizing apparent that those samples containing Renacit 7,
agents, dispersants, and internal lubricants. They increa-
se stock plasticity, improve flow properties in extrusions, mixed under the same conditions as those containing
injection moldings, and considerably reduce mold Aktiplast M, exhibit about twice the Mooney spread of
fouling. The products below contain a very small amount
of chemical peptizer to facilitate mastication.
those mixed with the Aktiplast M. This confirms the
suspicion that even within a single batch, there are
Aktiplast F Mixture of activated zinc salts of mainly areas that are more highly peptized than others, thus
unsaturated higher molecular weight
fatty acids. creating zones of varying degrees of carbon black
dispersion and consequently zones of differing viscosi-
Aktiplast M Mixture of activated zinc salts of mainly
saturated higher molecular weight fatty ties. This is explicit evidence of what we discussed.
acids.

Rhenosin 402 Mixture of activated alkylated

Molecular weight and molecular weight distribution
naphthenic/aromatic resins with zinc play extremely important roles in polymer processibili-
salts of higher MW mainly unsaturated ty and the ultimate physical properties of the vulcani-
fatty acids.
sate. The goal during peptization is to break all the
Rhenosin 403 Mixture of activated alkylated chains in the middle, resulting in relatively long chain
naphthenic/aromatic resins with zinc
salts of higher MW mainly saturated
fragments, rather than to chop a lesser fraction of the
fatty acids. polymer chains into tiny pieces. In either case, the mea-
sured average molecular weight may be the same; how-
ever, the manner in which the polymer processed would as the DEFO Hardness or DEFO Elasticity Test, then
vary greatly. The data in Figure 16 show the improve- you see that the DEFO Hardness numbers spread any-
ments possible using diluted chemical peptizers over where from 1100 to 525. A similarly large spread is
straight powdered chemical peptizers. seen with the DEFO Elasticity numbers, which are
In this set of data, we are looking at the development of from 29, 30, and 34 for the chemical peptizers to 17 and
MW where we are using or applying the various diluted 18 for the RCC diluted peptizers. That is a significant
process aids versus a powdered chemical peptizer and difference. The DEFO Elasticity numbers are essen-
even stearic acid. tially cut in half with the RCC diluted peptizers. It goes
without saying that the lower the DEFO Elasticity
Number, the easier it will be to process the stock
Fig. 16: Molecular Weight
through a cold feed extruder.
MW Mn Mz U = Mw –1
Mn

Aktiplast M 450,000 170,000 810,000 1.77

Fig. 17: Mastication and Processability
Renacit 7 320,000 110,000 260,000 1.76 Laboratory
receipe (phr) 1 2 3 4 5 6
Aktiplast T 520,000 160,000 990,000 2.22
Light
Aktiplast PP 610,000 190,000 1.100,000 2.23 Crepe 5L 100 = = = = =
Renacit 7 0.15 0.3 – – – –
Stearic Acid 750,000 240,000 1.300,000 2.14
Aktiplast M – – – – 2 3
Without 520,000 190,000 870,000 1.71 other Proc.
Mastic. Aid prom. – – 0.15 0.3 – –
SMR 10 mixed 2.0 minutes at 120°C
ML 1+4/
100°C 53 42 47 39 38 39
0.04 Mn

Mv DEFO/80°C 1100/29 800/30 950/34 750/29 625/18 525/17

0.03 Mw Blending Procedure
WEIGHT FRACTION

MGPC Temperature 120°C

Mastication Time 5 Min
W(M)

