symposium on globalsymposium on global ict … · expansion ppm/k standard fr-4 high-tg phenolic...

Symposium on GlobalSymposium on GlobalICT Environmental Initiatives

Brussels 27 – 28 October 2009

Symposium on Global ICT Environmental Initiatives

Agendao Indicators and Trends towards environment-friendly Laminateso Availabilityo Availabilityo Reliability, Processabilityo Price

© TECHNOLAM GmbH 2



„Driving Forces of Halogen free Materials“„Driving Forces of Halogen free Materials

© TECHNOLAM GmbH 3


CCurrent legal situationo Directive of the European Parliament RoHS doesn‘t concern TBBPAo NGOs proposing European Parliament revising RoHSo NGOs proposing European Parliament revising RoHS

© TECHNOLAM GmbH 4


o European Environmental Bureau143 member organisations in 31 countries143 member organisations in 31 countries

o International Chemical Secretariatstrives to brigde the gap between industrystrives to brigde the gap between industry, NGOs and policy circles

o Clean Production ActionUS based environmental NGO

© TECHNOLAM GmbH 5


f SDraft Position Paper on RoHS revisiono consider both, the direct impact of substances and the impacts of

transformation products at end of lifetransformation products at end of lifeo thereby supporting a general phase-out of brominated and chlorinated

organic substances in Electrical and Electronic Equipment (EEE)

© TECHNOLAM GmbH 6


Brominated Flame Retardents can form Dioxins and fFurans if burned under sub-optimal conditions

O

H2C O OC

CH3

CH3

CH2CH H2C CH2HCO OC

CH3

CH3

OHCH2CHH2C H2C CH2HC

O

O OC

CH3

CH3

OH

Br Br

Br Br

CH3Br Br Br O Br

Br O Br

Br

HO C OHCH3 Br

Dioxin

Br O Br

Br BrTBBPA

Furan© TECHNOLAM GmbH 7


Gwww.greenpeace.org/international/campaigns/toxics/electronics/how-the-companies-line-up

Greenpeace

© TECHNOLAM GmbH 8


C “Halogen Free means „Low Halogen Content“JPCA-ES-01-1999 IPC-4101C*

o maximum Br: 900 ppmo maximum Br: 900 ppmo maximum Cl: 900 ppmo max. Br + Cl: 1500 ppm*

IEC 61249-2-21* 10 iNEMI members*

© TECHNOLAM GmbH 9


fYear

Application 2006 2007 2008 2009

Japanese OEMs

Projected Timeline for Halogen Free Electronics

p

Notebook*

LCD TV

Hard Disk Drive

Game Console*

Camcorder/DSC

Mobile Phone*

DVD Player

European OEMs

Notebook & Desktop*

Automotives

Mobile Phone

ted

befo

re 2

006

Mobile Phone

N. American OEMs

Notebook & Desktop

Mobile Phone

*con

vertChip Processor

Hard Disk Drive

© TECHNOLAM GmbH 10


Halogen free spec Bromine and Chlorine Limit

Br, Cl ≤ 900ppmBr+Cl ≤ 1500ppm Deadline

Nokia Br or Cl ≤ 900ppm all products by 2008

Sony Ericsson x all models on market after 1st January 2008Sony-Ericsson x all models on market after 1st January 2008

Lenovo x alle products from 2009

Dell x all new products lauched after Jan. 1, 2010

LG x all products from 2010

SonyBr or Cl ≤ 900ppm new models by end of 2010

Samsung x all new models from Jan. 2010

Toshiba x all remaining uses of BFRs in notebook PCs by 2009a e a g uses o s oteboo Cs by 009

