Science & Technology of Blooming

of Rubber Chemicals & its

Prevention
Bob Francis – Flexsys Asia Pacific
17/2/2006

Responsible Care
A Public Commitment
 Contents

 Introduction
 Mechanism of Blooming
 Merits & Demerits of Blooming
 Effect of Rubber Chemicals’ Bloom on Compound Tack
 Effect of Blooming Vulcanizing Chemicals on Vulcanizate
Properties
 Factors affecting Blooming of Rubber Chemicals
 Detection & Estimation of Rubber Chemical Bloom
 Summary & Conclusions

Responsible Care
A Public Commitment
 Dictionary Definition
 Bloom
a. A waxy or powdery whitish to bluish coating on the surface of
certain plant parts, as on cabbage leaves or on a plum or grape.
b. A similar coating, as on newly minted coins.
c. Grayish blotches or streaks on the surface of chocolate
produced by the formation of cocoa butter crystals.
d. Chemistry See efflorescence.

 Efflorescence
a. The deposit that results from the process of efflorescing. Also
called bloom.
b. The process of efflorescing.
c. A growth of salt crystals on a surface caused by evaporation of
salt-laden water.

Courtesy of the Free Dictionary by Farlex

Responsible Care
A Public Commitment
 Bloom vs Diffusion
 Bloom:
May occur when a partly soluble additive is used at a
loading in excess of its solubility at a given temperature.
Bloom doesn’t occur from an unsaturated solution.

 Diffusion:
The movement of a soluble material prompted by a
concentration gradient
Fick’s 1st Law: ‘The flux of diffusing particles is
proportional to the gradient of their concentration’

 Bloom is an outcome of a diffusion process

Responsible Care
A Public Commitment
 Bloom
 For bloom to develop, it needs a surface (typically with air)

 Blooms result from a diffusion process to a surface. The molecules migrate

through the compound to form a high stability supersaturated solution on the
surface

 Under favourable conditions this solution destabilises and crystals form

 For the molecules to migrate they need to be partially soluble in the matrix

 There can be subtleties as to whether a surface ‘film’ is actually a bloom.

Blooms are solids not liquids.

 Blooms can be bi-products of the vulcanizing reactions (eg ZDCs from

thiurams, phthalimide from CTP, resotropin from SRH systems)

Responsible Care
A Public Commitment
 Curative Diffusion in NR
(17days@45C)
10
Log Conc. (wt.%)

1 With curatives initially No curatives initially

TBBS
0.1
DTDM
0.01
MBTS
0.001 CTP
-1.25 -0.75 -0.25 0.25 0.75 1.25 1.75

Distance From Interface (cm)

Responsible Care
A Public Commitment
 Molecular Weight (size)
 A study in NR showed the following tendency for migration:

DTDM (236) > TBBS (238) > CTP (261) > MBTS (332)

Decreasing rate of migration

Larger molecules diffuse slower

(not just MW,also a steric hindrance
effect)
Responsible Care
A Public Commitment
 Temperature & Concentration

 The rate of diffusion increases with increasing

temperature

 Higher concentration increases the rate of diffusion

Responsible Care
A Public Commitment
 Merits & Demerits of Blooming
 Influential for tackifying, ozone protection
 Problematic for: tack retention interply
adhesion visual appearance contact staining antidegradant
loss

Diffusion is necessary for the functionality of tackifiers &

antiozonants
Blooming is considered undesirable as it is generally in
excess to the need

Responsible Care
A Public Commitment
 Antiozonants
 An antiozonant used in excess of its solubility has two
driving forces affecting its appearance at the surface

Bloom & Diffusion

 An ideal antiozonant would be totally soluble & show rapid

migration to the surface to replace that depleted by its
reactivity & not be easily removed from the surface (high
persistence, low volatility)

77PD > 6PPD > IPPD > DTPD

Decreasing Solubility

Responsible Care
A Public Commitment
 Petroleum Waxes
 Types
Paraffin (low temp. solubility & mobility)
Microcrystalline (high MW,high temp solubility/mobility)
 Characterized by balance of:
Migration & solubility in rubber, both Temp. dependent
 Sufficient bloom formation on surface provides protection
 Limitations:
Can inhibit tack & adhesion
Wax film is brittle & suitable only as static protectant
Once film is ruptured the surface is unprotected
High concs. (>2.5phr) reduces fatigue resistance

Responsible Care
A Public Commitment
 Wax composition
 Alkanes – give rapid migration but a brittle film with low
adhesion & poor ‘depot’ properties
 Isoalkanes - improve the film properties
 Cycloaliphatics - improve plasticity & adhesion

