Polymers

SPECIALTY FOR POLYMER COMPOUNDS

ENSACO® TIMCAL TIMREX® TIMCAL TIMREX® TIMCAL Coke TIMREX® TIMCAL Dispersion

imerys-graphite-and-carbon.com Imerys Graphite & Carbon

WHO ARE WE? IMERYS Graphite & Carbon has a strong tradition and history in carbon manufactur- ing. Its first manufacturing operation was founded in 1908. Today, IMERYS Graphite & Carbon facilities produce and market a large variety of synthetic and natural graphite powders, conductive carbon and water-based dispersions of consistent high quality. Adhering to a philosophy of Total Quality Management and continuous process improve- ment, all Imerys Graphite & Carbon manufacturing plants comply with ISO 9001:2008. IMERYS Graphite & Carbon is committed to produce highly specialized graphite and carbon materials for today’s and tomorrow’s customers needs. IMERYS Graphite & Carbon belongs to IMERYS, the world leader in mineral-based specialties for industry.

WHERE ARE With headquarters located in Switzerland, IMERYS Graphite & Carbon has an inter- WE LOCATED? national presence with production facilities and commercial offices located in key markets around the globe. The Group’s industrial and commercial activities are man- aged by an experienced multinational team of more than 430 employees from many countries on three continents.

For the updated list of commercial offices and distributors please visit www.imerys-graphite-and-carbon.com

Lac-des-Îles, Canada HQ Bodio, Switzerland Changzhou, China Mining, purification and sieving of Graphitization and processing of Manufacturing of descaling agents natural graphite flakes synthetic graphite, manufacturing of and processing of natural graphite water-based dispersions, processing of natural graphite and coke, and manufacturing and processing of silicon carbide

Terrebonne, Canada Willebroek, Belgium Fuji, Japan Exfoliation of natural graphite, Manufacturing and processing of Manufacturing of water-based processing of natural and synthetic conductive carbon black dispersions graphite

WHAT IS OUR MISSION? To promote our economic, social and cultural advance- ment with enthusiasm, efficiency and dynamism by of- fering value, reliability and quality to ensure the lasting success of our customers.

WHAT IS OUR VISION? To be the worldwide leader and to be recognized as the reference for innovative capability in the field of carbon powder-based solutions.

2 Contents

ENSACO® conductive carbon black TIMREX® graphite and coke Specialty carbons for polymer compounds

THE PRODUCTS

• Introduction to ENSACO® conductive carbon black p. 4

• Introduction to TIMREX® graphite and coke p. 5

• ENSACO® conductive carbon black for polymer compounds p. 6

• TIMREX® graphite and coke for polymer compounds p. 8

TYPICAL APPLICATIONS FOR ENSACO® CONDUCTIVE CARBON BLACK

• Electrically conductive plastics p. 10

• Rubber p. 14

• Power cables and accessories p. 17

TYPICAL APPLICATIONS FOR TIMREX® GRAPHITE AND COKE

• Self lubricating polymers p. 18

• Filled PTFE p. 20

• Thermally conductive polymers p. 22

3 Introduction to ENSACO® conductive carbon black

Conductive carbon blacks are carbon blacks with high to very high stucture (or void volume) allowing the retention of a carbon network at low to very low filler content. The void volume can originate from the interstices between the carbon black particles, due to their complex arrangement, and from the porosity. THE PRODUCTS

HOW ENSACO® The Imerys Graphite & Carbon carbon black process has been developed around 1980 CONDUCTIVE CARBON and is commercially exploited since 1982. The plant uses most modern technology. BLACKS ARE PRODUCED The process is based on partial oil oxidation of carbochemical and petrochemical origin. The major difference with other partial combustion carbon black technologies lies in the aerodynamic and thermodynamic conditions: •• low velocity; •• no quench; •• no additives.

This leads to a material with no or nearly no sieve residue on the 325 mesh sieve and allows the highest possible purity. The granulation process has been developed to achieve an homogeneously consist- ent product maintaining an outstanding dispersibility. It is in fact a free-flowing soft flake characterised by a homogeneous and very low crushing strength that guaran- tees the absence of bigger and harder agglomerates. The process enables the production of easily dispersible low surface area conductive carbon blacks as well as very high surface area conductive carbon blacks. The unique combination of high structure and low surface area also contributes to give outstand- ing dispersibility and smooth surface finish. The low surface area materials show a chain-like structure comparable to acetylene black. The very high surface area materi- als belong to the extra conductive (EC) family. Although ENSACO® carbon blacks are slightly more graphitic than furnace blacks, they are quite close to the latter ones as far as reinforcement is concerned. ENSACO® carbon blacks combine to a certain extent both the properties of furnace and acetylene black, reaching the optimal compromise.

100 nm TEM picture of ENSACO® 250G carbon black showing STM picture of the surface of ENSACO® 250G carbon the high level of aggregation. black 5x5 nm. By courtesy of University of Louvain (Louvain-La-Neuve) By courtesy Prof. Donnet - Mulhouse

100 nm

SEM picture of ENSACO® 250G carbon black illustrating the high void volume. By courtesy of University of Louvain (Louvain-La-Neuve)

4 Introduction to TIMREX® graphite and coke

Graphite finds wide application thanks to its favourable combination of properties such as: •• low friction, chemical inertness and absence of inherent abrasiveness; •• high thermal conductivity, thermal stability and electrical conductivity;

•• film forming ability on metal surfaces; THE PRODUCTS •• relatively inoffensive nature of both powders and products of combustion.

