designing high performance thermoplastics for halogen free...

DSM Engineering Plastics

1

Designing High Performance Thermoplastics forHalogen Free Electronics

Dr. Ir. W. F. NijenhuisDSM Engineering PlasticsOctober 2009

Living Solutions for People, Planet and Profit


Designing high performance thermoplastic materials for halogen free electronics


A global leader in sustainability, now and in the future

DSM Values: “We can’t be successful in a world that fails”

Page 2Global partner for high performance solutions



DSM Engineering Plastics: bringing sustainability to life

1. Halogen free flame retardant gradesAlready available in Stanyl, Akulon, Arnitel, Arnite and Xantar

2. Eco Footprint –Weight Reduction / Life time extensionMetal-to-plastic and Rubber-to-plastic conversion / Smart Design /Stanyl Diablo and Arnitel C

3. Product StewardshipControl of hazardous substances / Legislation and standardization / REACH

4. DSM Triple P PolicyAnnual triple P report / Dow Jones Sustainability Index / World Food Program

5. RecyclingRegrind Studies / Recycling: own technology / IP position

6. Innovation in White BiotechnologyBio-based raw materials / Biopolymers (EcoPaXX)



Understanding the market and the total value chain

Complex change with large consequences: need partnership andco-operation throughout the whole value chain

Polymer Compound Molder Component System OEM End user

Key for electronics:halogen free materials



Material perspective:• Each material has its own intrinsic strengths and weaknesses

• Optimizing in one direction often results in sacrifices somewhere else

• Final performance of plastic materials is always the combination of allingredients used (polymer and additives)

• Preferably performance of polymers is improved by additive technology(lower investments), but

- Sometimes limited commercial ingredients available- Available ingredients may not give the required performance- Ingredient choice for high temperature plastics is limited (need to be stable at

high processing temperatures)

• Performance as measured by standard material tests may not berepresentative for final use in application

How to use non-material related features (design, mother board architecture)?

How to set common standard for the industry?

Dilemma: how to get optimum performance/cost solutions?



Protective layer: char formation, blowing agent present: intumescent,thermal shielding

Modes of action of flame retardants

Combustiblegases

Flame

Polymer pyrolysis

O2 (air)heat

Cooling (heat sink), endothermicbreakdown reactions (MgOH)

Dilution by inert gases:water or N2

Flame inhibitors (flame poisoning),interference with radical reactions (Cl, Br, P)



Current halogen free solution in existing HTPAs

Conventional halogen free FR package:

Based on radical reaction in gas phase:degradation products may also interferewith polymer, leading to undesired sideeffects (further degradation)

Net result (based oncombination/interaction of flame retardantand polymer):•reduction of mechanical performance•reduction of flow•screw corrosion•blooming

Two solutions possible:•new flame retardant•new polymer

Page 7



Stanyl Roadmap in E&E

Halogen Free:V0 or HB rating

Market Needs

DSM solutions to address market needs

New FRpackage

New basepolymerwith existing FR

New generation StanylHalogen Free Flame Retardant

Stanyl ForTii

Roadmap 1 Roadmap 2

Stanyl HB series

New Stanyl High Flow(HB)

HB V0 V0



New generation Stanyl Halogen Free- Completely changing FR package (V0) -

DSM new flame retardant packageVery robust flammabilityDSM: high investment, strong commitment to E&E market over past 20yrs

Key benefits for connector manufacturers :Very good flow capability –between TS250F6D and 46HF5040Corrosion behavior is significantly improved over competitionCompletely corrosion free under developmentSuperb mechanical strength over competition

New generation Stanyl Halogen FreeFlame Retardant:

First commercial grade introduced September2009:

CR310: 30% GF FR, V-0

Roadmap 1



Stanyl ForTii- Completely changing polymer (V0) -

Stanyl ForTii : DSM’s new range of high temperature PolyamidesFirst new polymer in the new millennium !Unique polymer: has highest Tg and TmLow moisture uptake, excellent blister resistance (Jedec level 2)Good combination flow/mechanicalsSignificant corrosion improvementLow warpageDesigned to fit with halogen free FR (combination FR-polymer determines the performance)

Stanyl ForTii :The ‘first new polymer of the 21st century’

Roadmap 2



Trial run halogen free HTPA (PA66/6T) material (24 hour every day, 2 weeks)à screw andbarrel show severe corrosion with competitor material (left), but hardly any corrosion withStanyl ForTii (right)

StanylForTii

CompetitorHTPA

No corrosion after 2 wksSevere corrosion after 2wks

Initial stage

Stanyl ForTii Processing: corrosion test of halogen free HTPA- Head-to-head benchmark at same conditions on same screw type -



What makes ForTii (PA4T) so special ?