 Waxes with a low softening point are more soluble & re-
dissolve at higher environmental temperatures risking
under-protection
 Waxes with a high softening point diffuse too slowly
risking under-protection
 Microcrystalline waxes need careful selection to
accomplish static ozone protection

Responsible Care
A Public Commitment
 Wax Mobility vs Solubility

Amount Mobility
of bloom solubility

Temperature

Responsible Care
A Public Commitment
 Impact on Tack
 Tackifiers function to some extent by plasticizing & softening,
reducing the viscosity & elastic behaviour of the rubber
 This has the effect of smoothing the surface facilitating inter-
surface adhesion
 Part of their functionality relies on diffusion of polar molecules
to the surface of less-polar elastomers
 Chemicals which co-migrate to the surface can interfere with
the tack (eg waxes, sulfur, antidegradants, oils)
 Environmental factors such as humidity & UV also can result in
reactions to reduce tack
 Frequently, hydrocarbon solvents are used to ‘freshen’ stocks
to remove tack-limiting blooms during tyre construction

Responsible Care
A Public Commitment
 TMQ components - Days to form bloom

TMQ
degree of condensation

0 5 10 15 20 25 30 35

days

Ref: “Non Blooming High Performance Antidegradant”

(N.Inui, H. Nagasaki and T. Yamaguchi, Osaka) presented
at Tyretech ‘92
Responsible Care
A Public Commitment
 More elastic,
fewer points of
inter-surface
contact

Addition of
plasticizing resins

More plastic,
numerous points
of inter-
surface contact

Responsible Care
A Public Commitment
 Sulfur Bloom
 One of the major problems in tack retention is sulfur bloom
 This is due to the limited solubility of sulfur in rubbers at room
temperature
10

8 SBR
Solubility, [%]

6 NR
4
2 IIR

0
30 40 50 60 70 80 90 100
Temperature [°C]

Responsible Care
A Public Commitment
 RHOMBIC SULPHUR

• Only slightly soluble in rubber at

room temperatures

- SULPHUR BLOOM
- REDUCED TACK
- REDUCED INTERPLY
ADHESION
Responsible Care
A Public Commitment
 INSOLUBLE SULPHUR :

• Polymeric (large molecules)

• Insoluble in rubber

• Metastable, slowly reverts to Rhombic

sulphur more-so at high temps
Responsible Care
A Public Commitment
 INSOLUBLE SULPHUR

- NO SULPHUR MIGRATION
- NO SULPHUR BLOOM
- TACK RETENTION
- INCREASED SCORCH TIME
But more difficult to disperse
Responsible Care
A Public Commitment
 Factors influencing Sulfur bloom
 Quality of the Insoluble Sulfur (starting IS content &
thermal stability) & its phr in the compound

 Degradation of Insoluble Sulfur due to storage near basic

chemicals (HMT, HMMM, ammonia, DCBS, TBBS, CBS, DPG…)

