3M Advanced Materials Division Bene fits and Use of Polym ...3M Advanced Materials Division. Bene...

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


• 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


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


Processes that Benefit from PPA

Melt Fracture Elimination with PPA

L L DPE without PPA L L DPE with PPA

vs.


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


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


Die Buildup Reduction

Without PPA With PPA

vs.


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.



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.


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.


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.



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


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


Using a PPA


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


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


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



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


Typical Additives used in Polyethylene

Mechanisms (Modes) of Interference


• 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


Abrasion

Abrasion

Adsorption

MeO xide


PPA

PPA

PPA

Adsorption

Chemical Reaction


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


PPA Coating Equilibrium ModelPPA coating is a dynamic process

Additive interference can affect all 3 steps

N uc leation Growth Removal


Mode Nucleation Growth Removal

Die Site Competition

Abrasion

Adsorption

Chemical Interference


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


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


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


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


• 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


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


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


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


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


Factors to Consider when S electing a PPA


▪ 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


PPA Use in Recycled MaterialsIndustrial waste and P C R case studies

PPAs for Recycling Applications


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


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


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


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


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


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


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


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


Die build up – 3 0 minutes

Die build-up postponed with PPA in both formulations

PET Reference + 50 0 ppm PPA-7

blue

black


Conc lusions for PPA in Recycling


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


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


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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