0.02
Mz
Equipment Laboratory Mill

0.01
What does that mean? I would like to explain in a few
words the test that we conduct to identify this (Fig. 18).
0 We very simply make up a 1.5 cm thick rubber pad of
0 1 2 3 4 5
M/Mn uncured rubber and, at a defined temperature, identify
or find the weight that pushes or squeezes the rubber
cylinder from 10 mm down to 4 mm. This weight, or
We know that the MW of the NR before mastication that number, i.e. the weight that we identify that does
must be greater than 750,000 because that is the value the job, is called the DEFO Hardness. The weight is
of the mix containing stearic acid. The likelihood that it removed from the rubber cylinder and the rebound is
increases after mastication with stearic acid is virtually measured. The distance the rubber rebounds within 30
zero. Renacit 7 has definitely cut back the most on the seconds is recorded as a reciprocal and that reciprocal
molecular weight, followed by Aktiplast M, which con- value becomes the DEFO Elasticity number. As a
tains a small booster. Next is Aktiplast T, which is very result, the higher the rebound, as a reciprocal number,
soluble in the rubber. It does change the molecular the lower the DEFO Elasticity value, the better the pro-
weight. As you may very well suspect, Aktiplast PP, cessibility of the rubber. As previously shown, the Akti-
being largely saturated and thus less soluble, shows the plast treated NR parts have half the DEFO Elasticity
least aggressive attack on the molecular weight and is values compared to the chemical peptizers.
the closest to the performance of stearic acid.
Let us discuss in greater detail Aktiplast F and M and
We said earlier that NR compounds processed with ei- chemical peptizers in relation to how long it takes to
ther Renacit 7, a chemical peptizer, or an activated zinc disperse carbon black into an NR/SBR compound (Fig.
soap, will show totally different processibility. One of 19). When you compare stearic acid with a chemically
the ways RCC uses to identify this difference is with the peptized zinc soap, the results are in favor of the zinc
DEFO analyses: DEFO Hardness and DEFO Elasticity soap. It only takes Aktiplast M about a third of the time
Test. to disperse the carbon black compared to the stearic
acid. Aktiplast M, compared to the Renacit 7, the
We have used this test to show the differences between chemical peptizer, shows a mixing time reduction of
Renacit 7, Aktiplast M and a third processing promoter almost 50%.
(Fig. 17). Although they have similar ML(1+4) which is
minor, the rubber does not show any obvious differ- The Figures 20–23 will illustrate through power con-
ences. If numbers measured at 100 °C, with a spread sumption charts what was done. The carbon black
from about 53 to 38, you submit the same piece of rub- dispersion time was measured from the time the ram
ber to a different test method or analysis that we refer to came down, which is shown by the first notch, to the
 Fig. 18: DEFO Hardness/DEFO Elasticity – Fig. 20: Stearic Acid
Test method Power Consumption Chart
1. a. Make up 15 mm thick pads of the uncured rubber
at a maximum of 100°C. Then punch out a cylindrical
test piece, 10 mm diameter and 10 mm in height.
b. At 80°C, try to find the weight it takes (in grams)
to squeeze this cylinder from 10 to 4 mm within 30
seconds. This weight is referred to as DEFO Hardness.
c. Remove the weight from the cylinder. After 30
seconds, measure the amount of recovery of the cylin-
der in 1/10 mm. This is referred to as DEFO Elasticity.
2. DH is also a suitable means to measure the plasticity
or the softness of the rubber or a compound. DE is a Carbon Black Incorporation Time: 63 seconds
very suitable measure of the internal elastic properties of
the compound.
Low DE – values point out good processability, smooth Fig. 21: Renacit 7
flow, low die – swelling and shrinkage. High DE number
Power Consumption Chart
points at inner crosslinkage high shrinkage and less
favorable processability.

Carbon Black Incorporation Time: 45 seconds

Fig. 22: Aktiplast F

Power Consumption Chart

Fig. 19: Carbon Black Incorporation as a Function of

Peptizing Agent
Recipe (phr) A B C D
SIR 10 96.0
SBR 1516 4.0
Carbon Black N-330 60.0
Naphtolen ZD 8.0
Vulkanox 4010 1.2
Vulkanox 4020 0.8
Vulkanox HS 1.0
Antilux 654 1.2 Carbon Black Incorporation Time: 45 seconds
ZnO Special 3.0
Vulkacit® DOTG 0.2
Vulkacit TMTD 0.2
Vulkacit TBBS 1.0 Fig. 23: Aktiplast M
Sulfur 2.0 Power Consumption Chart
Rhenogran CTP-80 0.3
Stearic Acid 2.0 1.0 1.0 1.0
Renacit 7 – 0.2 – –
Aktiplast F – – 2.0 –
Aktiplast M – – – 2.0
Carbon Black
Incorporation 63.0 45.0 45.0 24.0
(seconds)

first peak. After reaching the first peak, there is a

steady drop off in the curve. This drop-off can be identi-
fied as a homogenizing phase.
Carbon Black Incorporation Time: 24 seconds

