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EBB 220/3

ELASTOMER & LATEX

Introduction
The word rubber comes from the materials from the rubber tree
name Havea Brasiliensis
The different between raw rubber and vulcanized rubber or
elastomer:

1.Raw rubber either natural rubber or synthetic rubber


are materials that has plastic properties and can be
reshaping at high temperature and not sutaible for
applications.
2.Elastomer is the words that used for vulcanized rubber,
vulcanisate or crosslinking rubber

Raw rubber vs Elastomer

Raw rubber no crosslinking

Elastomer crosslinking

In beginning all products from rubber are


made from natural rubber that are
produced from materials from natural
rubber tree called latex.
Synthetic rubber are produced from
reactions of low molecular weight
materials called monomer to produce
long chain molecule called polymer
Elastic properties are produced by mixing
raw rubber with specific additives during
rubber compounding
Latex being collected from a
tapped rubber tree

When rubber was heated the chemical reactions occur, the process
called vulcanization or curing.
Process where rubber molecules were tied together at specific place
called crosslinks

The crosslinks will prevent the slippage of molecules.


Elastomer are elastic materials that can deformed when forced being
applied and back to the original shape when release the forced.

The words elastomer comes from elastic polymer.

Function of crosslinks

Stretch

Retract

Rubber processing
Raw Rubber
Mastication process
Compounding
Rubber Compound

Forming process
Vulcanization process
Vulcanize rubber/
End product

Mastication Process

Mastication is mechanical shearing process using two roll mill or


internal mixer) to
Reduce the molecular weight,
Reduce the viscosity and
soften the raw rubber.

After mastication the processing will be much easier and


increased the effectiveness of dispersions of compounding
ingredients.
The mastication is compulsory for natural rubber due to high
molecular weight in nature (around 105-106 )

Compounding Process
Rubber compounding is the way of making useful products from
raw rubber
The process involved the addition of additives to change the
masticated raw rubber to rubber compound before a forming
process.
The compounding process used the two roll mill or internal mixer

General rubber compounding formulation


Elastomer/ Raw rubber
Fillers
Softener
Antioxidant
Stearic Acid
Zinc Oxide
Accelerator
Sulphur

Total

100
50
5
1
1
5
1
2

165

**
Parts per hundred rubber (pphr) All the ingredients used
in a compound formulation are normally given in amounts
based on a total of 100 parts of the rubber or combination of
rubber used.

Compounding Ingredients
Each ingredient has a specific function either in processing,
vulcanization or end use of the products.
The various ingredients may be classified according to their
specific functions in the following groups:
1. Fillers
As reinforcement or cost reduction. Eg. carbon black or non black
fillers
2. Plasticizers or softeners
Extenders, processing aids, special plasticizers
3. Age resistors or antidegradants
Antioxidants, antiozonants, special age resistors
4. Vulcanizing or curing ingredients
vulcanization agents , accelerators and activator
5. Special-purpose ingredients
Coloring pigments, blowing agents, flame retardants, antistatics
agents retarders, peptizers

Sulphur vulcanization
Sulfur is the oldest vulcanization agent for unsaturated rubbers
used in rubber practice
The crosslinking produced can have a monosulphide and
polysulphide or both depending on the vulcanization systems
used
Sulphur vulcanization systems can be divided into 3 systems
depending on the relative amount of sulphur & accelerator used.
The three systems can be differentiated through the types of
crosslinking produced and the main chain modification after
vulcanization

Network structure of sulphur vulcanizate

Sulphur vulcanization systems


System

Sulphur content
(pphr)

Accelerator
contents (pphr)

Conventional vulcanization
(CV)

2.0-3.5

1.0-0.5

Semi- Efficient vulcanization


(semi-EV)

1.0-2.0
(or sulphur donor)

2.5-1.0

Efficient vulcanization (EV)

0.-1.0
(or sulphur donor)

6.0-2.0

Sulphur donor sulphur vulcanization


systems without sulphur but gives a sulphur
during vulcanization (for example sulphur
from accelerator)

Depends on product:
Good Strength- CV system
Good Ageing- EV
Semi EV- in between

Efficient
vulcanization

Conventional
vulcanization

In CV- there are many S-S link, EV has many C-S link. Depend on bond
energy, for ageing C-S is more difficult to break compared to S-S (thus
EV shows good ageing properties).

