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3M A dvanced Materials Division
Benefits and Use of PolymerProcessing Additives
SPE FlexPackCon 2019
John Prindl
Polymer Processing Additives
© 3M 2019. A ll Rights Reserved. 2
Topics Covered
What are they?
What do they do?
How do they do what they do?Factors influencing performance
Selection guidelines
Highlighted Applications
Key Takeaways
© 3M 2019. A ll Rights Reserved. 3
• PPAs can positively impact your process and/or the finished article
• Other additives in the formulation can impact PPA performance
• Optimization of total additive package and processing conditions is importantfor maximum PPA effectiveness
• PPA selection and use level optimization is important
• PPA can help enhance the processing of recycled materials
3M™ Dynamar™ PPAs
PPA = Polymer Processing Additive
Fluoropolymer-based additives used at very low concentrations (ppm)to improve the extrusion processing of plastics
© 3M 2019. A ll Rights Reserved. 4
Benefits and Applications
• Elimination of melt fracture• Reduction in operating pressure• Reduction of die build-up• Reduction in gel formation• Faster color transitions
Effective at low concentrations with noeffect on surface or physical properties:▪ 2 0 0 – 150 0 ppm for melt fracture elimination
▪ 20– 3 0 0 ppm for die build-up elimination
© 3M 20 189 . A ll Rights Reserved. 5
Extrusion processes where the shear rate istypically less than or equal to 2 0 0 0 sec-1
• Blown Film
• C a st Film• Continuous Extrusion
Blow Molding
• Pipe/Tubing
• Fiber Extrusion
• Wire and Cable
• Concentrate Compounding
© 3M 2019. A ll Rights Reserved. 6
Processes that Benefit from PPA
Melt Fracture Elimination with PPA
L L DPE without PPA L L DPE with PPA
vs.
© 3M 2019. A ll Rights Reserved. 7
Die Wall
Cross- linked and Oxidized Gel Reduction with PPA
• Oxidized species stick to die wall• Act as a site for other oxidation to
occur – to the polymer• C a uses a localized high
concentration of oxidized species• Leads to cross- linking
PPAs for Gel ReductionMechanism for Gel Formation
© 3M 2019. A ll Rights Reserved. 8
PPA
PPAs for Gel ReductionMechanism for Gel Formation
Cross- linked and Oxidized Gel Reduction with PPA
Die Wall
• PPA coats the die wall and preventsbuild-up
• Fluoropolymer is thermally stableunlike the low M W components
© 3M 2019. A ll Rights Reserved. 9
Die Buildup Reduction
Without PPA With PPA
vs.
© 3M 2019. A ll Rights Reserved. 10
LLDPE + 6 % TiO 2LLDPE + 6 % TiO 2 +
250ppm PPA
• Elimination of die buildup
• Improved gaugeuniformity
• Pressure reduction• Reduction in gel formation
Cast F ilm
vs.
© 3M 2019. A ll Rights Reserved. 11
© 3M 2019. A ll Rights Reserved. 12
55 min
5 0
45
4 0
35
3 0
25
2 0
15
10
5
N o PPA W ith PPA
Carb
onBl
ack
Nat
ural
Color Changeover Time Reduction
S tart
vs.
© 3M 2018. A ll Rights Reserved. 12
Pipe Applications
No PPA With PPA
Long term hydrostatic stressproperties of HDPE are notaffected by using PPAs
i
• Elimination of surface defects
• Reduction of extrusionpressure
• Reduction of processingtemperature
• Improved output
vs.
© 3M 2019. A ll Rights Reserved. 13
Blow Molding
• Reduction of processing and parisontemperatures → Reduction of cycletime
• Increased gloss• Consistent surface finish –
removal of die lines• Reduction in warpage• Reduction in color changeover time
Control With FX 5911
0
10
20
30
40
50
60
StartNo PPA
EndWith PPA
StartNo PPA
EndWith PPA
60°G
loss
Outside Surface Inside Surface
Gloss Improvement
vs.
© 3M 2019. A ll Rights Reserved. 14
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PPA Mechanism
One of the proposed mechanisms:Upon die exit, the outer layer of the melt is stretched bythe elastic recovery of the flow profile.