The distribution of the carbon black, i.e. the dispersing

phase, should definitely be considered completed after Another positive feature of Aktiplast M when used in a
reaching the first peak. From these power consumption typical SMR 20/BR stock pertains to mix time (Fig.
charts, stearic acid requires 63 seconds and Renacit 7 24). This feature can be seen in this very complicated,
requires 45 seconds, compared to Aktiplast M that only highly loaded retread stock containing both NR and
requires 24 seconds to completely disperse the carbon BR, two different kinds of filler, and a relatively low
black into the compound. dosage of oil. The Aktiplast M makes it possible to put
this same compound together in 8.5 minutes; whereas, Analysis showed that there is no unmixed or undisper-
it takes 12 minutes and three passes for the conven- sed carbon black. In addition, the Aktiplast M version
tional mix to be put into a useable state. shows a lower ML(1+4), which translates into much
better extrusion speed.

Fig. 24: Aktiplast M in a Retread Stock In Figure 26 and 27 we will again study our mixing phi-
Recipes (phr): A B losophy using Aktiplast M in a NR batch. The purpose
(3 pass mix) (2 pass mix) of the experiment was to analyze the contribution of
SMR 20 60 60 zinc soaps in terms of carbon black dispersion. Two
BR 40 40
identical stocks were mixed, one with and one without
Rhenosin 145A 1.5 1.5
Aktiplast M – 2 Aktiplast M, for each type of carbon black from low
Tread Black 45.6 45.6 surface area to high surface area. And you can see in
HiSil 18.1 18.1 each of the recipes using Aktiplast M, it enlarges the
Stearic acid 2 2
Zinc oxide 4 4 polymer area resulting in much higher tensile strength
6-PPD 1.5 1.5 values over the control. A closer examination of the
TMQ 1.0 1.0 data reveals that the improvement in carbon black
Antilux 654 0.7 0.7
Oil 15 15 dispersion becomes more evident with increasing car-
TBBS 0.9 0.9 bon black surface area for stocks containing Aktiplast
PVI 0.2 0.2 M versus those stocks without Aktiplast M. The other
Sulfur 1.5 1.5
Total mix time (minutes) 12.0 8.5
physical properties are quite comparable.
ML(1+4)100°C: 70 69
Extrusion speed (cm/min.): 102 111
Extrusion output (g/min.): 97 105 Fig. 26: Improving dispersion of high surface area
300% Modulus (MPa): 11.0 11.7 carbon black with zinc soaps
Tensile strength (MPa): 20.3 20.4
Recipes (phr):
Elongation at Break (%): 530 520
SMR-20 70
Tan Delta (Yerzley): 0.320 0.286
Polybutadiene 30
Dynamic Modulus (MPa): 12.8 11.8
Zinc Oxide 3.5
Stearic Acid 1.6
6-PPD 1.5
Comparing the physicals of the two stocks, it is pretty TMD 1.5
obvious, that they are very similar. The only apparent MOR 0.9
Sulfur 1.5
difference between the two stocks is that the one mixed
110.4
with Aktiplast M features a much lower Tan Delta, Mixing Procedure:
which indicates lower heat buildup and thus better life- First Cycle: 80 RPM, water on one-half
time of the tire.
Load rubber and Aktiplast M (if present) ram down
0’ Start time
Aktiplast M is especially suitable in very highly loaded 50’’ Raise ram, add all ingredients except
compounds, which is demonstrated in a typical bead Santocure MOR and sulfur
2’ Raise ram, sweep, ram down
filler stock (Fig. 25). This compound is a highly loaded
3–1/2’’ Raise ram, discharge
NR/SBR compound with low oil. As you will note, Pass through open mill
the compound containing Aktiplast M mixes easily in Second Cycle: 80 RPM, water off