These properties are a consequence of the lamellar graphite structure and the ani- sotropic nature of chemical bonding between carbon atoms. In graphite, three sp2 hybrid orbitals (each containing one electron) are formed from the 2s and two of the 2p orbitals of each carbon atom and participate in covalent bonding with three sur- rounding carbon atoms in the graphite planes. The fourth electron is located in the remaining 2p orbital, which projects above and below the graphite plane, to form part of a polyaromatic π-system.

Delocalisation of electrons in π-electron system is the reason of graphite’s high sta- bility and electrical conductivity. Interlamellar bonding was once thought to be weak and mainly the result of Van der Waals forces, however, it now appears that interla- mellar bonding is reinforced by π-electron interactions. Graphite is therefore not in- trinsically a solid lubricant and requires the presence of adsorbed vapours to maintain low friction and wear.

HOW TIMREX® TIMREX® PRIMARY SYNTHETIC GRAPHITE GRAPHITE AND TIMREX® primary synthetic graphite is produced in a unique highly controlled graphiti- COKE POWDERS ARE zation process which assures narrow specifications and unequalled consistent quality PRODUCED thanks to: monitoring of all production and processing stages, strict final inspection, and clearly defined development processes. TIMREX® primary synthetic graphite shows unique properties thanks to the combi- nation of a consistent purity, perfect crystalline structure and well defined texture.

TIMREX® NATURAL FLAKE GRAPHITE TIMREX® natural flake graphite is produced in a wide range of products distinguished by particle size distribution, chemistry and carbon content. Imerys Graphite & Carbon mines the graphite from its own source in Lac-des-Îles, Quebec, Canada. Further pro- cessing can be done either in Lac-des-Îles or in our processing plant in Terrebonne, Quebec, Canada. All TIMREX® “naturals” are thoroughly controlled in our laborato- ries to ensure quality, consistency and total customer satisfaction.

TIMREX® COKE TIMREX® coke is calcined at appropriate temperature with low ash and sulphur content, well defined texture and consistent particle size distribution.

Lc c

c/2

SEM picture of TIMREX® Graphite showing the c/2 = Interlayer distance perfect crystalline structure. Lc = Crystallite height

5 ENSACO® conductive carbon black for polymer compounds

TYPICAL VALUES THE PRODUCTS

PROPERTY TEST METHOD UNIT ENSACO® 150G ENSACO® 210G ENSACO® 250G ENSACO® 260G ENSACO® 350G

Form Granules (*) Granules Granules (*) Granules Granules

BET nitrogen surface area m2/g 50 55 65 70 770 ASTM D3037

OAN absorption ml/100 g 165 155 190 190 320 ASTM D2414 (1)

COAN crushed OAN ml/100 g 95 95 104 104 270 ASTM D2414 (1)

Pour density kg/m3 190 210 170 170 135 ASTM D1513

Moisture (as packed) % 0.1 0.1 0.1 0.1 1 max ASTM D1509

Sieve residue 325 mesh (45 μm) ppm 2 2 2 2 10 ASTM D1514

Ash content % 0.1 0.1 0.01 0.01 0.03 ASTM D1506

Volatile content % 0.2 max 0.2 max 0.2 max 0.2 max 0.3 max TIMCAL Method 02 (2)

Sulphur content % 0.5 max 0.5 max 0.02 0.02 0.02 ASTM D1619

Toluene extract % 0.1 max 0.1 max 0.1 max 0.1 max 0.1 max ASTM D4527

pH 8–11 8–11 8–11 8–11 8–11 ASTM D1512

Volume resistivity Ohm.cm 2000 max (3) 500 max (3) 10 max (3) 5 max (3) 20 max (4) TIMCAL Method 11 (3) (4)

(1) Spring: 0.9 lbs/inch; 10 g of carbon black (2) Weight loss during heating between 105 and 950°C (3) 25% carbon black in HDPE Finathene 47100 (4) 15% carbon black in HDPE Finathene 47100

(*) ENSACO® 150 and ENSACO® 250 are also available in powder form.

6 TYPICAL EFFECTS ON POLYMER COMPOUNDS THE PRODUCTS

PROPERTY ENSACO® 150G ENSACO® 210G ENSACO® 250G ENSACO® 260G ENSACO® 350G

Form Granules (*) Granules Granules (*) Granules Granules

BET nitrogen surface area 50 55 65 70 770 (m2/g)

OAN oil absorption 165 155 190 190 320 (ml/100 g)

Conductivity     

Dispersibility     

Purity     

Water absorption very low very low very low very low high

Surface smoothness     

Electrical/mechanical      properties balance

Resistance to shear     

MRG Comments to Easy strippable (mechanical All polymers application domains insulation shields rubber goods)

excellent  very good  good  quite good  difficult 

(*) ENSACO® 150 and ENSACO® 250 are also available in powder form.

7 TIMREX® graphite and coke for polymer compounds

TYPICAL VALUES

PARTICLE SIZE RANGE GRADE ASH SCOTT SURFACE AREA BET 2 THE PRODUCTS (µm) (%) DENSITY (m /g) (g/cm3) Synthetic graphite KS graphite KS6 0.06 0.07 26.0 KS15 0.05 0.07 20.0 KS5-25 0.03 0.23 8.6 KS44 0.06 0.19 9.0 KS5-44 0.02 0.31 5.9 KS150 0.06 0.42 3.0

0 25 50 75 150 SFG graphite SFG6 0.07 0.07 17.0 SFG44 0.07 0.19 5.0 SFG150 0.03 0.29* 2.5

