Chemical Foaming Agents
Hydrocerol®
BASICS
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BU Masterbatches - RBL Europe, Product Management Additives, 01.06.2013
Table of Contents
What are chemical foaming agents?
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Hydrocerol® in Extrusion
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Hydrocerol® in Injection Molding
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Direct Gassing = Physical Foaming
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Tools
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Contact
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What are chemical
foaming agents?
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Why foaming?
– Cost reduction
– Weight reduction
– Material savings
– Reducing Carbon Footprint
– Better thermal insulation properties
– Higher stiffness-to-weight ratio
– Processing aid in injection molding
- Decreasing cooling times
- Higher Injection Speed
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Examples of use
BMW 3series dashboard carrier, PPO and PP-GF
Danone Activia yogurt cup, PS and PLA
Artificial wine corks, PE, TPE
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The principle
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Exothermic and Endothermic chemical foaming
agents
Exothermic
Endothermic
Exothermic CFA’s like
Endothermic CFA´s like
• azodicarbonamide
• sodium bicarbonate
• sulfonylhydrazide
• citric acid and its salts
• 5-phenyltetrazole etc.
generate heat
absorb heat
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Exothermic and Endothermic chemical foaming
agents
CFA (endo)
CFA (exo)
+∆E
+∆E1
CO2
+ H2O
+ inorg. byproducts
N2
+ ∆E2
+ org. byproducts
T
DSC-Curve
Endothermic Decomposition
E+
DSC-Curve
Exothermic Decomposition
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Exothermic chemical foaming agents
Chemistry
Azodicarbonamide
Decomp.
range [°C]
Chemical Structure
Foaming Agent
H 2N
ADC
CO
N
N
CO
NH 2
Modified ADC
Oxybis( benzenesulfonylhydrazide)
5-Phenyltetrazole
OBSH
H 2N
NH
SO 2
O
5 - PT
N
N
N
C
SO 2 NH
NH 2
Gas yield
[ml/g]
Main
gases
N2 , CO,
CO2, (NH3 )
205 – 215
280 – 320
155 - 220
150 – 300
140 – 165
120 – 150
N 2 , H2 O
240 – 250
190 –210
N2
215 - 235
120 – 140
N2, CO2
110 – 140
120 –140
N 2 , H2 O
N
H
p-Toluylensulfonylsemicarbazid
TSS
p-Toluylensulfonylhydrazid
TSH
H3C
SO 2 NH
H3C
NH
SO 2 NH
CONH 2
NH 2
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Endothermic chemical foaming agents
Chemistry
Production of Sodium bicarbonate
Na Cl + NH3 + H2O + CO2
NaHCO3 + NH4Cl
Decomposition of Sodium bicarbonate
2 NaHCO3
Na2CO3 + H2O + CO2
Decomposition of Citric acid
H2C COOH
H2C
HO C COOH
H2C COOH
C COOH
H2C COOH
Citric Acid
Itaconic Acid
+ CO2 +
H2O
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Endothermic chemical foaming agents
Properties
Decomposition range
I
I
I
Processing temperature of polymer
I
I
I
I
I
I
I
I
I
I
Citrate
Citrate/Bicarbonate-Mix
Bicarbonate/Citrate-Mix
Bicarbonate
I
I
105
I
120
I
135
I
150
I
165
I
180
I
195
I
210
I
225
I
240
I
255
I
270
°C
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What about Universal Chemical Foaming Agents?
– Melt temperature would have to be high enough to ensure a complete decomposition
– Carrier Polymer would have to fit into the matrix of the target resin
– Pressure of the polymer melt would have to be kept high enough to keep the gas
dissolved
AND
– The different gasses (N2 , CO2) have differences in gas solubility in the polymer melt
– Incompatible gas / polymer combinations can cause problems
A tailor-made solution is needed for every process
Hydrocerol® in Extrusion
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Scope of use and applications
– Weight reduction: 10 - 50%
– Thermoforming of extruded sheets
– Co-Extrusion in all common layer structures
– Lower heat transfer
– Food contact approved grades
– Films, sheets, profiles and pipes, etc.
– PE, PP, PS, PET, PVC, PLA etc.
– Hydrocerol PEX standard range
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Parameters
Rapid Pressure Build-up:
High pressure is the key condition to
keep the evolved gas dissolved in the
melt
No Pressure-Drop:
Pressure-Drop (e.g. at melt sieves) can
cause pre-foaming problems
Sufficient Melt Strength :
The dissolved gas decreases the melt
viscosity. Lower MFI (2 - 3 times) may be
required (co-extrusion !!)