eleven minutes.
Load all ingredients, ram down
0’ Start time
50’’ Raise ram, scrape, ram down
Fig. 25: Aktiplast M in a Bead Filler Compound 1–1/2’’ Raise ram, discharge
Pass through mill
Recipes (phr): A B
SMR 20 75 75
SBR 25 25 Now we will look at the contributions of Aktiplast
Aktiplast M – 2.5 M-50 dispersion in combination with other process aids
Rhenosin 145A – 2.0
Carbon Black N 660 75 75 as it applies to rubber compounding (Fig. 28). In this
Zinc oxide 5 5 demonstration, an engine mount compound was mixed
Naphthenic oil 4.5 4.5 where flow properties are of the utmost importance.
Stearic acid 1.0 1.0
TMQ antioxidant 2.5 2.5
We will attempt to show a correlation between carbon
Hardening resin 13.5 13.5 black distribution and flowability of the compound. The
Sulfenamide 1.0 1.0 properties will be compared between the control stock
Sulfur 1.7 1.7
mixed with a chemical peptizer versus a stock mixed
Hexa 1.5 1.5
Total mix time (min.): 13.5 11.0 with a combination of a diluted chemical peptizer
Undispersed carbon black: yes no known as Poly-Dispersion® Aktiplast M-50, a saturated
ML(1+4)100°C: 88 75 zinc soap designed to improve flow and Aflux 12.
Mooney Scorch @ 270°F (min.): 8.0 9.0
200% Modulus (MPa): 10.3 11.7 Remember, the Aflux 12 is very poorly soluble in NR.
Tensile strength (MPa): 11.7 14.5
Elongation at break (%): 250 280 From the data presented here, you can see that the
Extrusion speed (cm/min.): 156 169
Extrusion output (g/min.): 120 122 ML(1+4) numbers are very close. The modulus values
of the compound mixed with the blend of processing
promoters is higher due to the removal of part of the oil
Fig. 29: New Aktiplast Products for Improved Silica
to compensate for the plasticking effect of the soaps Dispersion
and the blends that were added. The important conclu-
Recipe (phr): 1 2 3 4
sion is a much improved flowability as illustrated by
Buna VSL 1955–S25 96
the spider mold. Buna CB 24 30
Vulkasil N 70
Carbon black N-110 10
Fig. 27: Zinc Soaps excel in dispersing high surface SI 69–50% 12.5
area Carbon Blacks ZnO 3
Stearic Acid 1
A A’ B B’ C C’ Vulkanox HS 1
Compound 110.4 110.4 110.4 110.4 110.4 110.4 Vulkanox 4020 1.5
Aktiplast M 2 – 2 – 2 – Antilux 654 1.5
Carbon N-330 65 65 – – – – Aromatic Oil 20
Carbon N-220 – – 65 65 – – Aktiplast ST 5 – – –
Carbon N-110 – – – – 65 65 Aktiplast GT – 5 – –
Naphthenic Oil 15 16 15 16 15 16 Aflux 12 – – 5 –
ML1+4(100°C) 89 >200 >200 >200 >200 >200 Sulfur 1.5
DPG 2
Cure @ 330°F CBS 1.5
Mooney Scorch @ 120°C (min.)
T2 1.8 1.7 1.8 1.7 1.8 1.9
t5 28:10 25:50 32:41 24:44
T90 4.4 4.0 4.7 4.2 4.3 4.3
T35 38:22 36:03 36:07 35:03
Minimum 19.3 24.0 23.6 26.7 29.4 32.5
Maximum 79.7 79.0 79.2 75.2 78.4 75.8 Rheometer data @ 160°C
Cure 10’ @ 330°F t10 (min.) 2.56 2.52 1.52 1.48
t90 (min.) 6.32 6.36 6.28 6.08
Modulus, PSI
Fmin (Nm) 0.05 0.06 0.06 0.07
100% 590 610 750 750 630 720
Fmax-Fmin (Nm) 0.51 0.53 0.61 0.61
200% 1480 1480 1750 1680 1530 1500
300% 2410 2350 2760 2620 2530 2410 Physical properties (cure 20 min. @ 150°C)
Tensile PSI 3410 3270 3450 3220 3650 2940 Hardness Sh A 59 57 58 58
Elongation% 430 420 370 370 430 360 Elasticity, % 37 37 36 39
Shore A 71 71 72 71 74 74 Modulus, MPa
Die C Tear1 471 450 434 440 432 402 100% 2.19 1.97 1.96 1.99
Rebound% 47 45 42 42 42 42 300% 8.34 6.96 8.12 8.40
1
Ibsf/in Tensile Strength, MPa 14.65 14.87 16.12 15.94
Elongation, % 473 555 497 480