0 25 50 75 150

T graphite T15 0.08 0.10 13.0 T44 0.07 0.18 10.0 T75 0.07 0.21 9.8

0 25 50 75 150

Natural graphite PP flake PP10 <5 0.05 10.0 graphite PP44 <5 0.11 4.8

0 25 50 75 150

LSG flake LSG10 <1 0.08 9.3 graphite LSG44 <1 0.20 5.4

0 25 50 75 150 Cumulative size Large flake min. 80% <150 mesh (105 µm) M150 <6 0.4* 1.9 graphite min. 80% >150 mesh (105 µm) 80X150 <6 0.6* 0.9

Coke Oversize control 10.0 PC coke min. 98% <45 µm (air jet sieving) PC40-OC 0.15 0.47* max. 0,1% >106 µm (air jet sieving)

GRADE ASH DENSITY PARTICLE SOLID (%) (g/cm3) SIZE CONTENT 20°C DISTRIBU- (%) TION d90 (µm) Water-based dispersion LB dispersion LB1300 0.10 1.17 6.5 27.5

GRADE ASH SCOTT FORM D90 (%) DENSITY (µm) (g/cm3) Special grade

C-THERM™ C-THERM™001 <0.3 0.15* soft granules

C-THERM™011 <2.5 0.15* soft granules

C-THERM™002 <0.3 0.04* powder 81

C-THERM™012 <2.5 0.04* powder

* bulk density

8 MEET CONDUCTIVITY TARGETS WITH DEDICATED IMERYS GRAPHITE & CARBON ADDITIVES

9 TYPICAL APPLICATIONS FOR ENSACO® CONDUCTIVE CARBON BLACK APPLICATIONS PLASTICS SOME TYPICALFINAL COMPOUND OF ACONDUCTIVE THE PREPARATION BLACK CONDUCTIVE CARBON THE SELECTIONOFA 10 Electrically conductiveplastics ENSACO on ENSACO In the following pages there are some of the results of experimental work carried out • • • • • • • • • • • polymer (splitfeedingtechnology). quires the use of twin screw feeders and separate introduction on an already molten LCM. Thefeedingoflowbulkdensity, softflake-typecarbonblacksintoextrudersre- clude internalmixers,twinscrewextruders,singlekneadermachinesand Suitable mixingequipmentsforthepreparationofblackconductivecompoundsin- • • • • The selectionoftheconductivecarbonblackwillalsoinfluence: sample preparationtechnique. the moreappropriatesystem.Thesecurvesarevalidforagivenformulationand age –areausefulcomparativetooltopredicttheconductivityinplaceandselect Percolation curves–correlatingthevolumeresistivityandcarbonblackpercent- sion andprocessing. Low surfaceareaconductivecarbonblacksshowaparticularadvantageondisper may alsoinfluencethefinalconductivityofparts. parameters liketheadditivesinpresence,compoundingorprocessingconditions needed toachievetherequiredconductivity. Nevertheless,inaminorway, other The higherthestructureofcarbonblack,lowerlevelblack polymer isthetypeandlevelofcarbonblackused. The mainparameterinfluencingthefinalconductivityofafinishedpartingiven are determiningtheoverallelectricalandmechanicalperformance. plastics. The combination of the polymer type and grade and the carbon black grade (Results inotherpolymers,fullstudiesandpublications are availableuponrequest). tions andsamplepreparationtechniquementioned. The datashownherearegivenasorientationandvalid fortheparticularformula- • • • • • • • • • • • • • • • UV protectionandpigmentation. PTC switches; sensors; heating element; antistatic flooring; places, etc.; health: medicalapplications,cleanroomequipments,articlesforantistaticwork- computer: antistaticarticlesfor&accessories,CDplayer, etc.; mobilephoneparts,wheels,containers,bins,pallets,etc.; transport: let, electrostaticallypaintableparts,etc.; automotive industry:fuelinjectionsystems,anticorrosiontankin- films: antistaticandconductivefilms,packaginggarbagebags,etc.; handling ofelectroniccomponents:carrierboxes,trays,tapes,etc.; the overallprice–performanceratio. the mechanicalproperties(polymerpropertyretention,reinforcement); the surfaceappearanceoffinishedmaterial(numberdefects); flow index,extrusionthroughput); the compoundingbehaviour(dispersibility, resistancetoshear, mixingcycle,melt ® conductivecarbonblacksfindtheirapplicationsinanunlimitednumberof ® conductivecarbonblacksindifferentpolymercompounds. - ENSACO HDPE CARBON BLACKSIN ® CONDUCTIVE Resistivity vsmixingtime-25%carbonblack Resistivity vsmixingtime-18%carbonblack At aconcentrationveryneartothepercolationlevel,whenovermixed,ENSACO Various carbonblacksinHDPE tivity whenovermixed.ENSACO At aconcentrationfarabovethepercolationlevel,bothblacksareverystableinresis- working conditions. offers ahigherconsistencyinresistivityresultingfromitsshearstabilityextreme The higherthestructureofcarbonblack,lowerpercolationthreshold. Influence ofthecarbonblacktypeonresistivity Volume resistivity (Ohm.cm) Volume resistivity (Ohm.cm) Volume resistivity (Ohm.cm) 100 200 300 400 500 600 700 800 10 10 10 10 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 0.1 3.0 10 0 3 5 7 9 0 4 4 5 5 10 6 6 20 7 7 ® 260Gshowsaconsistentlowerresistivity. 30 Carbon blackconcentration(%) Brabender mixingtime(min) Brabender mixingtime(min) 8 8 40 9 9 50 10 10 Processing: compressionmoulding. Brabender internalmixer. Compounding: laboratory ENSACO ENSACO ENSACO ENSACO ENSACO ENSACO ENSACO ® ® ® ® ® ® ® 350G 260G 250G 260G 250G 260G 250G ® 260G 260G 11