• Stanyl PA46 is the only aliphatic high performance polyamide and has an excellentperformance profile due to the unique C4 chemistry (diamine exclusively used by DSM).

• For PA4T a unique synergy is created based on the C4 chemistry and the use ofaromatic units (T), resulting in another unique polymer combining the best of bothworlds:

- good flow, excellent mechanical properties, high heat resistance- higher melting point, lower moisture uptake, excellent dimensional stability

• Aliphatic material: contains straight or branched chain of carbon atoms

• Aromatic material: contains a closed ring of carbon atoms

C

O

OHO C

O

H

C

H

H

C

H

H

N

H

C

H

H

C

H

H

C

H

H

CCC

OO

C

H

H

C

H

H

C

H

H

C

H

H

N

H



220

230

240

250

260

270

280

290

300

310

Stan

yl N

C11

00A

Stan

yl F

orTi

i F11

Stan

yl N

C11

04A

Stan

yl N

C11

04B

Stan

yl T

S250

F8

Stan

yl T

S250

F6D

Zyte

l HTN

FR

52G

30BL

Zyte

l HTN

FR

52G

30N

H

Griv

ory

HT

XE40

27 (F

E818

8)

Griv

ory

HT

XE40

52 (F

E818

9)

Gen

esta

r G13

02

Gen

esta

r GN

2332

Vect

ra E

130i

Vect

ra E

473i

Sum

ikas

uper

E68

07LH

F

Xyda

r MG

350

Zeni

te 5

5201

Ryt

on R

-4-2

00

HD

T 1.

8MPa

[°C

]Very high HDT of Stanyl ForTiiensures excellent co-planarity

after re-flow

Low HDT of most LCPsleads to significant

warpage after reflow soldering

Warpage after reflow- Highest stiffness at reflow temperature range (incl hot spots) -


LCP warpage issue in long form factor connectors- Example SMT DDR3, DDR SODIMM, high pin-count FPC -

Warpage direction before ReflowAverage warpage around +0.2 mm

Warpage direction after ReflowAverage warpage around -0.3mm

Due to the high delta changes (0.5 mm), there will be an open circuit at both ends resulting in an electricalfailure.

With such a high deformation, designers will have difficulties to predict the warpage during their design.Gating location improvement, introduction of ribs and slots may not be able to compensate the high deltachanges.

LCP based solution:A metallic clamp to press the connector onto the PCB throughout the entire reflow process. This will lead tohigher costs, more space is needed, the PCB needs additional drilling to fix the clamp, clamp may needscrews.

Flip in warpagedirection


ForTii warpage solution for long form factor connectors- Example SMT DDR3, DDR SODIMM, high pin-count FPC -

Warpage direction before ReflowAverage warpage around +0.07 mm

Warpage direction after ReflowAverage warpage around +0.10mm

Stanyl ForTii exhibits high stiffness at high temperatures. Deformation is very minimal.

The delta change is insignificant, much easier for designers to predict the warpage when using ForTii.Design allows to omit metallic clamps or additional PCB drilling without electrical failures.

ForTii is halogen free, JEDEC MSL level 2 and provides all polyamide advantages such as high

• High toughness• Excellent flexural strength• Excellent weld line strength• High pin insertion forces

Identical warpagedirection

Globally the first approvedmaterial for SMT DDR3

for servers and workstations

∆=0.03mm



Laser Direct Structuring

1.01 mm

3.77 mm

2.42

mm

Stanyl ForTii offers excellentprocessing characteristicssuitable also for micro-molding.Laser direct structuring gradeprovides designer highestflexibility and new structuralconcepts such as MEMspackages with tough polyamides.