Fig. 28: Aktiplast M and Aflux 12 in an engine mount

compound
Fig. 30: New Aktiplast Products for Improved Silica
Recipes (phr): A B Dispersion
Natural rubber 100 100 Recipe (phr): 1 2 3 4
Carbon Black N 330 28 28
Zinc oxide 3.5 3.5 Buna VSL 1955–S25 96
Oil 5 3 Buna CB 24 30
Stearic acid 1.5 1.5 Vulkasil N 70
6-PPD 1.5 1.5 Carbon black N-110 10
Antilux 654 0.8 0.8 SI 69–50% 12.5
BLE 25 1.5 1.5 ZnO 3
Poly-Dispersion Aktiplast M-50 – 3.0 Stearic Acid 1
Aflux 12 – 3 Vulkanox HS 1
other proc. prom. 0.2 – Vulkanox 4020 1.5
Sulfur 3 3 Antilux 654 1.5
TBBS 0.9 0.9 Aromatic Oil 20
Aktiplast ST 5 – – –
ML(1+4)100°C: 44 42 Aktiplast GT – 5 – –
300% Modulus (MPa): 4.8 5.0 Aflux 12 – – 5 –
Tensile strength (MPa): 21.4 21.6 Sulfur 1.5
Elongation at break (%): 630 610 DPG 2
CBS 1.5
Viscoelastic Properties 20 min. @ 150°C
0°C
tan 0.379 0.366 0.350 0.341
A B E’ 10.932 11.134 10.544 8.528
E’’ 4.147 4.084 3.928 2.915
E* 11.693 11.860 11.620 9.013
60°C
tan 0.110 0.112 0.109 0.108
E’ 5.104 5.389 5.129 5.239
In recent times, the efficient and homogeneous disper- E’’ 0.575 0.604 0.563 0.567
sion of silica has become a top priority objective. Two E* 5.138 5.423 5.160 5.270
new products, Aktiplast GT and Aktiplast ST have been Rheovulcameter (170°C, 70 bar, 12s, 10min)
developed to solve this problem (Fig. 29, 30). As you IM output (mm3/s) 133 135 105.5 99.25
IM volume (mm3) 1762 1807 1442 1362
can see, the addition of Aktiplast ST generates greatly
improved extrusion output, improved molding charac- Laboratory Extruder d=20 mm, 18d, 100°C
Extrusion Rate (cm/min) 1.494 1.608 1.436 1.468
teristics, and longer Mooney scorch compared to the Extrusion Output (g/min) 187.4 195.8 169.1 171.1
control data. The Tan Delta measured at 0°C is higher
than the control which translates into very good wet that is self-reinforcing. Therefore, in the control com-
traction. At the same time, the Tan Delta measured at pound, even though the majority of the carbon black
60°C is the same as the control stock, indicating that moves into the BR, we see normally high tensile
there will be no difference in heat buildup. strength because NR has a natural reinforcing activity.
And at the same, the different phases between the poly-
Aktiplast GT is another alternative. The use of Aktiplast mers are very obvious, resulting in poor tear strength
GT at 5 phr greatly improves processibility and physi- numbers. With the Rhenosin 145A, the different phases
cal properties over those of the control compound, but are eliminated and more filler is being forced into the
not to the same extent as the Aktiplast ST. NR phase. This increases the shear between the NR and
the BR matrix and quite naturally generates a slightly
The only potential deficit might be the slight decrease decreased tensile value because more filler is in the
in 300% modulus, but even there, we find that the NR. But on the other hand, you have dramatically
300% modulus for the Aktiplast ST is not much differ- improved tear strength of the overall compound be-