TYPICAL APPLICATIONS FOR ENSACO® CONDUCTIVE CARBON BLACK TYPICAL APPLICATIONS FOR ENSACO® CONDUCTIVE CARBON BLACK ENSACO 12 ENSACO LDPE CARBON BLACKSIN CARBON BLACKSINPP Electrically conductiveplastics ® CONDUCTIVE CONDUCTIVE overcome thisphenomenon. to thepercolation,morevisibleisthateffect.Aconcentration safetymargincan Injection mouldinggeneratesmoreshearthancompression moulding.Theclosest Influence ofcarbonblackloadingandprocessingon the resistivity PPH MI54(230°C/5kg)withvariousconductivecarbonblacks est impactonfluidityreduction. At same structure level, the carbon black with the lowest surface area has the small- ity andmeltflowindex Influence ofthecarbonblacktypeonresistivity. Relationbetweenresistiv- Various carbonblackinLDPEMFI0.3and36(g/10min) higher themeltflowindexofstartingpolymer, thelowerpercolationthreshold. that maybecomingfromtheeasierdispersionresultinginsmoothercompounding.The equal structure,thecarbonblackoflowersurfaceareagetsanadvantageonresistivity The higherthestructureofcarbonblack,lowerpercolationthreshold.At the resistivity polymeronInfluence ofthecarbonblacktypeandMFIstarting Volume resistivity (Ohm.cm) Volume resistivity (Ohm.cm) Volume resistivity (Ohm.cm) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 0 1 2 3 4 5 6 0 1 2 3 4 0 2 4 6 8 0 0 171 5 strands 24 10 pellets +pressed 15 10 plaques 10 6 20 Carbon blackconcentration(%) MFI (230°C/5kg)(g/10min) injection moulding 4.6E +10 25 pellets + 30 54 100 35 Processing: injectionmoulding. screw extruder. Compounding: ZSK25twin and realizationoftapes. twin screwextruderHaakePTW16 Compounding andprocessing: Processing: compressionmoulding. Brabender internalmixer. Compounding: laboratory ENSACO ENSACO -ye L 36 LD 0.3 LD 36 LD P-type 0.3 LD P-type N472 N472 13.5% ENSACO 15% ENSACO ENSACO high surfacearea high structure N472 low surfacearea high structure ® ® ® 5G LD0.3 250G 250G 5G LD36 250G ® ® 250G 250G ENSACO CARBON BLACKSINPC ® CONDUCTIVE Tensile strengthinfunctionofvolumeresistivity Tensile strengthforbothcarbonblacksisalmostatthesamelevel. Izod impactstrength,notched,infunctionofvolumeresistivity most mechanicalpropertiesarestillbetter. Volume resistivityinfunctionofcarbonblackloading Although theconcentrationforpercolationisdoublelevelwithENSACO Influence ofthecarbonblacktypeonmechanicalandrheologicalperformances Influence ofthecarbonblacktypeonresistivity Tensile strength (MPa) Izod (kJ/m2) Volume resistivity (log (Ohm.cm)) 60 10 11 12 10 11 12 61 62 63 64 65 66 67 68 1 5 6 7 8 9 2 3 4 5 6 7 8 9 4 1 1 0 2 2 3 3 10 4 4 5 5 6 6 10 7 7 Volume resistivity(log(Ohm.cm)) Volume resistivity(log(Ohm.cm)) Carbon blackconcentration(%) 8 8 9 9 10 10 10 11 11 100 12 12 Processing: injectionmoulding. screw extruder. Compounding: ZSK57twin Processing: injectionmoulding. screw extruder. Compounding: ZSK57twin ENSACO ENSACO ENSACO ENSACO ENSACO ENSACO ® ® ® ® ® ® 350G 250G 350G 250G 350G 250G ® 250G, 13