 Pre-weighing of IS with accelerators in same bag + in-

compound effects of these basic chemicals

 Temperature & time (heat history) during mixing & processing

Responsible Care
A Public Commitment
 Bloom Tendency
Evaluation of the risk of blooming
If final soluble sulfur concentration is equal or greater than 1.5 ---> will bloom Formula phr SS = (100-%I.S) * phr TS /100
if in between 1.0 - 1.5 --> possible bloom
phr SOLUBLE SULFUR in compounds
** 95.0 0.050 0.100 0.150 0.200 0.250 0.300 0.350 0.400
92.5 0.075 0.150 0.225 0.300 0.375 0.450 0.525 0.600
HTS can be considered as 90.0 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800
% IS remaining 87.5 0.125 0.250 0.375 0.500 0.625 0.750 0.875 1.000
in rubber compound 85.0 0.150 0.300 0.450 0.600 0.750 0.900 1.050 1.200
** = 82.5 0.175 0.350 0.525 0.700 0.875 1.050 1.225 1.400
ADDING 100 % of sulfur 80.0 0.200 0.400 0.600 0.800 1.000 1.200 1.400 1.600
in rubber compound 77.5 0.225 0.450 0.675 0.900 1.125 1.350 1.575 1.800
after milling the IS remaining 75.0 0.250 0.500 0.750 1.000 1.250 1.500 1.750 2.000
is=95.0 %mean that in the compound 72.5 0.275 0.550 0.825 1.100 1.375 1.650 1.925 2.200
there is 5 % soluble sulfur 70.0 0.300 0.600 0.900 1.200 1.500 1.800 2.100 2.400
+ - 0.050 phr of soluble sulfur 67.5 0.325 0.650 0.975 1.300 1.625 1.950 2.275 2.600
in the mixed compound 65.0 0.350 0.700 1.050 1.400 1.750 2.100 2.450 2.800
62.5 0.375 0.750 1.125 1.500 1.875 2.250 2.625 3.000
60.0 0.400 0.800 1.200 1.600 2.000 2.400 2.800 3.200
57.5 0.425 0.850 1.275 1.700 2.125 2.550 2.975 3.400
55.0 0.450 0.900 1.350 1.800 2.250 2.700 3.150 3.600
52.5 0.475 0.950 1.425 1.900 2.375 2.850 3.325 3.800
50.0 0.500 1.000 1.500 2.000 2.500 3.000 3.500 4.000
47.5 0.525 1.050 1.575 2.100 2.625 3.150 3.675 4.200
45.0 0.550 1.100 1.650 2.200 2.750 3.300 3.850 4.400
soluble S 42.5 0.575 1.150 1.725 2.300 2.875 3.450 4.025 4.600
< 1.0 phr : no bloom 40.0 0.600 1.200 1.800 2.400 3.000 3.600 4.200 4.800
1-1.5 phr : bloom possible 37.5 0.625 1.250 1.875 2.500 3.125 3.750 4.375 5.000
>1.5 phr : bloom likely 35.0 0.650 1.300 1.950 2.600 3.250 3.900 4.550 5.200
32.5 0.675 1.350 2.025 2.700 3.375 4.050 4.725 5.400
30.0 0.700 1.400 2.100 2.800 3.500 4.200 4.900 5.600
27.5 0.725 1.450 2.175 2.900 3.625 4.350 5.075 5.800
25.0 0.750 1.500 2.250 3.000 3.750 4.500 5.250 6.000
1 2 3 4 5 6 7 8
phr TOTAL SULFUR in compound

Responsible Care
A Public Commitment
 %Sol. Sulfur through steel skim processing
(factory example)

0.6

0.5

0.4 Bloom likely >

0.8% (1.5phr)
% SS

0.3

0.2
Theoretical max soluble sulfur
0.1 of this cmpd is 3.2%
0

Prior tointo
Ex Banbury
mixing
warm up calender feed
strip
cal. Wind-up Tyre building

sol. S is 0.08%

Responsible Care
A Public Commitment
 Sulfur Migration
 Migration of IS only occurs after it has reverted to a
soluble form
 The rate of migration depends on concentration &
temperature
 Above 130°C there is no difference in the migration
characteristics of insoluble & soluble S (its one & the same)

 Soluble sulfur will readily migrate across a rubber interface

to equilibrate concentration differences. The magnitude is a
function of time, temp. & distance

Responsible Care
A Public Commitment
 Effect of blooming vulcanizing
chemicals on vulcanizate performance
 Visual

 Ozone protection

 Contact staining (esp. PPDs)

 ES&H

 Interply adhesion (durability, retreadability etc)

Responsible Care
A Public Commitment
Relation of wax bloom to static ozone
protection
250

200
Ozone Resistance, hours

>208
150

100

50

0 NR/BR Sidewall
0 50 100 150 200 
1 phr Santoflex 6PPD

Wax Bloom, µ g/cm2

Responsible Care
A Public Commitment
 Diffusion of Antiozonant in Passenger Tyre
Carcass & Sidewall
2 2

1 .5 1 .5 Sidewall
% By Weight

Sidewall 1
1
6PPD

Carcass
0 .5 0 .5

Carcass
0 0
0 2 4 6 8 0 2 4 6 8

Weeks aging at R.T. Weeks aging at R.T.

Responsible Care
A Public Commitment
Carcass Reservoir Concept : Tyre Tests
Good 8
Road Test
7

5
Sidewall Crack

Wheel Test
4
Rating

0
0 0.5 1 1.5 2
Bad

Responsible Care
phr Antiozonant in Carcass A Public Commitment
 Change in Antidegradant Concentration
in Tyre Sidewall Area (due to migration)

100
6PPD
90 in Carcass
% Retained Antidegradant

80
70
60
50 6PPD
in Sidewall
40
30 DTPD
in Sidewall
20
DTPD
10 in Carcass
0
After After 3 Months 7 Months 12 Months
Processing Curing Aging Aging Aging

Responsible Care
A Public Commitment
Change in Antidegradant Concentration
In Tyre Tread Area (due to migration)
6PPD
in Tread
100
90 6PPD
% Retained Antidegradant

in Carcass
80
70
6PPD
60 in Base
50
40 DTPD
in Base
30
20
77PD
10 77PD in Carcass
in Tread
0
After After 3 Months 7 Months 12 Months
Processing Curing Aging Aging Aging

