Understanding BLOOM

Prepared by KP Ho
- Performance Additives

Introduction
Bloom is caused by the migration of solid or liquid compounding
materials which have a limited solubility in the polymer matrix.

Bloom includes dry bloom and wet bloom which is also known as exudation,
bleeding or oily bloom.
Very common, bloom refers to the initial formation of star-shaped clusters
when solid compounding materials re-crystallize at the vulcanisate surface.
This is due to the fact that many of the rubber compounding materials have
limited compatibility with the elastomer and separate out at the latest after
vulcanizing and subsequent cooling to room temperature. Blooming is a
diffusion controlled process.
Development of bloom can be stimulated mechanical or chemically.
e.g. a chemical stimulation is the occurrence of whitish or grayish fingerprints
on vulcanisate. This is caused by acetic acid contained in perspiration.

Introduction
Bloom-like Phenomena
1.
True blooms
2.
Modified blooms protective coats
3.
Pseudo blooms surface degradation of rubber itself
4.
Surface contamination
5.
Staining or discoloration
6.
Hazing

Simple Tests to identify bloom type

1. Did bloom develop on storage?

No

Yes

Surface contamination
or organic haze

No

2. Does it disappear on heating?

Oxidized anti-degradant
Surface degradation
or basic zinc stearate

Yes
3. Can it be removed with a solvent wipe?
No
Yes

True Bloom

Try other solvents

Yes

No
Yes
Try complex agent
No
Haze due to organics

Other instrumental analysis : Multiple Internal Reflectance infra-red spectroscopy (MIR)

: Scanning Electron Microscopy (SEM)

Color changes
and their significance in Bloom analysis
1. Is the color change light induced? (mask part of sample for reference)
Grey/Brown
- amine antioxidant
Pink
- phenolic antioxidant
2. Is the color change heat induced?
If yes with stickiness/embrittlement
If yes without stickiness/embrittlement

- oxidative degradation
- amine antioxidant

3. Is the color change patchy?

Reaction of external contamination with rubber chemicals
4. Does color change appear after laundering or contact with metal?
Copper/Iron reaction with dithiocarbamates
5. Does color change accompany poor ageing?
Further evidence for copper/iron contamination

Blooming of Crystalline Substances

- such as paraffin waxes or sulphur
Limited solubility in a given elastomer and a dosage level above the
solubility limit are the main causes for a substance to develop bloom.
Most chemicals are more soluble in hot rubber than cold rubber.
Also, they are more soluble in unvulcanized rubber than vulcanized rubber.
A substance completely soluble in the rubber at mixing temperatures is mostly
compatible with the elastomer in the uncured state. After vulcanizing and as
soon as the vulcanizate cools the substance will begin to crystallize.
The crystal growth within the cross-section of the rubber is limited by strain
development around the crystals. At the vulcanizate surface crystal growth will
continue due to much less strain. The concentration gradient will cause the
solute substance in the bulk to migrate to the surface and the crystal in the bulk
to dissolve. Migration will end when all material above the solubility limit has
formed crystals at the surface.

Protective Waxes
The wax layer acts as a physical barrier in order to protect vulcanizate
against ozone attack.
Paraffin Waxes
- Mainly consist on n-paraffin (n-alkenes) with small amount of branched
paraffin (iso-alkenes).
- Generic formula CnH2n+2 where n=18 to 50.
Microcrystalline Waxes
- Mainly branched chain with some naphthenic content.
- H/Cs have approx. 34 to >70 C-atoms. Therefore, higher average MW
and higher Mpt. compared to paraffin wax.
In general wax dosage varies between 3 and 12phr.
For more dynamic applications, e.g. tires and conveyor belts the dosage
can be as low as approx. 1.5phr. Additional protection through effective
antiozonants is a must in these cases.
For cellular rubber wax may be used at up to 20phr.

Sulphur Bloom

A curse to the rubber industry

Usually happened when vulcanizates are under-cure.

Also, the level used is significantly above their solubility limit within the
based polymer(s).
Particle size of sulphur is critical. A 10% retain on 200 mesh screen is
essential. High coarseness gives uneven concentrations and spotty bloom
leading to either stain or spots on vulcanizate.
Insoluble sulphur is recommended to prevent bloom. Taking note that
processing temperature and storage conditions must be taken care.

Types of Sulphur
Two basic types of sulphur Soluble & Insoluble

Phase

Crystalline
S-Rings
(SOLUBLE in CS2)

Amorphous
S-chain
(INSOLUBLE in CS2)

Symbol

Form & Remark

Rhombic modification
M.pt. 113 deg C.