TYPICAL APPLICATIONS FOR ENSACO® CONDUCTIVE CARBON BLACK TYPICAL APPLICATIONS FOR ENSACO® CONDUCTIVE CARBON BLACK Rubber 14 ENSACO mechanical propertiesandprocessingatagoodlevel. it occursthattheconductivecarbonblackisusedbyitsowninordertomaintain is veryoftentheonlysolution.Insomespecificcases,especiallyinspecialpolymers, ing onlyoneofthenumerousphysicalrequirements,usecarbonblackblends Specifications ofrubbercompoundsbeingusuallyquitecomplexandconductivitybe- black canbepredicted. ity, structurebeinganadditiveproperty, thecombinationsofconductiveandnormal bon blacks.Ascarbonblackstructureistheparameterdeterminingconductiv- are oftenusedtogivethefinalboostacompoundalreadyfilledwithothercar tive carbonblackshavetheadvantagetoreachconductivitiesatlowerloadingand also conductivitytothecompoundswhenusedinsufficientlyhighloading,conduc- by nature.Althoughthecommoncarbonblacksareconductivenatureandimpart reinforcing orsemireinforcingcarbonblack.Theyarehighstructurematerialsbulky carbon blacksarebeforeallblacks,tobemixedandhandledasanyother Carbon blackisoneofthemainingredientsanyrubbercompound.Conductive on ENSACO In the following pages there are some of the results of experimental work carried out • • • • A fewnon-conductiveapplications: • • • • pounder cantakeprofitofthelowsurfaceareaandhighstructurethoseblacks: studies andpublicationsareavailableuponrequest. tions andsamplepreparationtechniquementioned.Results inotherpolymers,full The datashownherearegivenasorientationandvalid fortheparticularformula- ENSACO • • • • • • • A fewconductiveapplications: ENSACO 260, are,duetotheirveryeasydispersion,quiteperforminginmostrubbercompounds. tivity isconcerned.Especiallythelowsurfaceareacarbonblacks,grades150,250and • • • • • • • • • • • • • • • articles exposedtochippingandchunking. membranes; textile coating; antivibration systems; very gooddispersion,mechanicalperformanceatthinlayer. very goodtearstrength; good thermalaging; low hysteresiswithrelativelyhighhardness; seals. shoe soles; cylinder coating; hoses forfuel,conveyingofpowders,etc.; conveyer belts; flooring; belt covercompounds; ® ® ® 350isalsousedinsomecompoundswheresmalladditionsarerequired. carbonblacksare,quiteclosetofurnaceasfarthereinforcingac- 150 and 250 are alsousedinnon conducting applications where the com- ® conductivecarbonblacksindifferentrubbercompounds. - By courtesyofBayer COMPOUND CONVEYOR BELT COVER CONDUCTIVE CR COMPOUND NBR CONDUCTIVEHOSE By courtesyofBayer Stearic acid Rhenogran ETU-80 ZnO powder Ingralen 450 Vulkanox 4020 Vulkanox DDA ENSACO N-472 MgO powder Buna CB10 Bayprene 610(CR) Amax Methyl thuads Sulphur DOP Stearic acid ZnO N-550 N-472 ENSACO NBR NT3945 ® ® 250 250 0.5 0.2 5 15 0.5 1.5 30 ENSACO Compound A 4 2 100 ENSACO Compound A 100 0.4 0.5 25 30 40 2 2 4 ® ® 250 250 0.5 0.2 5 15 0.5 1.5 B 30 4 2 100 N-472 Compound B N-472 Compound 100 0.4 0.5 30 40 25 2 2 4 Tear Strength(N/mm) Resistivity (Ohm.cm) Modulus 500%(MPa) Elongation atbreak(%) Stress-strain Shore AHardness Vulcanizate dataunagedatRT Mooney ML(1+4)at100°C t90% (min) Modulus 300%(MPa) Modulus 100%(MPa) Tensile Strength(MPa) Resistivity (Ohm.cm) 70°C Compression set24hat Modulus 500%(MPa) Modulus 300%(MPa) Modulus 100%(MPa) Modulus 50%(MPa) Tensile strength(MPa) Elongation atbreak(%) Stress-strain Shore Ahardness Vulcanizate dataunagedatRT Mooney ML(1+4)at100°C t90% (min) Dispersion ratingDIK (%) ENSACO Compound A ENSACO Compound A 11.46 32.4 12.6 70.9 45.7 13.8 16.1 23.4 20.7 86.8 339 100 676 8.6 3.9 9.2 2.4 1.2 79 18 62 62 ® ® 250 250 B N-472 Compound N-472 Compound B 11.37 31.8 14.4 72.2 47.2 10.3 14.8 360 311 20.6 11.5 22.4 21.8 85.8 4.6 800 540 2.7 1.4 19 64 64 15

TYPICAL APPLICATIONS FOR ENSACO® CONDUCTIVE CARBON BLACK TYPICAL APPLICATIONS FOR ENSACO® CONDUCTIVE CARBON BLACK Experimental dataprovidedbyDuPontDowElastomers,Japan COMPOUNDS FKM CONDUCTIVE 16 MgO MT black(N990) VITON A-32J- SCF N-472% N-472 SCF Ca(OH) ENSACO VPA-2 Total phr MT black% ENSACO 100 100 120 140 160 180 Shore A Log resistivity(Ohm.cm) Mooney viscosityML(1+10’),100°C 20 40 60 80 10 20 30 40 50 60 70 80 90 10 12 14 0 0 2 4 6 8 0 2 ® ® 250G% 250G 1 1 1 Fluoroelastomer 2 2 2 3 3 3 4 4 4 127.0 15.7 100 0.0 0.0 20 3 1 3 1 - - 5 5 5 6 117.0 100 8.5 0.0 0.0 10 6 6 3 2 3 1 - - (*) 7 8 8 8 127.0 15.7 100 0.0 0.0 20 3 3 3 1 - - 9 9 9 137.0 21.9 100 for 10min. Vulcanizate propertiesat177°C (*) Rejectedbecauseuncurable. Compression set(%) t 90%(min) 0.0 0.0 30 20 10 20 30 40 50 60 70 10 12 14 16 18 3 4 3 1 - - 0 0 2 4 6 8 1 1 117.0 100 0.0 8.5 0.0 10 3 5 3 1 - - 2 2 3 3 127.0 15.7 100 0.0 0.0 20 3 6 3 1 - - 4 4 137.0 21.9 100 5 5 0.0 0.0 30 3 7 3 1 - - 6 6 137.0 14.6 100 7.3 0.0 10 20 3 8 3 1 - 8 8 9 9 147.0 13.6 13.6 100 0.0 20 20 3 9 3 1 - COMPOUNDS NBR STRIPPABLE TYPICAL EVA/ Power cablesandaccessories SEMICON COMPOUNDS TYPICAL EEA/EBA pounds quiteoftenblendsofEVA andNBRareused. Typical polymer compositions are polyolefins or copolymers; for strippable com- peeling device. strippable oreasylayershavetopeeledofbyhandusingaspecific cific adhesionstrengthbetweentheinsulatinglayerandinsulatorshield.These For strippableoreasycompoundstheserequirementsareaddedtoaspe- electrical conductivity, asmooth or even supersmooth surface finish,andhigh purity. shields. Therequirementsforthosecompoundsarebesidesprocessing,asufficient Conductive carbonblackisusedinsemiconcompoundsforconductorandinsulator Levaprene 450 N-550 Protrusion (N°/m Specific netmixingenergy(kWh/kg) MFI (g/10min) Die pressure(bar) Carbon blackdispersion:<3µ Resistivity @90°C Resistivity @RT Mixing cond.L/D15;FeedBC;Truput 30 Peroxide ENSACO ENSACO EBA EEA Perbunan NT8625 Antilux 654 Rhenogran P60 Zn stearate ENSACO N-472 Rhenovin DDA-70 Rhenofit TAC/CS Percadox BC-408 Viscosity ML(4+1) Rheometer@180 t90% Tensile strength(MPa) Non aged(diff.aged) Mechanical properties Elongation atbreak(%) Modulus 100%(MPa) Shore A - after21days(N) - after3days(N) Peel strengthhotair100°C(N) Volume resistivity(Ohm.cm) ® ® ® 250 210 250 TYPICAL EEA/EBASEMICON COMPOUNDS 2 ) m N-472 Compound 16.5 (-19) 215 (-58) 87 (+7) 210 1.4 4.3 3.6 90 40 10 10 40 56 11 3 1 5 5 5 7 EEA Compound ENSACO Compound 16.9 (-15) 180 (-50) 90 (+4) 0.313 23.12 6600 97.9 12.2 229 100 7.2 1.4 4.3 3.6 40 37 30 90 40 10 10 44 ® 0 3 1 5 3 4 3 210 EBA Compound ENSACO Compound 16.9 (-15) 170 (-53) 89 (+7) 0.326 21.39 99.4 12.7 239 100 410 5.6 1.4 4.3 3.8 40 22 30 90 40 10 10 48 ® 0 3 1 5 4 3 4 250 17

