17. February 2014

Frank Neuber

Applications & Development Manager - NORAM

Additives Masterbatches BU Clariant Corporation

INNOVATION TAKES ROOT 2014

Utilizing HYDROCEROL™Chemical Foaming Agents to Reduce Density and Material Cost in PLA Sheet for Thermo-formables

CONTENTS

1) Clariant Corporation Introduction

2) Why Reduce Density - Economic Benefits of Density/Material Reduction Explained

3) How to Achieve Density Reduction - Chemical Foaming Agents (CFA’s) Explained

4) Keeping the Best Structure and Physicals – CESA-extend Explained

5) Comparative Examples from Clariant EU and NORAM

6) Summary and Conclusions

7) Citations & References

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1) CLARIANT : A world leader in specialty chemicals

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Clariant focuses on creating value by investing in future profitable and sustainable growth.

KEY FACTSSales 2012 (CHF m)

6 038

More than

100Group companies worldwide

EBITDA 2012 (CHF m)before exceptionals

802

End 2012

~21 202employees

Represented in

76countries worldwide

7Business Units

(incl. discontinued operations)

CLARIANT MASTERBATCHES

MasterbatchesClariant Masterbatches is the leading manufacturer of colorand additive concentrates and technical compounds for the plastics industry; supplying the packaging, consumer goods, medical, textile and automotive industries.

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2) Returning to the subject…Why Reduce Density ?

Economics. The same article made with less material is more economically attractive.

Example: 40 thermoformed PLA trays (from sheet) weigh a pound (454g), and these can now be made using 20% less PLA

This PLA application can yield a net savings of ~ $165,000 per each $1MM of PLA.

Or,… make 20% more sheet with same amount of PLA.

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Cost Savings Explained from Foaming PLA (from Clariant’s CFA Value Calculator)

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Value Units Value

Resin Cost $USD per pound $1.00

Resin Specific Gravity grams per cubic centimeter 1.24

Hydrocerol CFA Cost $USD per pound $3.50

Hydrocerol CFA Dose Percent 1.0%

Density Reduction Percent 20.0%

Annual Volume of Resin Processed Pounds 1,000,000

As-Is With HYDROCEROL

Annual Volume of Resin Processed 1,000,000 800,000

Annual Volume of HYDROCEROL Processed 0 10,000

Annual Resin Cost $1,000,000 $800,000

Annual HYDROCEROL Cost $35,000

TOTAL Annual Material Cost $1,000,000 $835,000

Annual Net Savings with HYDROCEROL $165,000

Cost Savings Achievable with Foam PLA - continued

(from Clariant’s CFA Value Calculator)

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Hydrocerol Price =========> $ 3.50 Hydrocerol Dose =====> 1.00% Starting Resin Price ==> $ 1.00

Density Reduction Percent RESIN COST PER POUND

$ 0.88 $ 0.90 $ 0.92 $ 0.94 $ 0.96 $ 0.98 $ 1.00 $ 1.02 $ 1.04 $ 1.06 $ 1.08 $ 1.10 $ 1.12 $ 1.14

12% Savings per pound ==> $0.079 $0.082 $0.085 $0.087 $0.090 $0.092 $0.095 $0.098 $0.100 $0.103 $0.105 $0.108 $0.111 $0.113

14% Savings per pound ==> $0.097 $0.100 $0.103 $0.106 $0.109 $0.112 $0.115 $0.118 $0.121 $0.124 $0.127 $0.130 $0.133 $0.136

16% Savings per pound ==> $0.115 $0.118 $0.121 $0.125 $0.128 $0.132 $0.135 $0.138 $0.142 $0.145 $0.149 $0.152 $0.155 $0.159

18% Savings per pound ==> $0.132 $0.136 $0.140 $0.144 $0.147 $0.151 $0.155 $0.159 $0.163 $0.166 $0.170 $0.174 $0.178 $0.182

20% Savings per pound $0.150 $0.154 $0.158 $0.162 $0.167 $0.171 $0.175 $0.179 $0.183 $0.188 $0.192 $0.196 $0.200 $0.204

22% Savings per pound ==> $0.167 $0.172 $0.177 $0.181 $0.186 $0.190 $0.195 $0.200 $0.204 $0.209 $0.213 $0.218 $0.223 $0.227

24% Savings per pound ==> $0.185 $0.190 $0.195 $0.200 $0.205 $0.210 $0.215 $0.220 $0.225 $0.230 $0.235 $0.240 $0.245 $0.250

26% Savings per pound ==> $0.203 $0.208 $0.213 $0.219 $0.224 $0.230 $0.235 $0.240 $0.246 $0.251 $0.257 $0.262 $0.267 $0.273

28% Savings per pound ==> $0.220 $0.226 $0.232 $0.238 $0.243 $0.249 $0.255 $0.261 $0.267 $0.272 $0.278 $0.284 $0.290 $0.296

30% Savings per pound ==> $0.238 $0.244 $0.250 $0.256 $0.263 $0.269 $0.275 $0.281 $0.287 $0.294 $0.300 $0.306 $0.312 $0.318

($0.050)

$0.000

$0.050

$0.100

$0.150

$0.200

$0.250

$0.300

$0.350

12% 14% 16% 18% 20% 22% 24% 26% 28% 30%

Savi

ngs

per P

ound

Percent Weight ReductionN S i

3) How to Achieve Density Reductions? CFA

“..♫.tiny bubbles ”

Explained: Chemical foaming agents (CFA’s) release gasses (CO2 for PLA) which displace polymer, forming a microscopic foam structure.

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Common Endothermic CFA’s explained:

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What about the water produced...in a polyester?

– Clariant has formulated its Hydrocerol CFA’s with water and Lewis acid scavengers to capture the water generated from common endothermic CFA ingredients, which can hydrolyzea polyester [read PLA].