Responsible Care
A Public Commitment
Effect of Storage/Service conditions
on Antidegradant Concentration
% Retention of Antidegradant
Akron Texas Texas
One Static 1 Year Static
Year 16 Mos. +48,000 Miles

Tread
6PPD 98.4 71.6 22.8
7PPD 12.8 0.0 0.0

Tread Base
6PPD 66.5 48.7 22.0
7PPD 42.8 37.8 17.0

Carcass Under Tread

6PPD 88.6 75.7 20.3

Sidewall
6PPD 46.0 22.0 8.0
DTPD 28.6 17.8 11.8

Carcass Under Sidewall

6PPD 97.1 59.6 18.3
(None Added) DTPD 11.4 6.3 3.8

Responsible Care
A Public Commitment
 O3 Protection vs. 6PPD level

110
% Relative Ozone Resistance

100

90

80

70

60
3.0 phr 2.5 phr 2.0 phr 1.5 phr

Responsible Care
A Public Commitment
 Reservoir Effect
 It is generally recognized that the carcass needs some
level of 6PPD to act as a ‘reservoir’ to be able to
migrate through to the tread or sidewall to replace
reacted & lost 6PPD

Responsible Care
A Public Commitment
 ES&H
EU Classification based on ecotoxicological properties
 Dangerous for the environment

Several antidegradants & accelerators are

environmentally hazardous

Responsible Care
A Public Commitment
 Skin contact
 Many individuals suffer skin allergies (Type IV
hypersensitivity)

 Bloom presents the chemical to the surface where it can

be transferred to skin through handling

 Whilst this is not ‘life-threatening’, it can cause severe

inconvenience & discomfort to sensitised individuals

Responsible Care
A Public Commitment
 Interply Adhesion
 Exposure of NR & IR to sunlight or O3 produces a thin film on
the surface of the compound. This film restricts migration of
the polymer chains across a plied-up interface
 Consequently both tack in the uncured compound & interply bond
strength in the cured compound are reduced
 The effects of sunlight can be greatly reduced through the use
of antidegradants such as 6PPD
 But Antiozonants react with O3 to form a protective film which
acts as a barrier to the mobility of the polymer chains &
thereafter reduces interply adhesion
 Also, as the number of double bonds at the surface is reduced
after O3 attack, a lower crosslink density is expected

Responsible Care
A Public Commitment
Effect of Sunlight on the Tack of NR
and SBR
200

160
Tack (lbs/in2)

120
SBR
80
NR

40

0
0 15 30 45 60
Sunlight Exposure Time, minutes

Responsible Care
A Public Commitment
Effect of Ozone on Tack--15pphm
Concentration
Exposure

1 Day 2 Days
70
60
50
Tack (lb/in2)

40
30
20
10
0
SBR NR/SBR NR

Responsible Care
A Public Commitment
Effect of Ozone/Humidity on Interply
Adhesion

Adhesion Rating

Compound Initial 16hrs @ 16hrs @ 16hrs @ 15pphm

15pphm O3 and 25pphm O3 and O3 and 60% RH
30% RH 30% RH

NR 5 2-3 1 1

IR 5 4-5 2-1 2-1

SBR 5 4-5 3-4 3-4

Adhesion Rating: 1 2 3 4 5
Bad  Good

NR stock more affected by O3 + humidity

Responsible Care
A Public Commitment
Effect of 5pphm Ozone on Interply
Adhesion
5
Adhesion Rating

0
0 4 8 12 16 20
Exposure Time, hours

Responsible Care
A Public Commitment
Effect of Sunlight on Cured Interply
Adhesion-NR

Exposure
Time, minutes 0 15 60 90

Rating 5 4-5 1-2 1

Green compound exposure to Sunlight is

quite damaging to subsequent ply adhesion

Responsible Care
A Public Commitment
Effect of Antiozonants in NR on cured
Interply Adhesion After O3 Exposure

Antiozonant Initial Rating after 16h @

(1 phr) Rating 15pphm O3
None 5 1
TMQ 5 1
6PPD 5 1
IPPD 5 1
77PD 5 1

No apparent benefit!