Mono-clinic modification
M.pt. 119 deg C

Mother-of-pearl like modification

M.pt. 107 deg C

Sometimes could be micro-crystalline.

Obtained as insoluble amorphous residue by
extraction with CS2 when quenching the melt
after it has been heated at various
temperatures.

When sulphur is insoluble in CS2, it is again insoluble in rubber polymers

Factors to be noted
with Insoluble Sulphur

Insoluble sulphur agglomerates due to electro-static charge, thus very

difficult to disperse

Insoluble sulphur reverts into soluble sulphur at above 80 deg C

Blending and dispersion of insoluble sulphur must take place at

temperature below the critical reversion point

Applies to any further processing, like extruding and calendering

Inorganic and organic bases (oxides and hydroxides), oxygen containing

solvents and cationic wetting agents can also increase tendency to revert

Take note on accelerators system in which the activators are not too
alkaline

MBT (Accelerator M) should never be used with insoluble sulphur

Even NOT to store insoluble sulphur next to MBT

Sulphur Solubility in Standard Polymers

Accelerators
TMTD(Tetramethyl thiuram disulphide) is well known to cause bloom,
particularly when used as sulphurless curing system. A whitish bloom is
formed which consists of its reaction product ZDMC (This applied similarly
for TMTM which gives higher yield of ZDMC).
Bloom can occur at only 0.5phr although it is occasionally used at 3phr
without any blooming problems in some cases.
Replacing part of TMTD with TETD and/or DDTS(Dimehtyl diphenyl
thiuramdisulphide) could avoid bloom. Simultaneously, use of mercapto or
sulphenamide type accelerators can be helpful.
TBTD is totally soluble in most rubbers and so is the ZDBC reaction
product formed. So it does not bloom.

Accelerators (cont)

Solubility of Compounding Materials in Cyclohexane at RT (g/100g)

(Cyclohexane is used as a model for NR)
ZMBT

0.01

Zn Stearic

0.1

DOTG

0.3

MBT

0.3

MBTS

0.3

TMTD

0.3

TMTM

0.3

ZDMC

0.5

DPG

0.8

OTOS

0.8

Sulphur

2.0

TETD

4.0

Stearic Acid

5.0

DTDM

7.5

CBS

8.0

OBTS

14.0

ZDBC

16.0

Accelerators (cont)

Solubility of Accelerators in EPDM

EPDM has low unsaturation and therefore required high levels of effective
accelerators with sulphur for high state of cure.
Accelerator combinations is used because of the low solubility of the polar
accelerators in the unpolar elastomer less effective and bloom.
Accelerator
CuDMC
TeDMC

Sol. Limit (phr) Accelerator

0.3
ZDBC

Sol. Limit (phr)

2.0

TMTD
TMTD
ZDMC

0.5 0.7

CBS
MBS
TBBS

2.5

DTDM
TETD
ZDEC

0.7 0.9

MBT
MBTS

3.0

Solubility drops with increasing ethylene content

Naphthenic oil is better than paraffinic oil for improved solubility
Stearic acid has a slight solubilizing effect

Peroxides
Bloom does not occur with most peroxides.

But two decomposition products of Bis-(tert-butylperoxyisopropyl)-benzene

may cause bloom.
The chemicals responsible for a whitish dry bloom are the high molecular
alcohols m- and p-dihydroxyl diisopropyl benzene.
The other decomposition products are either rubber soluble or volatile such
as acetone and methane.

Plasticizers
Compatibility between the plasticizer/oil and the elastomers mainly governs the
tendency for bloom.
e.g. 2phr paraffinic oil in NBR vulcanizate can result in an undesirable greasy
surface due to excessive bleeding of the plasticizer.
Similarly, 5phr paraffinic oil can bloom (exude) heavily from CR vulcanizate.
Naphthenic oil can be used in CR at 20-25phr without bloom problems.
Aromatic oils are very compatible with CR. However, high level Ar.Oil may cause
sticking to equipment. Stickiness is much reduced by adding some naphthenic oil
that have a certain lubricating effect.
Waxes, petroleum jelly, blown asphalt and coal tar can reduce the compatibility of
oil in CR.

Antistatic plasticizers are known to cause heavy bloom when used above their
solubility limit. In the case for silica filled compound with antistatic plasticizer,
undesirable bleeding can be avoided by eliminating DEG which is often used as an
activator in the formulation.