– These advancements have allowed us to apply Hydrocerol CFA’s in previously “off limit” applications, such as thin films, thin trays, trays needing cold impact integrity, etc.

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Hydrocerol CFA’s…..We’ve Evolved.

Early attempts 2008 attempts Current Accomplishments

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4) Keeping the Best Physicals - How we do it

Trade secret, of course, but we can share a few details, below:

1) Improved PLA integrity; i.e. HDT, m.w. retention, gas cell nucleation, etc.

2) Developed the process to optimize the reaction, gas capture and laminar

flow needed when changing the polymer viscosity and apparent density.

3) Controlled the typical hydrolysis effects on polyesters, from using endo-

thermic CFA’s; i.e. scavenged released moisture and repaired hydrolyzed

and sheared PLA chains, increasing their melt strength and ability to form

the cellular structure. Using Clariant’s patented CESA-extend™ (CE)

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CE Rebuilds Polymers

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“ HOW

DOES IT

DO THAT ?”

CE Chemistry14

“I will explain.”

CESA®-extend is a multi-functional, oligomeric material:

- Very high epoxy functionality

- Unique mix of functionalities to maximize chain end-group branching without cross-linking or gel formation

- Rejoins cleaved ends to increase the molecular weight and melt strength

The great John Houseman from the movie The Paperchase

Extender in Hydrolyzed and Sheared Polyesters15

CE epoxy-functionality

Sheared or HydrolyzedPolyester lower m.w. chains

Higher m.w. Polyester Final product

5) Early Example- Unprotected Foaming

– 1% Hydrocerol CT3108

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Improved Examples - Protected Polymer Foaming

– 1% Hydrocerol CT 3108 + 1% CESA-extend

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Side–by–Side Comparison of Structures – EU Foam

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Unprotected Protected

Some Notable EU Machine and Energy Efficiencies

– Hydrocerol CFA alone dropped Head PSI to 2675 (from 3260 standard)

– Hydrocerol + Extender increased Head PSI to 3100 (viscosity increase)

– Amp load decreased to 28 (from 31 for standard Non-foamed) = 9.67% red.

- Foam Melt Temperatures = 178.4 F (versus Standard of 186.1 F)

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North American Developmental Results

– Pushed the Density reduction in mono-layer sheet to 28%

– Tri-Layer sheet (20:60:20) with up to 18% total density reduction (i.e. 30% density/material reduction in centerlayer) matches un-foamed standard sheets of same thickness for surface and impact physicals

– Proceeding with major select OEM’s per above-stated

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Example– NORAM Developments in 0.65mm sheet

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Example NORAM Developments in 0.65 mm PLA sheet

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Foamed Articles made with PLA

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Supporting Data:Density Reduction* vs. Hydrocerol Dose

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CFA% Avg. Density

STD PLA 0 1.2504

CFA 8607 Only 1 0.9966

CFA 8607 + 0.8%493 1 1.0819

CFA 8607 + 0.8%493 1.5 1.0085

CFA 8607 + 0.8%493 2 0.8972

0

0.2

0.4

0.6

0.8

1

1.2

1.4

0 0.5 1 1.5 2 2.5

Density(g/cc)

% Hydrocerol 8607 (with 0.8% Extender 493)

** Density determined by both Archimedes Principle Method and He displacement pycnometry

Supporting Data – MFR** with Hydrocerol and CE

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CFA%

MFR (210C,2.16Kg),(g/10Min.)

STD PLA 0 6.7

CFA 8607 Only 1 26.2

CFA 8607 + 0.8%493 1 16.5

CFA 8607 + 0.8%493 1.5 17.8

CFA 8607 + 0.8%493 2 21.9

0

5

10

15

20

25

30

1 2 3 4 5

CFA%

MFR(210C,2.16Kg),(g/10Min.)

**MFR determined on Tinius Olsen Melt Indexer

6) Summary & Conclusions:

PLA may be foamed to reduce density / material cost, with Additives which have FDA compliancy for Indirect Food Contact

The process conditions which allow its optimization are critical to success: temperatures, pressures, cooling, etc.

Extender technology rebuilds PLA melt strength and allows greater density reductions while maintaining physicals

Competitive economies versus “traditional” polymers like PS may be achieved with Hydrocerol CFA and CESA-extend technology in PLA.

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7) Citations & References:– [1] Wiesner, Müller: “The right Chemical Foaming Agent for your Application” 6th

International Conference, Blowing Agents and Foaming Processes, May 2004, Hamburg, Germany

– [2] Lübke, Wiesner: “Developments of New High Temperature Chemical Foaming Agents”, 4th International Conference, Blowing Agents and Foaming Processes, May 27 – 28, 2002 in Heidelberg / Germany

– [3] Wegner, J.: “Additives for foamed sheets” Kunststoffe 1/2005, Carl Hanser Verlag,

– [4] Groeseling, Mirko: ”Chain extender – brancher for polyester”, Clariant internal presentation, 9/2001

– [5] Villalobos, Marco; Awojulu, Abiodon; Turco, Gregory: “The Process of Recycling of Polyesters with Polymeric Chain Extenders”, published in Polymer Science and Engineering, Feb. 21, 2005

– [6] Pilla, Srikanth; Kim, Seong G.; Auer, George K.; Gong, Shaoquin; Park, Chul: “Microcellular Extrusion Foaming of Polylactide with Chain Extender” published in Polymer Science and Engineering, Aug. 1, 2009

– [7] Keefe, Lawrence; Hydrocerol CFA Savings Calculator; Clariant MasterbatchesLLC, public interactive document, published in Winchester, VA, Feb. 1, 2013

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QUESTIONS ?