Peroxide vulcanization
Organic peroxides as curing agent.

Especially for saturated rubbers which do not contain any reactive


group capable of forming x-links.
Peroxide does not enter into the polymer chains but produces radicals
which form C-to-C linkages with adjacent polymer chains
The peroxide decompose at vulcanization temp & form free radicals.
These free radicals would extract H atom from polymer chains and
form bonding, leaving polymer radicals. The polymer radical will react
with adjacent polymer radical to form crosslink.

Eg. dicumyl peroxide, zinc peroxide, benzoyl peroxide, 2,4chlorobenzoyl peroxide

Forming Process
After all the compounding ingredients have
been properly mixed the compounded green
stock is tacky and thermoplastics
In this plastic condition, the stock can be
shaped by the applications of force.
This can be accomplished for example, by
squeezing it betweens rolls (calendering) or
pushing through an orifice having the desired
shape (tubing or extruding).

Vulcanization Process
After the green stock has been formed to the desired
shape, it needs to be converted to an elastic materials
vulcanization process usually under pressure at elevated
temperature using different techniques such as

Press vulcanization
Open vulcanization/ autoclave
Continuous vulcanization
Chemically the process involves insertation of crosslinks
between the polymer macromolecules through the actions
of vulcanizing ingredients.
The crosslinking of rubber also referring as curing it a
process whereby a raw materials is converted into a useful
product.

Press Vulcanization
Press vulcanization takes place in press that
supply heat and pressure.
Examples of press vulcanization
Compression Molding
Transfer Molding
Injection Molding

Compression Moulding

Most of rubber products produced using this method.

Rubber compound is placed in each cavity of the mold and


closed and placed in hydraulic press.

Under the applied of hydraulic pressure (4-6 MPa) at


elevated temperature (140-200C) using the cure time
obtained from rheometer curve.

After mould is closed the stock will flow and completely


fill the mould cavity

The mould is maintained closed under pressure for a


prescribed time at particular moulding temperature the
mould is then removed from the press and opened to
remove the moulded part.

Molding press

Before

After

Transfer Moulding
This is a variation on compression moulding and involves
loading a pre-formed blank of rubber in a cavity connected
to the mould cavity by a runner.
The blank is compressed when the mould closes and is
forced under pressure into the mould cavity.

Before

After

Open Vulcanization/Autoclaves
Autoclaves, known as 'curing pans' or 'vulcanisers
Its a pressure vessels filled with steam that are used to cure
rubber articles not contained in moulds (hose, extruded
section, coated cloth, retread tyres, and small cable
batches).
Most are horizontal with vertical autoclaves now rare. They
can have either quick opening doors or multi-bolted doors.

Continuous Vulcanization
Products produced on a continuous process such as rubber
covered cable and strip are continuously cured, rather than
on a batch basis.
There are various methods but each one is sited just after
the exit die of the extruder or calender.

Finishing Process

Many rubber articles require finishing operations after


vulcanization.

For example, the flash attached to moulded parts must be


removed before the parts are ready for use carried out by
hand trimming using scissors or knives.

Some rubber parts are painted to give them an attractive finish or


more often to protect against ozone, oils, acids, chemicals ant the
like. The paints are usually rubber based.

Items such as seals and windshield wiper blades may require


surface treatment with chlorine, bromine or fluorine in water.
The halogenated surface will have lower friction than the
untreated surface while the bulk will be unaffected.

The finishing operations of extruded articles include coiling,


cutting to specific length and washing.