Origin of Sharkskin
© 3M 2019. A ll Rights Reserved. 16
PPA Mechanism
• Immiscible droplets in polyolefin matrix• High affinity for metal die wall• Dynamic, low surface
energy coating• Allows melt to flow through
die more easily
© 3M 2019. A ll Rights Reserved. 17
Using a PPA
© 3M 2019. A ll Rights Reserved. 18
When the die is coated, there is slip at the die wall, g iving a blunt flow profile.
LightMicroscopy
Reflection D I C
1000x
10µm/div
PPA Coating
PPA Coating on Gold Plated Die
© 3M 2019. A ll Rights Reserved. 19
S.E.M.3 0 0 0 x Mag.EDX Analysis
X-Ray Intensity Maps
SEM Carbon
Fluorine
10 µm
© 3M 2019. A ll Rights Reserved. 2 0
Profilometry – Y Average
Metal Shim
© 3M 2019. A ll Rights Reserved. 21
PPA Coating Equilibrium ModelPPA coating is a dynamic process
Additive selection and process factors can affect all 3 steps
N uc leation Growth Removal
i
© 3M 2019. A ll Rights Reserved. 22
© 3M 2019. A ll Rights Reserved. 23
Additive Interactions
A ntioxidants
S lip A gentsPig ments
F illers
L ubricants A ntiblocks
L ig ht S tabilizers
A ntistatsPPA
PPAs do not adversely affect theperformance of other additives.
Some additives can affect PPAperformance.
i
© 3M 2019. A ll Rights Reserved. 24
Typical Additives used in Polyethylene
Mechanisms (Modes) of Interference
© 3M 2019. A ll Rights Reserved. 25
• Abrasion• Removes PPA coating
• Adsorption• Affects coating growth process (concentration effect)
• Competition for metal die wall• Affects nucleation (PPA deposition on die wall)
• Chemical reaction• C a n affect nucleation, growth and removal
DieWallPPA Coating
© 3M 2019. A ll Rights Reserved. 26
Abrasion
Abrasion
Adsorption
MeO xide
© 3M 2019. A ll Rights Reserved. 27
PPA
PPA
PPA
Adsorption
Chemical Reaction
© 3M 2019. A ll Rights Reserved. 28
C h emical Reac tion
PPAH A L S
DieWall
PPAC aS t
C aS t
C aS t
PPAC aS tC aS t
PPA
C aS t PPA
PPA
PPAPPA
C aS t
Die Site Competition
C o mpetition for the Die Wall
© 3M 2019. A ll Rights Reserved. 29
PPA Coating Equilibrium ModelPPA coating is a dynamic process
Additive interference can affect all 3 steps
N uc leation Growth Removal
© 3M 2019. A ll Rights Reserved. 3 0
Mode Nucleation Growth Removal
Die Site Competition
Abrasion
Adsorption
Chemical Interference
© 3M 2019. A ll Rights Reserved. 31
PPA Performance T estingOptimal Conditions & Additive Interactions
Blown Film Line Testing
Blown Film Trials
0 min 15 min 3 0 min 45 min
0
20
4 0
6 0
8 0
100
0 10 20 3 0 4 0 50 6 0 70 8 0 9 0 100 110
Mel
tFra
ctur
eRe
mai
ning
(%
)
Time (minutes)
Melt FractureElimination Curve
In this example:Time to clear melt fracture =10 0 minutesi
© 3M 2019. A ll Rights Reserved. 32
Example: Effect of PPA TypeMinimum Level Study
PPA -3
20.0
0.0
40.0
6 0.0
80.0
Increasing PPA Levels100.0
120.0
0 6 0 120 180
Mel
tFra
ctur
eRe
mai
ning
,%
Time (minutes)
FX 5920A
FX 5927
3 0 0 ppm 6 0 0 ppm 9 0 0 ppm
Improved PPA Performance
100 % Melt Fracturewithout PPA
PPA -5
0.9 MI hexene LLDPE, 0 .918 density6 0 0 0 ppm AB+ 1000ppm Slip, 4 10° F, 220 s-1
© 3M 2019. A ll Rights Reserved. 33
34© 3M 2019. A ll Rights Reserved.