Responsible Care
A Public Commitment
Effect of Antioxidants in NR on Cured
Interply Adhesion After O3 Exposure

Antiozonant Initial Rating after 16h @

(1 phr) Rating 15pphm O 3
None 5 1
TBMC 5 2
TMQ 5 2

Antioxidants do not form an ozonide film to

limit subsequent cured adhesion

Responsible Care
A Public Commitment
Effect of Fast Blooming Waxes in NR on
Cured Interply Adhesion After O3
Exposure

Wax Initial Rating after 16h @ 15pphm O3

Loading Rating
None 5 1
Wax #1 - 5 5
1phr
Wax #2 - 5 5
1phr

Wax is beneficial in protecting in-process

components

Responsible Care
A Public Commitment
Effect of antioxidants in NR on Cured
Interply Adhesion After UV Exposure

Exposure Time, 0 15 60 90
minutes

Antioxidant (1 Ratings
phr)
None 5 4-5 1-2 1
TMQ 5 5 5 5
6PPD 5 5 5 5
ADPA 5 4-4 2 1
DTPD 5 5 5 5
MBI 5 - - 1-2
TBMC 5 4 3 2

Responsible Care
A Public Commitment
Effect of Fast Blooming Wax in NR on
Cured Interply Adhesion After UV
Exposure

Rating
Wax/ AO 0 Minutes 60 Minutes
Loading UV UV Exposure
Exposure
None 5 1
Wax- 2phr 5 3
Wax- 2phr; 5 5
6PPD - 1phr

Responsible Care
A Public Commitment
 Lab Measurements of Diffusion
 Uncured stocks, butt-joined, pressed & stored for
differing conditions

S S
t t
o Stock #2 Stock #2 o
c No curative c
No curative
k k
# #
1 1

5
5
phr
phr

12.7 63.5 mm 63.5 mm 12.7

Responsible Care
A Public Commitment
 Test methodology
 After 3, 7, or 17 days @ either 23°C or 45°C, strips
were cut at measured distances from the interface

 2 mm3 pieces were cut, weighed into amber bottles &

extracted for 24hrs

 The quantitative assessments were made by reverse

phase HPLC

Responsible Care
A Public Commitment
 Procedure 2
Compound with experimental
AO

Control without AO

Compound with experimental

AO

Diffusion coefficient determination (mould)

Responsible Care
A Public Commitment
Determination of diffusion coefficient, D, cm2/sec
(Classical diffusion theory)

D = (π l2/16) * (Tan2α (from plot)/∆ m2α )

l= thickness of the vulcanizate plate, cm

Tanα = Determine from the plot
∆ m = Weight increase in the central plate at equilibrium

Responsible Care
A Public Commitment
 The method:
• The increase of AOz in central vulcanizate plate to be
followed by the measurement of the weight increase.
The decrease of the mass of the side plates to be
measured simultaneously. The equilibrium will occur
when “central” and “side” plates each reach a constant
weight.

•Plot the increase mass (∆ mt, gram) versus square root

of ∆ t½
From the plot determine tangent α

Responsible Care
A Public Commitment
A typical plot

Responsible Care
A Public Commitment
Diffusion coefficient (cm2/s) of IPPD and 6PPD determined
by this technique, effect of temperature

Rubbers Temp. °C IPPD 6PPD

-9 -9
NR 10 3.40 * 10 1.70 * 10
-8 -8
38 2.56* 10 1.39* 10

-8 -9
SBR 1500 38 1.03* 10 6.13* 10

-8 -9
NR/BR 10 1.16 * 10 7.82 * 10
-8 -8
38 6.89* 10 4.55* 10

Responsible Care
A Public Commitment
The time required for the saturation
of the central plate
Rubber Temperature, °C IPPD 6PPD

-9 -9
NR 10°C 3.40*10 1.70*10
Saturation days 57 60

-8 -8
38°C 2.56*10 1.39*10
Saturation days 13 16

-7 -8
62°C 1.19*10 7.05*10
Saturation days 4 4

Mobility greatly affected by temperature

Responsible Care
A Public Commitment
 Other Test Methods
 Visual assessments

 Radioactive tracing

 Microinterferometry (an optical method, suitable only for gum stocks)

 Wet swabs or dry scraping followed by extract analysis via

instrumental techniques such as FTIR, GC/Flow Injection Analysis-MS

Responsible Care
A Public Commitment
 Developments
 Flexsys has done considerable R&D on the development of
long-lasting antioxidants & antiozonants

 Polymer-bound products slow the diffusion (eg Q-Flex

QDI)

 Molecular size is another strong variable

 Flexsys continues to improve the thermal stability of our

Crystex Insoluble Sulfur to maintain this as the most
bloom resistant IS

Responsible Care
A Public Commitment
 Chemical Additives’ Migration
 Curatives & antidegradants will migrate throughout a
rubber compound, both in the uncured & cured states

 The extent of migration is a function of additive type,

loading, its reactivity with other ingredients, & the
environmental / service conditions

 Optimum compound performance is, in part, a result of

designing the compound taking these factors into account

Responsible Care
A Public Commitment
Responsible Care
A Public Commitment