TYPICAL APPLICATIONS FOR ENSACO® CONDUCTIVE CARBON BLACK Self lubricating polymers

The choice of a polymer-based self lubricating solid for a particular application depends mainly upon the operating conditions of: temperature, chemical environment and the maximum values of pressure (p) and sliding speed (v). For each polymer or composite material, a pv limit is quoted, which corresponds to the pressure times the sliding speed at which the material fails, either due to unacceptable deformation, or to the high fric- tional energy dissipated causes surface melting, softening and excessive wear. The pv limit of a polymeric material may be increased by increasing its mechanical GRAPHITE AND COKE

® strength (resistance to deformation), thermal conductivity (reduction in surface tem- peratures) and by decreasing friction (reduces frictional heating). In practice, thermo- plastics (with the exception of PTFE) are mainly used as pure solids, since their wear resistance and frictional coefficient, are satisfactory for most applications. Solid lubri- cant fillers or fibre reinforcement (glass fibres, carbon fibres, textiles) are only em- ployed under the more extreme conditions of load and speed. The major polymers employed as self lubricating solids/composites, are illustrated below.

Graphite powder is widely used in polymer composites, either alone or in combination with reinforcing fibres, PTFE or various inorganic fillers, e.g. mica, talc. Applications include gears, dry sliding bearings, seals, automotive and micro-mechanical parts.

The properties of graphite which favour its use in polymer composites are: •• low friction lamellar solid (reduces friction); •• tendency to form a transfer film on the countersurface (assists in wear reduc- ®

TYPICAL APPLICATIONS FOR TIMREX TYPICAL APPLICATIONS tion, particularly when graphite is applied as water based dispersion i.e. TIMREX LB1300); •• high thermal conductivity (decreases temperature rise due to frictional heating); •• electrical conductivity (prevent build-up of static charge which may be a problem in some cases); •• chemically inert (used in conjunction with PTFE in corrosive environments); •• high thermal stability (favours use in high temperature applications, e.g. polyimide graphite composites may be used up to 350 °C).

Incorporation of graphite powder into a thermoplastic polymer will generally result in a reduction in the friction coefficient (with the exception of PTFE) but rarely improves the wear resistance. This behaviour is illustrated in the two graphs, which show the mean friction coefficient and specific wear rate for a stainless steel ball (ø = 5 mm) rub- bing on discs of graphite filled polystyrene and polyamide at constant load (32.5 N) and speed (0.03 m/s). The specific wear rates of the graphite-polymer composites were calculated from the diameters of the wear tracks and the contact geometry.

In the case of polystyrene, addition of 30–50% of a high purity macrocrystalline syn- thetic graphite (TIMREX® T75), reduced both friction and wear rate. With polyamide however, addition of a graphite similar to TIMREX® T75 reduced the friction coeffi- cient, but caused a slight increase in the wear rate, with the finer particle size powder (TIMREX® KS6) giving the better result. In the case of low density and , graphite incorporation causes both an increase in friction and wear.

18 The results described above are thought to be related to the strength of adhesion at the polymer-graphite interface, which depends upon the wettability of the powder by the molten polymer, powder surface area to volume ratio, surface chemistry, etc. In simple terms, polystyrene shows a strong affinity for the graphite surface, while poly- olefins show a weak affinity. Interfacial adhesion increases with increasing powder surface area to volume ratio, or decreasing particle size. For this reason relatively fine graphite powders (95%<15 microns) are recommended GRAPHITE AND COKE for thermoplastics. The strength of thermosetting polymers is much less sensitive to ® filler-polymer interactions, therefore coarser graphite powders may be used (typically 95%<75 microns). For thermoplastics, the viscosity of the polymer-graphite melt dur- ing extrusion/moulding will also depend on the graphite particle size, which should be appropriate. Excessive graphite surface area may also lead to void formation in the finished composite, due to desorption of physisorbed vapours in the hot melt. High graphite purity is generally desirable in order to minimize wear, although this param- eter is unlikely to be important in the presence of abrasive fillers (glass fibre, carbon fibre).