Effect of Processing TemperatureEffect of Temperature on PPA Coating Dynamics
C 6 mL L DPE, 1.0 MI, 0.918d, 7500 ppm AB, 1500 ppm S L IP, 180 s-1, 36 mil die gap, 1200 ppm PPA-5
PPA Deposition PPA Removal
0
20
4 0
6 0
8 0
100
120
0 6 0 120 0 6 0
Time (minutes)120 180 240
%M
eltF
ract
ure
3 6 0 ° F (182 °C )4 0 5°F (207°C )450 °F (232°C )
Effect of Shear Rate & Tem peratureTemperature and Shear Rate
L ow Shear Rate = 150s-1
High Shear Rate = 4 0 0s -1
L ow Temperature = 380 °FHigh Temperature = 450 °F
(48 mil die gap)(24 mil die gap)(193°C)(232°C)
Test Conditions:• Minimum Level Study• Resin: Hexene, Z -N, 0.9MI, 0.918• Antiblock: 4 0 0 0ppm AB
The amount of PPA and Time to C lear meltfracture dec rease with inc reasing shear rate
• Consistent with shear stress role
• Confounded with die geometry
Moderate effec t of temperature onTime to C lear melt fracture.
10 0 ppm PPA -5 20 0 ppm PPA -5
© 3M 2019. A ll Rights Reserved. 35
Importance of Resin Stabilization Package
0
20
4 0
6 0
8 0
0 20
T ime, minutes
4 0 6 0
Perc
entM
eltF
ract
ure
Resin B
Resin C
100S imilarities in B and C
© 3M 2019. A ll Rights Reserved. 36
• Both 1MI, 0.918, C -4 L L DPE
• Same polymerization process
• Same level and type of PPA
D ifference between B and C
• Resin Stabilization Package
Well-stabilizedresin
Polymer Processing Additives and Anti-Ox idants…Extruding Under the Influence”, T. Blong, K. Focquet, C. L avallée
Blown Film Data, Melt Fracture Elimination
Blown Film Trial: Constant Level Example
20.0
T T C = 4 0 - 45 min
0.0
40.0
60.0
80.0
100.0
0 20 40 60 80 100
Time (minutes)120 140 160 180 200
%M
eltF
ract
ure
Rem
aini
ng
Resin AResin BResin CResin D
410ºF, 220 s-1
Formulations cleared very fastNo differentiation
© 3M 2019. A ll Rights Reserved. 37
Blown Film Trial: Constant Level Example
0.0
20.0
40.0
60.0
80.0
FormulationswithAntiblock(+ AB) contain 6000ppm100.0
0 20 40 60 80 100
Time (minutes)120 140 160 180 200
%M
letF
ract
ure
Rem
aini
ng
ResinAResin BResin CResin DResinA+ ABResin B + ABResin C + ABResin D + AB
ABT-2500 talc
410ºF, 220 s-1
Added 6 0 0 0 ppm AB to formulationsto c reate differentiation
© 3M 2019. A ll Rights Reserved. 38
Impact of ABs on PPA PerformanceTime to C lear MF (T TC M F)• Blown film conditions
• 4 0 0 ppm PPA-3
• C 6 LLDPE 0.9 MI (0.918 g /cc)
• 1500 ppm erucamide
• 7500 ppm antiblock
• 220 s-1
• 210°C (410°F) melt
© 3M 2019. A ll Rights Reserved. 39
Impact of ABs on PPA PerformanceTime to C lear MF (T TC M F)• Blown film conditions
• 4 0 0 ppm PPA-3
• C 6 LLDPE 0.9 MI (0.918 g /cc)
• 1500 ppm erucamide
• 7500 ppm antiblock
• 220 s-1
• 210°C (410°F) melt
© 3M 2019. A ll Rights Reserved. 4 0
Effect of Masterbatch Addition Method
3% PPA + 17.1% A Bin same MB
Base Resin+ Slip MB
3% PPA MB 50 % AB MB
Blown film with 350 ppm PPA -3,2 0 0 0 ppm AB, 750 ppm Erucamide (slip)
Combined Masterbatch (CMB)Separate Masterbatch (SMB)
Base Resin+ Slip MB
© 3M 2019. A ll Rights Reserved. 41
Impact of Com pounding on PPASMB vs C M B
• Blown film conditions• 350 ppm PPA-3• C 6 LLDPE 0.9 MI• 750 ppm erucamide• 2000 ppm antiblock
• 220s-1
• 210°C (410 °F) melt
© 3M 2019. A ll Rights Reserved. 42
Impact of Com pounding on PPASMB vs C M B
• Blown film conditions• 350 ppm PPA-3• C 6 LLDPE 0.9 MI• 750 ppm erucamide• 2000 ppm antiblock
• 220s-1
• 210°C (410 °F) melt
© 3M 2019. A ll Rights Reserved. 43
Factors to Consider when S electing a PPA
© 3M 2019. A ll Rights Reserved. 44
▪ H ost Resin C haracteristics• Type (LLDPE, LDPE, PP, etc.)• Molecular weight/Melt Index• MWD
▪ O ther A dditives in the Formulation• Chemical Interactions (HALS)• Physical Interactions (AB, TiO2)
▪ Target Benefit• Melt fracture elimination• Pressure reduction• Die buildup elimination
▪ A pplication• Blown film, pipe, Wire &Cable, etc.