Temperature:
Decomposition temperature of the CFA has
to be reached at least once during the
process
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Pressure Profile
pressure
pressure
conventional
extruder
extruder with
grooved feeding
zone
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Temperature Profile
plastic
Hydrocerol®
foam
temperature
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decomposition temperature
of the foaming agent
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Chemical Foaming
plastic
Hydrocerol®
Plastification
Reaction
Dispersion
Foaming
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Example of use:
PS sheets and trays
– Mono or co-ex films
– Slot die for chemical foaming, 10-30% weight reduction
Suitable Formulation:
– GPPS 50%
– HIPS 50%
– SBS copolymers as modifiers
– Nucleation: e.g. talc
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Foam structure in Extrusion
Hydrocerol® in Injection
Molding
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Advantages
For the plastic part:
compact
– Reduction of weight
– Elimination of sink mark
– Elimination of warpage / Improved dimensional accuracy
foamed
For the process:
– Improvement of flowability
– Reduction of injection pressure
– Reduction of clamping force (enables to use smaller machines)
– Faster cycle time
Hydrocerol ITP product range
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Equipment and Process
Hydrocerol® can usually be processed on every common injection molding machine.
The advantages are:
– Shut-of-nozzle to avoid premature foaming
Gates and flow path should be configured in a way as to allow a fast and even mold
filling
– A very good venting at the end of the flow path
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Case Study:
Mold venting
- Floater (PA66)
- HYDROCEROL ITP825
Drastic reduction of
clamping force
(improved venting)
Weight reduction 5%
Weight reduction 50%
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Important parameters
– Back Pressure
- A specific pressure of 40bar should be applied to avoid premature foaming
- Recommendation: use of shut-off nozzle/position control of the screw
– Holding Pressure
- Should be as low as possible (ideally zero) to allow nucleation and expansion of the
dissolved gas
– Shot weight
- Reduced, to give room for the gas to expand (needed if weight reduction is required)
– Injection Speed
- As high as possible, to prevent premature expansion of the gas and forming of silver
streaks
– Temperature profile
- Dependent on HYDROCEROL® grade - information can be extracted from technical
datasheet
Direct Gassing =
Physical Foaming
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Scope of use
– Extremely light foam (15 kg / m³)
– Special machinery
– Gas dosing unit
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Applications
– Food trays (PS)
– Pipe insulation (PE)
– Cable insulation (PE, PVC)
– XPS-boards
– Seals
– Profiles
– Food-trays
– Insulation boards
– CFA as a nucleant
– Hydrocerol NUC series
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Physical Foaming
plastic
GAS
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Hydrocerol in Direct Gassing
Nucleation
Nucleating Agents create centers for foam
cells.
Interruption of resin matrix leads to irregular
“spots” where the dissolved gas starts
separating easily.
The result are more and smaller cells.
Without or poor
passive nucleation
With active
Nucleation
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Hydrocerol in Direct Gassing
Active versus Passive Nucleation
Passive Nucleation
Active Nucleation
decomposition
HYDROCEROL
solid particles
foaming gas
foaming gas
gas from decomposition
solid particles
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Hydrocerol in Direct Gassing
Different dosages
– 2% Hydrocerol NUC 5510 (50% talc MB)
– 0,5% HYDROCEROL NUC 5540
(active/passive mixture)
– 0,3% HYDROCEROL NUC 5535 (active)
Tools
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Questionnaire
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Cost calculator
– Helps to create a commercial
scenario for weight reduction and
cost savings
– Finds break even point for balance of
weight reduction and additional costs
of CFA
– Can be discussed with customer or
used as an internal back up for
monitoring projects
Contact
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Contact
CLARIANT MASTERBATCHES
RBL EUROPE
Clariant SE
BU Masterbatches
Am Unisys-Park 1
D-65843 Sulzbach am Taunus
Tel: +49 6196 757 6276 / +49 6196 757 60
Fax: +49 6196 757 6113
WWW.CLARIANT.MASTERBATCHES.COM
[email protected]
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Disclaimer
This presentation contains certain statements
that are neither reported financial results nor
other historical information. This presentation
also includes forward-looking statements.
Because these forward-looking statements
are subject to risks and uncertainties, actual
future results may differ materially from those
expressed in or implied by the statements.
Many of these risks and uncertainties relate to
factors that are beyond Clariant’s ability to
control or estimate precisely, such as future
market conditions, currency fluctuations, the
behavior of other market participants, the
actions of governmental regulators and other
risk factors such as: the timing and strength of
new product offerings; pricing strategies of
competitors; the Company's ability to continue
to receive adequate products
from its vendors on acceptable terms, or at all,
and to continue to obtain sufficient financing to
meet its liquidity needs; and changes in the
political, social and regulatory framework in
which the Company operates or in economic
or technological trends or conditions, including
currency fluctuations, inflation and consumer
confidence, on a global, regional or national
basis.
Readers are cautioned not to place undue
reliance on these forward-looking statements,
which speak only as of the date of this
document. Clariant does not undertake any
obligation to publicly release any revisions to
these forward-looking statements to reflect
events or circumstances after the date of
these materials.