Ball/disc friction & wear data: polystyrene/graphite filler

-12 12 0.4 Wear Friction 10 /Nm)x10 3 0.3

8 FOR TIMREX TYPICAL APPLICATIONS Friction coefficient 6 0.2

Specific wear (m 4 0.1 2 Influence of graphite addition on the specific wear rate and friction 0 0 of polystyrene pure 30% 50% polystyrene TIMREX® T75 TIMREX® T75

Ball/disc friction & wear data: polyamide 6/graphite filler

-12 20 0.4 Wear Friction /Nm)x10 3 15 0.3 Friction coefficient 10 0.2 Specific wear (m 5 0.1 Influence of graphite addition on the specific wear rate and friction 0 0 of polyamide 6 pure 30% 30% polyamide TIMREX® KS6 TIMREX® KS44

The above mentioned results are the confirmation that TIMREX® graphite powder is an excellent additive to produce self-lubricat- ed polymers. The addition of TIMREX® graphite powder to the unfilled polymers allow for a reduction of the friction coefficient and in most of the cases to a reduction of the wear rate. These results are achieved by a synergic combinations of all the good properties of TIMREX® graphite powder that among the others are: the high degree of crystallinity, the extremely high purity, the optimal texture and the perfect particle size distribution. All of them linked by a common factor: the consistency!

19 Filled PTFE

Polytetrafluoroethylene (PTFE) exhibits a very low coefficient of friction and retains useful mechanical properties at temperatures from -260 to +260 °C for continuous use. The crystalline melting point is 327 °C, much higher than that of most other semi- crystalline polymers. Furthermore, PTFE is nearly inert chemically and does not adsorb water, leading to excellent dimensional stability. On the one hand, these char- acteristics of PTFE are very useful in the matrix polymer of polymer-based compos- ites which are used in sliding applications. On the other hand, PTFE is subjected to GRAPHITE AND COKE

® marked cold flow under stress (deformation and creep) and reveals the highest wear among the semicrystalline polymers. However, these disadvantages are very much improved by incorporating suitable fill- ers, allowing the use of PTFE in fields otherwise precluded to this polymer. The treated PTFE is generally known as filled-PTFE. There are many kinds of filled- PTFE composite because various fillers are incorporated into PTFE and one or more materials can be used simultaneously. Usually, these fillers are in form of powders or fibers intimately mixed with the PTFE. The addition of fillers to the PTFE improves or modifies its properties depending upon the nature and quantity of filler: •• remarkable increase in wear resistance; •• decrease of deformation under load and of creep; •• reduction of thermal expansion; •• some types of filler increase the thermal and electric conductivity.

TYPICAL APPLICATIONS FOR TIMREX TYPICAL APPLICATIONS Filled PTFE is often not as strong and resilient as virgin PTFE. Sometimes, the filler limits the resistance to chemical agents and modify the electrical properties.

TIMREX® GRAPHITE TIMREX® PC40-OC coke AND COKE FILLERS IN TIMREX® PC40-OC coke is calcined at high temperatures offering low sulphur con- FILLED-PTFE centration, low content of oversize particles, high apparent density and high chemi- cal stability against most chemical substances. TIMREX® PC40-OC coke is added to the virgin PTFE in a percentage by weight between 10 and 35% along with small percentage of graphite. Compounds made of PTFE and TIMREX® PC40-OC coke have excellent wear resist- ance and deformation strength and compared to the virgin PTFE, they have practi- cally unchanged chemical resistance and friction behaviour. Typical final materials that can be produced with coke filled PTFE are: engineering design components, slide bearings, valve housing and valve seats for chemi- cal applications, piston sealing and guiding elements for dry-running compressors.

TIMREX® KS44 synthetic graphite TIMREX® KS 44 is a primary synthetic graphite obtained by the full graphitisation of amor- phous carbon materials through the well known Acheson process. The process param- eters in the Acheson furnace such as temperatures and residential times are all optimised in order to achieve the perfect degree of crystallinity and the lowest level of impurities whereas others minor adjustments are made during the material sizing and conditioning. The percentage of TIMREX® KS44 used in the filled PTFE vary between 5 and 15%. TIMREX® KS44 can be used alone or in combination with glass or coke. TIMREX® KS44 lowers the coefficient of friction and is, therefore, often added to other types of filled PTFE for improving this property (and also to improve the lifetime of the cutting tools during for instance the production of gaskets and seals). It improves the de- formation under load, strength and, to a minor degree the wear. Like coke, it serves well in corrosive environments. PTFE filled with TIMREX® KS44 are often used in steering and shock-absorber gasket, bearings as well as in slide films for anti-static applications.

20 GRAPHITE AND COKE ®

INFLUENCE OF Wear resistance TIMREX®GRAPHITE Virgin PTFE shows much high wear as a result of the destruction of the banded struc- AND COKE FILLERS IN ture due to easy slippage between the crystalline lamellae in the bands. FILLED-PTFE The presence of well distributed carbon particles in the filled PTFE partially avoid the slippage between the crystalline lamellae in the bands and therefore the wear resist-

ance is improved. FOR TIMREX TYPICAL APPLICATIONS

Deformation strength Virgin PTFE deformation behaviour is somehow similar to the mechanism previously de- scribed. In someway the deformation phenomena could be explained by the tendency of slippage that occurs between the crystalline lamellae. However, in this case the presence of well distributed carbon particles in the filled PTFE offers only a partial explanation to the phenomena because also hardness of these particles is important in determine an improvement of the deformation behaviour.