▪ Proc ess C onditions• Temperature• Shear rate
▪ FDA C ompliance Requirements• Polymer Dependent• Conditions of Use Dependent
▪ C ost in Use
© 3M 2019. A ll Rights Reserved. 45
PPA Use in Recycled MaterialsIndustrial waste and P C R case studies
PPAs for Recycling Applications
© 3M 2019. A ll Rights Reserved. 46
3 C ase S tudiesObjectives:▪ Determine the benefits of using PPA recycled resin streams
▪ Evaluate the impact on PPA coating performance.
➢ Material S ource: Monomaterial vs multimaterial
➢ Additives Interactions: Effect of material quality and contamination
➢ PPA addition method: Formulation inclusion vs precoating the system
Case Study 1 – White PE F ilm
S ource Material
▪ 5-Layer Film
▪ Monomaterial
▪ Contains:
- Different types of PE
- Slip, AB, W hite Pigment
- PPA (~80 ppm in outer layers)
➢ Industrial waste
T est Plan
▪ Rheometer Test
- Pressure reduction
- Rheology
- Surface improvement
▪ Blown Film Test
- Melt fracture elimination
- Pressure reduction
- Output increase
© 3M 2019. A ll Rights Reserved. 47
Rheometer test – Pressure reduction
▪ By comparison, PPA -7 gives a higher pressure reduction (19%) than PPA-6 (14%)
210°C0
20
160
140
120
100
8 0
6 0
4 0
0 10 20 3 0TIM E (MIN )
4 0 50 6 0
PRES
SURE
(BAR
)
Recycled materialRecycled material + 500 ppm FX 5922 Recycled material + 500 ppm FX 5911
410°F
Recycled material + 50 0 ppm PPA -6 Recycled material + 50 0 ppm PPA -7
© 3M 2019. A ll Rights Reserved. 48
Rheometer test – Rheology - Surface
▪ PPAs can reduce the apparent shear stress in recycled industrial waste
▪ Melt fracture is removed with both PPAs
0
500 0 0
100 0 0 0
1500 0 0
2 00 0 0 0
30 0 0 0 0
2500 0 0
3500 0 0
4 0 0 0 0 0
0 2 00 4 0 0 6 0 0 8 0 0 100 0APPAREN T S HEAR RATE (1/S)
1200 1400 160 0 1800
APPA
REN
TSH
EAR
STRE
SS(P
A)Recycled material
Recycled material + 500 ppm FX 5922 Recycled material + 500 ppm FX 5911Recycled material + 50 0 ppm PPA -7
N o PPA
5 0 0 ppm PPA -7
5 0 0 ppm PPA -6
210°C410°F
Recycled material + 50 0 ppm PPA -6
© 3M 2019. A ll Rights Reserved. 49
Blown film test– Melt fracture elimination
TIM E (MIN )
▪ Melt fracture elimination is comparable for both PPAs
8 0
70
6 0
50
4 0
3 0
20
10
0
9 0
100
0 10 20 3 0 4 0 50 6 0 70 8 0 9 0
MEL
TFR
ACTU
RE(%
)500 ppm FX 5911 500 ppm FX 5922
50 0 ppm PPA -650 0 ppm PPA -7
© 3M 2019. A ll Rights Reserved. 5 0
215°C420°F
Pressure reduction & output increase in blown film
▪ PPAs can provide a pressure reduction in reprocessed industrial waste
▪ Can enable a significant incresase in output at comparable extrusion pressure
0
50
100
150
2 00
250
0 0 20 4 0 6 0TIM E (MIN )
8 0 100
PRES
SURE
(BAR
)
500 ppm FX 5911 500 ppm FX 5922
18
16
14
12
10
8
6
4
2
0 FX 5911 FX 5922
Out
put(
kg/h
r)
Output increase
after coating after rpm increase - up to initial pressure
+ 70 % + 51%
420°F215°C
50 0 ppm PPA -650 0 ppm PPA -7
PPA-7 PPA-6
© 3M 2019. A ll Rights Reserved. 51
Case Study 2: Black PE Pipe
Material S ource
▪ Recyled – Multimaterial
▪ Irrigation pipes application
▪ Contains:
- Recycled LDPE
- Carbon black
➢ Post Consumer
Test Plan
▪ Test die build up on capillary rheometer