Traditional materials such asLCPs are limited due to weld linestrength and leakage due todelamination.

Source: A. Pot et al, EMPC 2009

World’s smallest MEMS package



DSM product portfolio- Halogen free solutions available for all product lines -

Amorphous Semi-crystalline

PE PP

PS PVC

ABS PMMA

PEIPEEK

LCPPSU

PESPPS

PA6PA410PA66

PBT PET

POM

PC

mPPO Blends

Stanyl®

Arnitel®

Akulon®

EcoPaXX

Arnite®

Stanyl® ForTii

(Xantar®)

PA46PA4T

TPE-E

Performance

Volume

Arnitel XG: All solution pass UL standards and VW-1 testing andcomply to UL62, UL758 & tested per UL1581



Plastic’s industry trend

Halogen free is the hottest issue for Electronics

DSM invests heavily to cope with industry requirements• New generation flame retardant technology• New polymer• New product development• Continuous improvement on application knowledge & material science• New/expanded manufacturing capabilities

What is next?

• Post-industrial grades• Post consumer grades• Bio-based• Bio-degradable



Back-up slides



New Stanyl High Flow grades- HB solution -

Newly developed portfolio for super miniaturized connectors- Excellent flow capability- Incomparable mechanical properties- UL94 HB rated

Market trend: Most of Micro product do not require UL94 V-0(according to existing IEC60950-1 and upcoming IEC62368)

à USB 3.0 is specifying UL94 HBà USB 2.0 was revised to delete UL94 V-0 requirementà Mobile OEM, Nokia, Samsung, LG, SEMC, accept UL94 HB

New Stanyl High Flow (HB) :advancing miniaturization for connectors

* DSM’s proprietary Highflow technology



Positioning ForTii for electronics- well balanced material: excellent fit with halogen free and lead free soldering -

CTI

Flow

Stress at Break (Weldline)

Elongation at Break (Weldline)

Co-planarity

Solderability

HDT

Halfree feasibility

PA4T PA46 LCP PPA



PA4T: High stiffness above Tg at reflow temperatures ensureslow warpage after reflow and hence to lowest stress to PCB

LCP: Significant drop of stiffness at reflow temperatures leads towarpage after reflow and hecne to stress on teh PCB

Warpage after reflow- Highest stiffness at reflow temperature range (incl hot spots) -

1,00E+08

1,00E+09

1,00E+10

0,00 50,00 100,00 150,00 200,00 250,00 300,00 350,00

Temp (C)

G' (

Pa)

F11 (30%) Zytel HTN FR52G30NH Vectra E473i (30%) sumikasuper E6808LHF Ryton R4-200 (PPS)

HDT-A

260-288°C

At room temperature PPS, Sumikasuperand Vectra have high stiffness, followedby Stanyl ForTii and Zytel HTN

During reflow, Stanyl ForTii and SumikasuperHave highest stiffness, followed by VectraZytel HTN and PPSà this leads to warpage during assembly

No change of stiffnessStanyl ForTii

from 200-300°C



All solution pass UL standards and VWAll solution pass UL standards and VW--1 testing and comply to UL62, UL758 & tested1 testing and comply to UL62, UL758 & testedper UL1581per UL1581

Features Arnitel XG®- Halogen Free- No use of Plasticizers- Temperature rating of 105 °C- Excellent Chemical resistance- UV stability- High Flexibility- Color Stability- Zero re-investment on tooling- Excellent processing

Applications- Power cord Insulation & jacket- USB cable Jacket- Data Cable Jacket- DC power cable Insulation and Jacket- Over molding- PVC replacements

Arnitel for halogen free PVC replacement



EcoPaXX: a green bio-based engineering plastic

- 70% of the polymer is derived from renewableresources

- Renewable resources not competing with the foodchain

- Eco-footprint shows that EcoPaXX is carbon neutralfrom Cradle to Gate

EcoPaXX is a high performance engineering plastic:Thanks to:- A high melting point (248 oC), reduced water uptake and

excellent chemical resistance- Possible applications in automotive, E&E, General

Industries and/or Extrusion

designing high performance thermoplastics for halogen free...

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