ent from that of the control stock. cause the carbon black is nicely homogenized between
the two polymers. So, due to the increased shear, the
The next example shows the use of Rhenosin 145A in a end result is greatly improved performance in terms of
truck tread compound (Fig. 31). Rhenosin 145A is a groove cracking, and other problems that are well
resinous product described chemically as a blend of known in the tire application world.
aromatic, naphthenic, and paraffinic resins.The theory
behind the use of this product is very simple. Basically, Figure 32 is a colorful and dramatic demonstration
no matter what polymer you add it to, there will be showing the homogenizing performance of Rhenosin
something in the Rhenosin 145A that will be soluble in product line. For this demonstration, two polymers were
that polymer. Thus you can see that if you add it to a selected that are not compatible. One was an EPDM,
blend of polymers, some portion of the Rhenosin 145A which is totally nonpolar, and the other was an NBR,
will be soluble in each of the polymers and thus it will which is about as polar as anything can be. In order to
function as a homogenizing agent. make the demonstration easier to see, we added pig-
ments to the two polymers. The EPDM was pigmented
white and the NBR was pigmented red. Hence, it is
Fig. 31: Rhenosin 145A in an NR/BR truck tread
compound easy to see that after two minutes of mixing, the first
sample, which was mixed without the help of a homo-
Recipes (phr): A B
genizing agent, shows a lot of the white EPDM clusters
SMR-5 80 80 just lying undispersed in the red NBR matrix. However,
Buna CB 10 20 20
Aktiplast F 1.5 1.5 the second compound mixed two minutes with the
Carbon black N 330 60 60 homogenizing agent, showed no white colored EPDM.
Naftolen ZD 5 5 The next set of data (Fig. 33) distinguishes rather dra-
Vulkanox 4010 NA 2.5 2.5
Antilux 654 2 2 matically the differences between a processing pro-
Vulkanox HS 1 1 moter and a process oil. Process aids are plasticizers,
Zinc oxide 5 5 whether you like it or not, however, they perform com-
Rhenosin 145A – 6
ML(1+4)100°C: 67 54
pletely different from an oil. Although a lot of people
Rheometer data at 160°C: would always say ‘you know, we use oil as a process
t10 (min.): 1.36 1.00 aid’, we want to show conclusively that there is a big
t50 (min.): 3.52 4.40
difference between these two ingredients. Look at the
t90 (min.): 4.52 5.68
Mooney Scorch at 120°C differences you really obtain.
t5 (min.): 22.26 32.48
t35 (min.): 26.10 39.42
Physical properties (cured 15 minutes at 150°C): Fig. 32: Homogenization of EPDM and NBR Polymers
Hardness (Shore A): 65 61 using Rhenosin 145A
Elasticity (%): 43 38
Modulus 100% (MPa): 3.5 2.7 Without Rhenosin 145A after 2 mins. EPDM
Modulus 300% (MPa): 14.3 9.3 NBR/EPDM 70:30
Tear Strength (N/mm): 38.6 78.6
Tensile Strength (MPa): 17.1 16.0
Elongation at break (%): 350 360