Wistron x evaluation started at Q3 2008

Apple x all products beginning 2008

HP x new computing products launched in 2009


Intel x 45 nm FC from 2008


CPCB Laminate Market 2008 by Material Type

Composite 5,7 % Special 13 3 %

FR-4 High-Tg 15,8 %

Paper 11,0 %p , Special 13,3 %

RCC, other 0,5 %

Standard FR-4 45,2 %FR-4 Halogen Free 8,5 %

Source Prismark; total $ 8,0 Bn



Halogen Free Market 2008Others 8,1 %

Elite Materials10 2 %

ITEQ 4,5 %

Matsushita Electric28,8 %

Shengyi Sci. Tech11,7 %

10,2 %

Hitachi Chemical 12,6 %

Nan Ya Plastics24,1 %

Source and Graph, Prismark total 24,6 Mio. m²

© TECHNOLAM GmbH 14© TECHNOLAM GmbH 14


C fComposition of Laminates and their Functions

Copper Foil Glass Cloth Resin Matrix FillerCopper Foil Glass Cloth Resin Matrix Filler

Electric Circuit Dimensional Stability Heat Resistance Flammability

Signal line Low CTE x/y Bonding Low CTE z

Grounding Low Warpage Flammability High Stiffness

Heat Dissipation High Stiffness Dielectric

PropertiesHeatDissipation

High Tg

Low MoistureAbsorption



2 x CHCHH C H C CHHCO OCCH3

+ HO CCH3

OH

Br Br

Brominated Epoxy Resin

2 x CH2CHH2C

O

H2C CH2HC

O

O OCCH3

+ HO

Br

CCH3

OH

Br

O OCCH3

CH3

CH2CHH2C

O

H2C CH2HCO OCCH3

CH3

OHCH2CHH2C H2C CH2HC

O

O OCCH3

CH3

OH

Br Br

Br Br

General BFRs use di-functional epoxy as reactant.General BFRs use di functional epoxy as reactant.



Phosphorous Based Epoxy

OG OGOG

+H3C H3C

n

H3CCH2 CH2

PO On P

H

O O

H3COX

X = A or B

n

CH2 CH2X A or B

OB =

P

O

OOHA =

Phosphorous based epoxy must use multifunctional


Phosphorous based epoxy must use multifunctional type to keep Tg and thermal resistance.


Epoxy

di-functional multifunctionaldi functional multifunctional

toughness but lower higher heat resistance


gheat resistance

gbut more brittle


f CPerformance ComparisonUnit / Condition NPG NPGN-150

Resin System Halogen Free Halogen Free

Curing Agent Dicy PN

Peel Strength N/mm 1,54 1,66

Tg (DSC) °C 153

Tg (TMA) °C 143 140

CTE z / TE z

α1 45 49

α 227 221CTE z / TE z α2 227 221

% 50 °C ~ 260 °C 3,08 3,04

PCT ½ hWater Absorption % 0,295 0,254

288 °C solder dipping 4‘ ~ 4’30“ 6‘

te 1

,6 m

m

PCT 2 hWater Absorption % 0,439 0,348

288 °C solder dipping 2‘ ~ 2’30“ 4‘

Impact Test kJ/m² 65 82

Flame Resistance UL-94 V-0 V-0 est s

ampl

e: la

min

at


Flame Resistance UL 94 V 0 V 0 Te


Thermal Expansion Properties

Expansion ppm/K Standard FR-4 High-Tg phenolic filled High-Tg halogen free

CTE xCTE y

15 ~ 1815 ~ 18

13 ~ 1513 ~ 15

11 ~ 1311 ~ 13

CTE z before Tg 58 45 35CTE z after Tg 287 260 210

Test sample: laminate 1,6 mm



C f STCT Performance by HATS Tester

o 12 layer test vehicle 40 °C / + 145 °Co 12-layer test vehicle, - 40 C / + 145 C