Quality Control

Quality control is necessary to ensure the quality


of final products
During various stages, checking will be
performed on incoming materials, in process
materials and finished products.
The rubber manufacturer usually test the raw
materials to make sure that they are uniform
and of adequate quality
Control test are applied to various steps in the
manufacturing process. The test employed are
sensitive to any change in the rubber compound
resulting from errors.

Example of errors
1.
2.
3.
4.
5.

faulty compounding ingredients,


poor dispersion,
improper temperature control,
wrong sequence of addition
too short or too long mixing cycles.

The control scheme utilize mostly standardized physical


tests on both unvulcanized and vulcanized rubber
compounds.

Unvulcanized compound tests measurement of the viscosity, scorch time and


cure rate.

Vulcanized compound tests measurements density, hardness, tensile


modulus, tensile strength and elongation at break.

Materials

Function

Elastomer/raw rubber

Basic components in rubber compounding

Fillers

Used for reinforced or modified the mechanical


properties and also to reduced the cost

Plasticier

To ease the processing, to modify the specific


properties and also as extender

Anti oxidant

To protect the rubber from ageing

Accelerator

To increase vulcanization process and reduced the


time of vulcanization

Activator

To increased the accelerator efficiency

Vulcanization agent

Needed during vulcanization process to produced a


crosslinking

Other ingredients

Used for specified purpose such as for coloring,


retarder etc

Process

Function

Mastication

Mechanical shearing process to reduced the


molecular weight, viscosity and to soften the
rubber.

Compounding

Process of addition the rubber additives to


convert the raw rubber into rubber compound.

Forming

Process of convert the rubber compound into a


required size and shape with a forced.

Vulcanization

Process of convert the shape product to an


elastic materials with formation a crosslinking
under temperature and pressure

Final Operation

Final operation after vulcanization such as


trimming, paint or surface treatment

Quality Control

To ensure the quality of final product

Latex processing
Raw Latex
Latex compounding

Compounded Latex

Latex curing
Latex processing

Vulcanize latex/
End product

Introduction

Latex is defined as a dispersion of polymer in an aqueous


medium which is a dispersion of polymeric solids in water

Latex has two phases:


1.

The dispersed phase or discontinues phase consisting of small


particles of polymers (particle size < 5 micrometer in diameter)

2.

The dispersion medium or the continuous phase or serum (a dilute


aqueous solution)

Classification of latices
Latices are classified as:
1.

Natural latices obtained from plants

2.

Synthetic latices produced from emulsion polymerization


process

3.

Artificial latices produced by dispersing the appropriate bulk


polymer in an aqueous dispersion medium

4.

Modified latices produced by modification of existing type


of latex ( by grafting, crosslinking etc)

Natural rubber latex concentrate


The NR latex obtained from the plantation is called fresh or field latex

The field latex contains about 33% NR and thus not economical to be
used to make a latex products
The rubber content of the field latex need to be increased before it is
used in making latex products.
This is achieved by doing concentration process to the field latex
There are few methods that can be used to concentrate natural rubber
latex:
1. Concentration by creaming
2. Concentration by centrifugation
3. Concentration by evaporation

Preservations for latex concentrate


Preservation is necessary to prevent micro-organism from attacking the
non-rubber components of latex.
Latex which has been attacked by micro-organism has lower colloidal
stability and bad odour.
Concentrated latex is preserved for long-term storage. The most popular
preservative is ammonia.
There are two types ammonia preservation systems:
Low -ammonia latex (LA latex)

0.2 % m/m ammonia.


short term preservation
suitable for certain applications such as latex foam requires low ammonia content
in order for to gel properly.
secondary preservatives are added to LA latex for long term storage.

High ammonia latex (HA latex):


0.6 - 0.8 % m/m of ammonia
long term preservation

Investigation Latex Poperties


The properties of the latex are of interest because:

To gain better understanding of the physical and chemical


nature of the latex.

To determine the suitability of the latex for a particular


application.