▪ Evalauate different PPAs
▪ Evaluate effect of different PPA levels
© 3M 2019. A ll Rights Reserved. 52
Die build up – 15 minutes
▪ PPAs are in competition with otheradditives to migrate to the metal surface
→ Interaction and competition for the diewall
▪ A solution was found by precoating PPA without other additivesto postpone the DBU
Reference PPA-4 PPA-5 PPA-7
50 0 ppm
1000 ppm
Precoatingwithout C B
-1000 ppm
© 3M 2019. A ll Rights Reserved. 53
Case Study 3: PET Bottle Flakes
S ource Material
▪ PET transparent bottles ground to flakes
▪ Recycled – Multimaterial
▪ Fiber application
▪ Formulation Contains:
- black and blue pigments
➢Post Consumer
Test Plan
▪ Test die build up at 255°C (490 °F) oncappilary rheometer
© 3M 2019. A ll Rights Reserved. 54
Die build up – 3 0 minutes
Die build-up postponed with PPA in both formulations
PET Reference + 50 0 ppm PPA-7
blue
black
© 3M 2019. A ll Rights Reserved. 55
Conc lusions for PPA in Recycling
© 3M 2019. A ll Rights Reserved. 56
PPA benefits• Melt fracture elimination
• Pressure reduction → output increase• Die build up reduction (less cleaning and rupture)
Success of PPA depends on• Quality of the waste (industrial versus post-consumer waste)• Purity of the waste (monomaterial versus multimaterial)• Type and concentration of other additives• Application method
Summary
• PPAs → fluoropolymer based additives to improve extrusion processing• PPAs generally do not detract from the desired physical properties of final
product
• Generally used at low end-use levels (< 10 0 0 ppm)• PPA performance governed by many factors• PPAs show efficacy in recycled material systems• Key benefits: Elimination of melt fracture, pressure reduction and reduction of
die build-up.
PPAs enable higher productivity and delivery of consistent, high quality extruded products
© 3M 2019. A ll Rights Reserved. 57
Thank you.
Learn more at 3M.com/ppa
3M , Dynamar and Dyneon are trademarks of 3M Com pany.All other trademarks are the property of their respective owners.
Index to Abbreviations
© 3M 2019. A ll Rights Reserved. 50
PPAs:PPA 1PPA 2PPA 3PPA 4PPA 5PPA 6PPA 7
3M ™ Dynamar™ FX 59293M ™ Dynamar™ FX 96143M ™ Dynamar™ FX 59273M ™ Dynamar™ FX 96133M ™ Dynamar™ FX 5920 A3M ™ Dynamar™ FX 59223M ™ Dynamar™ FX 5911
Antiblocks:AB 1AB-2AB-3AB-4AB-5AB-6AB-7AB-8AB-9
A B T ® 2500Optibloc®8 Optibloc®10Polybloc™ Microbloc®Clear-B lo c® 8 0Minbloc® H C 1400Minex®7Sipernat® 44MS
Slip: ErucamideResin:Resin A: C 6 LLDPE, 0.9 MI, 0.918 g /ccResin B: proprietary resinResin C: proprietary resinResin D: C 6 LLDPE, 1.0MI, 0.918g/cc
Hindered amine light stabilizer:H A L S -1 Chimassorb® 944H A L S-2 Tinuvin 6 22Registered trademarks:
10) Chimassorb® : Ciba
1) Dynamar™ : 3M2) ABT® 2500 : Specialty Minerals Inc.3) Optibloc®: Specialty Minerals Inc.4) Polybloc™ Specialty Minerals Inc5) Microbloc® Specialty Minerals Inc6) Clear-Bloc® Specialty Minerals Inc7) Minbloc® Unimin Specialty Minerals Inc8) Minex® Unimin Specialty Minerals Inc.9) Sipernat® Evonik Degussa
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© 3M 2019. A ll Rights Reserved. 60