Material A condition pre-condition6 x reflow 245 °C

pre-condition6 x reflow 260 °C

Standard FR-4 162 - 247 150 - 266 142 - 227

Mid-TgPN / filled

> 1000 > 1000 800 - 900

Hi-Tg> 1000 > 1000 > 1000

PN / filled> 1000 > 1000 > 1000

Halogen Free > 1000 > 1000 > 1000



fProperties of Fillers

Natural SiO2 Fused SiO2 Mg(OH)2Natural SiO2 Fused SiO2 Mg(OH)2

Density [g/cm³] 2,50 2,50 2,36

Diameter [µm] 1,6 2,0 1,9

Fused SiO2Natural SiO2 Mg(OH)2 Al(OH)3



Performance Properties of Nan Ya Halogen Free Materials

NP-140 NP-155F NPG NPGN-150 NPG-170 NPGN-170 NPG-180 NPG-200

Resin system Br Epoxy

BrEpoxy

Halogen Free

Halogen Free

Halogen Free

Halogen Free

Halogen Free

Halogen Free

Curing agent Dicy PN Dicy PN Dicy PN PN PN

Tg (°C, DSC) 140 150 150 145(TMA) 170 170 190(DMA) 205(DMA)

CTE (%, 50~250 ) 4,1 3,4 2,4 2,4 2,3 2,4 2,2 2,050 250 )

T-260 (min) 25 >60 >60 >60 >60 >60 >60 >60

T-288 (min) 2 >40 >20 >40 >20 >40 >40 >40

Td (°C, TGA) 310 351 350 360 359 360 367 370

Dk @ 1GHz 4,50 4,58 4,60 4,50 4,42 4,53 4,82 4,40

Df @ 1GHz 0,016 0,017 0,012 0,013 0,012 0,013 0,015 0,013

Measurement on construction 4 x 7628


NPG: „G“ for Green MaterialsMeasurement on construction 4 x 7628


CInnerlayer Adhesion Comparison

Black Oxide Brown Oxide

Material Chemie A B C D

Standard FR-4 0,86 N/mm 0,67 N/mm 0,80 N/mm 0,62 N/mm

Halogen Free 0,57 N/mm 0,55 N/mm 0,53 N/mm 0,48 N/mm

Halogen Free New 0,65 N/mm 0,61 N/mm 0,63 N/mm 0,55 N/mm



CDrill Bit Wear Comparison

New Standard FR-4 PN+Filler Halogen Free Parameters

Ø 0,25 mmU/ i 200KU/min: 200Km/min: 2,9Hits: 3500



Drilling Test

Drilling ParameterDrilling Parameter

Type Ø Speed Infeed Retreat Thk Stack

Schmoll LZ 0,30 mm 160K U/min 3,4 m/min 11 m/min 1,6 2

Drill Bit Wear Comparison

1000 Hits 2000 Hits 3000 Hits

Halogen Free 24,46% 30,72% 36,52%

Halogen Free New 25,28% 27,32% 32,93%



Drilling Test

Drill Hole Precision NPG NPGN-150

Cp/Cpk 1,334 / 0,785 1,859 / 1,204

Target < 50 µm1325 / 48098 660 / 48104

2,75 % 1,37 %



C ff f CCost Effect for Halogen Free PCB

Standard FR-4 Halogen Free Factors

Laminate 1,0 1,2 ~ 1,5 HF Resin

Drilling 1,0 2,0 Reduced drill hits

Desmear 1,0 1,0 ~ 1,2 Increased cycle time

Index for4 ~ 6-layer PCB 1,0 1,10 ~ 1,15



SSummaryo Halogen free laminates contain more expensive epoxy resin and

flame retardant, that is not for freeflame retardant, that is not for freeo compared with other thermal resistant BFR-laminates there is no

difference in processing costso voluntary conversion is anticipating environmental legislation ando voluntary conversion is anticipating environmental legislation and

enables a settled and well approved changeo existing halogen free laminates perform well due to good heat

resistance and low thermal expansionresistance and low thermal expansiono demand from EEE-industry will accelerate further developments,

exposing the advantages of HF laminates



Thanks for your attention!Q &Q & A

Contact:Technolam GmbH

Contact:Nan Ya Plastics Corporation

www.technolam.deVolker Klafki+49 2241 [email protected]

www.npc.com.twLouis Lin+886 2 271 22211 [email protected]


symposium on globalsymposium on global ict … · expansion ppm/k standard fr-4 high-tg phenolic...

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