To assure the general quality of the latex

The test methods to evaluate latex properties can be


classified into three groups:
1.
2.
3.

Tests related to chemical composition


Tests related to colloidal stability
Tests related to physical properties

Latex Compounding

Process of addition of chemicals to the latex compounding

Latex containing these chemicals known as compounded latex.

Most chemicals added to the latex ~ in solid form therefore these


chemical need to be dispersed in water first before added to the
latex.

The dispersed chemicals prepared by grinding them together


with the dispersing agent in water.

The chemicals used in latex compounding can be divided into three


general classifications:
1. Surface active agents (surfactants)
2. Liquid phase modifier
3. Elastomer or rubber phase modifier

General latex compounding formulation


61.7% Elastomer/ Raw latex
10% KOH
50% Sulphur
50% Zinc Oxide
50% Accelerator
50% Antioxidant
60% Fillers

100
0.3
0.5
0.25
0.75
0.5
15

Total

117.3

**
Parts per hundred rubber (pphr) All the ingredients used
in a compound formulation are normally given in amounts
based on a total of 100 parts of the rubber or combination of
rubber used.

Latex Curing
Curing of latex process of introducing cross-links in the rubber
molecules.
The term vulcanisation used to describe cross-linking process involving
sulphur as cross-linking agent.
Two types of vulcanisation in latex:
pre-vulcanisation when the vulcanisation is done while the latex is
still in liquid state.
post-vulcanisation if the vulcanisation is done on latex film.

Latex that has been pre-vulcanised referred as pre-vulcanised latex or PV


latex (for pre-vulcanised natural rubber PVNR).
Appearance PVNR very similar to unvulcanised NR with maintained
fluidity.
The cross-linking only takes place in each individual particles.
particles in PVNR have the same shape, size & size distribution as those
in initial unvulcanised latex.

Preparation of sulphur-prevulcanised NR latex.

Latex

Stabilisers

Depends on
formulation

Vulcanising agents +
other ingredients

To get desired degree


of vulcanisation
After desired degree of
vulcanisation attained
latex is cooled and run off
into container

Strained & bulked

Vulcanisation
55-80C

Pre-vulcanised latex
Mature for 7 days at normal
ambient temperature
to improve uniformity

Maturation

Processing

Latex is constantly stirred


avoid formation of skin &
sedimentation of ingredients.
Various tests to check degree
of vulcanisation

Latex Dipping Process

Dipping process is used to make thin and hollow latex products


such as gloves, catheters and toys These products are called
dipped products.

In principle dipping process involves dipping cleaned formers


into compounded latex (prevulcanized or postvulcanized
compound)

Latex film will be formed around the former and product obtained
by drying and curing the films.

Latex dipping process can be classified into three methods:


1.

Straight or simple dipping no stabilize agency is used to form the films

2.

Coagulant dipping a direct coacervant is used to promote film formation

3.

Heat-sensitized dipping a heat sensitizer is used to promote film formation

How is a glove produced?


Collecting the raw material

After workers tap the rubber trees the raw material is


centrifuged with the effluent latex
After a 25 day maturity and stabilization period, the latex
is sent to the glove factory
Combined with chemical compounds according to the
glove specifications.
(formulation plays a major role in determining the quality of
the final product. )
On a single or double line, glove formers go through
stages of dipping, leaching, rinsing and drying.
(The speed of the line determines the thickness and
strength, the formers the texture and size of the glove)
After the forming process is completed, the gloves need
to remove harsh chemicals through a vulcanization and
leaching process. During the leaching phase protein is
minimized.
Washed and dried before they are inspected for testing.

Example of the exams question


Gives the rubber processing flow chart including the simple
definition of the processes involved.
Gives the general formulation to produce elastomer products
with simple elaborations ingredients used.
Briefly explain the vulcanization process.

Students Activity

In 5 minutes try to list how many points that you remember


the differences between elastomer and latex