In this particular truck tread compound, we have done

nothing more than add 6 phr of Rhenosin 145A. This
additive lowers the Mooney viscosity, but the main
advantage is that it greatly improves carbon black
dispersion.

Basically, Rhenosin 145A, being a resinous product

with multiple soluble ingredients, destroys the different
phases of NR and BR, thus preventing the majority of With Rhenosin 145A 10 phr after 2 mins. NBR
the carbon black from preferentially moving into the NBR/EPDM 70:30
BR. A well known fact is that NR is the only polymer
 Looking at a few specific properties, specifically the
Fig. 33: Recipe for Process Oil versus Aktiplast T
Study aging performance of the elongation, there is a differ-
ence of 37% for the oiled stock versus a 1% change for
SMR CV50 100
Carbon Black N330 55 the stock mixed with the processing promoter. This is a
ZnO Special 5 world of difference. The differences in processibility
Stearic Acid 1 are nicely demonstrated in the injection molded vol-
Vulkanox 4020 1
Vulkanox HS 1 ume.
Antilux 654 0.5
Vulkacit MOZ 0.9 The stock with the processing promoter shows more
Sulfur 1.5
165.9 phr than a 10% improvement over the other. Since this
compound is a lot tougher, you would expect that it
To demonstrate this phenomenon, we very shyly used would be more difficult to process, but the reverse is
13 parts of a naphthenic oil in the control stock and a true.
comparison stock in which we replaced 3 parts of the
oil with a zinc soap (Fig. 34). As we look at the data, we Another feature we feel is important to be remembered
see that the Mooney viscosity and Mooney scorch are is the knowledge that the Aktiplast line is composed of
the same. The rest of the data, especially the modulus, zinc soaps. To make things easier in this illustration
as you may expect, is a lot higher because of the lower (Fig. 35), we can think of them simply as a zinc steara-
oil content. But due to the increased solubility of the te. There is a reason for this as shown in the Rheogra-
zinc soap, some of this improvement is due to a much phs. Pay attention to the 25 Rheometer curves for bat-
tighter rubber matrix. The tensile strength inevitably ches that were mixed in which the zinc stearate activa-
increases due to better carbon black dispersion. Percent tor was formed by reacting zinc oxide and stearic acid.
elongation at break lowers, very simply because the You can see how very erratic these curves are.
rubber crosslinks are much tighter. The compression set
values are much lower compared to the control stock.
Fig. 35: Redrawn Rheometer Cure Curves
And last, but not least, if you look at the aging charac-
Time = 6 Range = 100 Temp = 360
teristics between the control stock and the one con- first 25 batches of 1987
taining less oil and the processing aid, you see a world without “Aktiplast T”
of difference. The compound with all oil ages poorly.
This would indicate that it has not been cured as well as
it could have been. The poor aging characteristics of
this compound show an obvious problem with the
compound.

Fig. 34: Comparison between Process oil and Redrawn Rheometer Cure Curves
Aktiplast T Time = 6 Range = 100 Temp = 360
last 25 batches of 1987
Compound 165.9 165.9 with “Aktiplast T”
Naphthenic Oil 13.0 10.0
Aktiplast T – 3.0
178.9 178.9
Mooney ML(1+4)100°C 37 37
Mooney Scorch 120°C
t5 – min. 40:39 39:22
t35 – min. 45:05 43:23
Vulcanizate 150°C/20 min.
Hardness – °ShA 53 59
Modulus – MPa
100 1.5 1.9
300 6.0 9.0
Since this was a CBS, i.e. sulfenamide cure, the like-
500 11 16
Tensile – MPa 20 24 lihood that the sulfenamide did not disperse is very,
Elongation – % 830 690 very low. In the next 25 batches of the run, we show the
Tear – N/mm 69 58 same compounds; however, these contain Aktiplast T.
Compression Set – %
168h/70°C 55 42 For these mixes, you can see that nothing has been
24h/70°C 34 25 changed about the compound, about the Banbury, about
24h/RT 16 15 the mixing, etc., yet you can see that the ODRs all fall
Hot Air Aging – 7d/70°C
Hardness – °ShA 57+4 60+1 much tighter together. We theorize that this is very sim-
Modulus – MPa ply a consequence of the Aktiplast being a soluble zinc
100 1.8 +20% 2.3 +21% stearate mixed up front in the compound which means
300 12 +53% 10 +9%
500 22 +73% 17 +3%
that time after time you are looking at the same activa-
Tensile – MPa 25 +10% 23.5 –2% tion for the cure.
Elongation – % 580 –37% 685 –1%
Tear – N/mm 50 –28% 57 –3%
In the conventional zinc oxide/stearic acid mix, the for-
Rheovulcameter (100°C/150°C Mold) mation of the zinc stearate is a function of the homoge-
Volume – ccm 1930 2165
Velocity (max) – ccm/sec 86 99
neity of the stock, which is probably different every
time.“
Registered trademarks of Rhein Chemie Rheinau Registered trademarks of Bayer AG:
GmbH resp. Rhein Chemie Corp.:
Aflux® Baypren®
Aktiplast® Disflamoll®
Antilux® Perbunan®
Poly-Dispersion® Renacit®
Rhenogran® Vulkacit®
Rhenomag® Vulkanol®
Rhenopren® Vulkanox®
Rhenosin® Vulkasil®
Rhenosorb®

® = registered trademarks

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way of trials – is given in good faith but without warranty, ity. Should, in spite of this, liability be established for any
and this also applies where proprietary rights of third damage, it will be limited to the value of the goods deliv-
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