Friction coefficient The coefficient of friction for various filled PTFE composites is weakly dependent upon the incorporated filler, because a thin PTFE film generally exists at the interface between the body and counter-body. Consequently the coefficient of friction is both similar in the filled PTFE and virgin PTFE. This evidence is true as long as no oversize particles are present in the filler. In fact the presence of oversize particles could lead to a radically modification of the coefficient of friction. Because of that in carbons as well as in other fillers is very important the control of oversize particles.

21 Thermally conductive polymers

WHAT IS THERMAL The ability of a material to conduct heat is known as its thermal conductivity. Thermal CONDUCTIVITY? conductivity itself is nothing else than the transportation of thermal energy from high to low temperature regions. Thermal energy within a crystalline solid is conducted by electrons and/or discrete vibrational energy packets (phonons*). Each effect, phon- ons and movement of free electrons, contributes to the rate at which thermal energy moves. Generally, either free electrons or phonons predominate in the system. GRAPHITE AND COKE

® *Phonons In the crystalline structures of a solid material, atoms excited into higher vibrational fre- quency impart vibrations into adjacent atoms via atomic bonds. This coupling creates waves which travel through the lattice structure of a material. In solid materials these lattice waves, or phonons, travel at the velocity of sound. During thermal conduction it is these waves which aid in the transport of energy.

THERMAL Graphite is an excellent solution for making polymers thermally conductive when elec- CONDUCTIVITY trical conductivity is also tolerated. Graphite operates by a phonon collision mecha- OF GRAPHITE nism, very different from the percolation mechanism occurring with metallic powders. This mechanism, together with the particular morphology of graphite particles, helps to meet the required thermal conductivity at lower additive levels without any abrasion issues. In addition, due to its particular structure, thermal conductivity is different in the different directions of the crystal. It is highly conducting along its layers (ab

TYPICAL APPLICATIONS FOR TIMREX TYPICAL APPLICATIONS direction or in-plane) and less conducting perpendicular to the layers (c direction or through-plane) because there is no bonding between the layers. In particular, expanded graphite is well known as an excellent thermally and electrically conductive additive for polymers. On the way to , high aspect ratio expanded graphite is thermally more conductive when compared to conventional carbon materi- als such as standard graphite and carbon fibres. However, the very low bulk density of expanded graphite makes it very difficult to feed into a polymer melt using com- mon feeding/mixing technologies. In order to overcome the feed issues encountered by compounders with expanded graphite, Imerys Graphite & Carbon has developed a range of products belonging to the TIMREX® C-THERM™ carbon-based product family.

GRADE FEATURES FORM ASH EFFECT ON CONTENT (%) THERMAL CONDUCTIVITY TIMREX® KS family Standard powder < 0.1 medium (spheroids) (through-plane +)

TIMREX® SFG family Standard powder < 0.1 medium (flakes) (in-plane +)

TIMREX® C-THERM™011 High aspect ratio soft granules < 2.5 high (pure)

TIMREX® C-THERM™001 High aspect ratio soft granules < 0.3 high (pure +)

22 THERMALLY Thermally conductive polymers are able to evenly distribute heat generated inter- CONDUCTIVE nally from a device and eliminate “hot spots.” Possible applications for thermally POLYMERS conductive plastics include heat sinks, geothermal pipes, LED light sockets, heat exchangers, appliance temperature sensors and many other industrial applications. Also thermally conductive elastomers can be found in a wide variety of industrial ap- plications such as gaskets, vibration dampening, interface materials, and heat sinks. As highlighted in the figure, the low thermal conductivity of virgin PPH (~0.38 W/m.K) GRAPHITE AND COKE

could be increased by one order of magnitude already at relatively low addition level ® (~3.5 W/m.K at 20% C-THERM™). The “through-plane” thermal conductivity is about the half of the longitudinal “in-plane” thermal conductivity. These results indicate that the anisotropy of the graphite particles is conferred to the final compound, due to their alignment during the injection molding process. This is an important property that has to be taken into account by design engineers. Of course, the thermal con- ductivity strongly depends not only on the sample orientation (direction) during the measurement, but also on the type of polymer, the sample history (type and condi- tions of compounding and processing) and the measurement method. A full set of measurements to determine mechanical properties in PP were performed and are available to customers. When tested at the same loadings, C-THERM™ im- parts similar mechanical properties as conventional carbon materials.

4.0 In-plane In-plane 3.5 inj > Through-plane

3.0 Through-plane FOR TIMREX TYPICAL APPLICATIONS 2.5 2.0 1.5 Thermal conductivity (W/m.K) 1.0 0.5 0 Virgin PPH 20% 20% 20% ENSACO® TIMREX® TIMREX® 250G KS25 C-THERM™

23 EUROPE

Imerys Graphite & Carbon Switzerland Ltd. Group Head Office • Strada Industriale 12 • 6743 Bodio • Switzerland Tel: +41 91 873 20 10 • Fax: +41 91 873 20 19 • [email protected]

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Imerys Graphite & Carbon Japan K.K. Tokyo Club Building 13F • 3-2-6 Kasumigaseki • Chiyoda-ku • Tokyo 100-0013 • Japan Tel: +81 3 551 032 50 • Fax: +81 3 551 032 51 • [email protected]

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AMERICAS

Imerys Graphite & Carbon USA Inc. 29299 Clemens Road 1-L • Westlake (OH) 44145 • USA Tel: +1 440 871 75 04 • Fax: +1 440 871 60 26 • [email protected]

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Imerys Graphite & Carbon is a trademark of the Imerys Group © 2014 Imerys Graphite & Carbon CH-Bodio. No part of this publication may be reproduced in any form without the prior written a uthorisation.

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