Antidegradants
Anti-ozonants
- Must react with ozone faster than the elastomer
- Must be available at the vulcanisate surface
- The reaction product with ozone (ozonide) must formed continuous
protection film against further ozone attack.
When totally soluble material is used the surface concentration will be
proportional to the dosage level and not change on storage.
The faster and the higher the surface concentration, the more effective the
anti-ozonants. The ranking as follow:-

IPPD (N-isopropyl-N-phenyl-p-phenylenediamine)
DTPD (N,N-Ditolyl-p-phenylenediamine)
6PPD (N-1,3-dimethyl butyl-N-p-phenylenediamine)
77PD (N,N-Bis-(1,4-dimethyl pentyl)-p-phenylenediamine

Antidegradants (cont)
Anti-oxidants
Blooming generally does not occur with phenolic and phosphite antioxidants
which have high solubility limit in rubber.
PBN which was widely used in former times, caused bloom at over 1.5
2phr.
PAN might be used up to 5phr without bloom.
Polymerized 2,2,4-Trimethyl-1,2-dihydroquinoline (TMQ) migrates to the
surface of uncured carbon black filled compound and causes a color change
from black to dark blue after stored for a period of several days.
The oligomers present in TMQ at concentrations depending upon the
production process have a higher solubility in rubber than the polymeric
substance. The blooming rate is shown as below:Polymeric TMQ > Tetramer > Trimer > Dimer > Monomer
More than 1000 components have been detected in TMQ. Impurities of that
kind have the tendency to revert insoluble sulphur to soluble type and for
subsequent sulphur bloom.

Retarders
Acid type retarders like Phthalic anhydride (PTA) and Salicylic acid
or
N-phenyl-N-(trichloromethyl-sulphenyl)-benzene sulphonamide
give no blooming so far.
Benzoic acid (not only as retarder but also as viscosity reducer, and at
high dosage to increase hardness) can migrate to vulcanizate surface.
-- transparent to whitish crystals like frost pattern on window pane on
steam cured vulcanizate.
Cyclohexylthiophthalimide (CTP) can cause a grayish bloom at
above 0.4 to 0.5 phr.

Lubricants
Zinc Soaps
Zinc stearate and most linear saturated fatty acids based zinc soaps have
very low solubility in rubber.
Zinc stearate can only be observed when the vulcanizate is slowly cooled and
diffusion to the rubber surface can take place.
Nevertheless, amines as accelerator decomposition products will complex and
solubilize the zinc, thus zinc stearate does not appear at the vulcanizate
surface. But when in contact with water vapor, insoluble basic zinc stearate
can be formed and bloom out.
Zinc soaps of branched or aromatic carboxylic acids are soluble in rubber.
They provide substantial improvement in creep and modulus reproducibility
compared with zinc stearate.
Fatty Acid Amides
Very limited solubility in this group of lubricants which bloom easily to
provide anti-block properties for polyolefin films at dosage of just 0.05%.
-typical e.g. are amides derived from stearic, oleic and erucic acid.

Resorcinol
Resorcinol has limited solubility in rubber so it blooms.
Its tendency of bloom increases in presence of Hexamethylene tetramine
(HMT).
A non-blooming derivative of resorcinol is available to users of RFS
(Resorcinol/Formaldehyde/Silica) adhesive system.

Fillers
Fillers are insoluble and cannot migrate.
In some cases, the exposure of fillers at vulcanizate surface is actually termed
as Frosting.
Frosting is caused by ozone attack and also ultra-violet degradation on
relaxed vulcanizate containing white fillers. Usually the frost is of white or
gray color.
Very often, frosting is mistaken as bloom by un-reacted accelerators and etc.
But frosting is confirmed as solvent washing or heating would not remove the
bloom layer.
Optimum filler dispersion will help to avoid frosting.

Colorants
Organic colorants which are not completely soluble can cause crystalline
bloom.
Inorganic colorants are insoluble and thus no bloom is generated.
Plate Out of colorants are known from plastic processing is caused by
insufficient compatibility of certain additives, such as plasticizers or
lubricants. Exudation of these additives take place on processing and part
of the colorant is transported by the additive to the surface.
Plate out can also occur with fillers.
Plate out deposits on calender bowls and extruder dies.

SUMMARY

This presentation does not really totally help you how to

eliminate or solve the blooming problem
BUT at least guide you how to prevent the tendency to occur.
The concept of
PREVENTION IS BETTER THAN CURE
is applied.