neue cnh-kunststoffe für neue...

Neue CNH-Kunststoffe für neue Anwendungen

Vortrag 15. Werkstoff-Forum, Hannover Messe 2015 Dr. Norbert Molitor, Josef Ludwig, Werner Ternka

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CONTENTS

(1) Carbon Nanohorns (CNH)(2) Motivation to use CNH in plastics(3) Testing of CNH filled plastics(4) Prototypes (granulate) for molding(5) Protoypes (thread) for 3D – printing(6) Outlook

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Description:Carbon Nanohorns (CNH)

Spheroidal aggregates of hornlike single-walled nanostructures: Length 20 – 150 nm, Diameter 3 – 25 nm

In Bulk-Material: agglomerates up to some µm sizeBulk density: 35 - 100 g/lSpecific Surface: > 200 m²/g (raw material),

with treatment > 1.000 m²/g Typical Pore-Ø: 10 - 100 nmPurity: > 95 % C, out of which

about 99 % in nanostructures

-> practical no amorphous carbon and no contamination resulting from the production process (just the impurities from the precursor)

(1) Characterization of Carbon NanohornsTI

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(2) Motivation

What could CNH contributeto improve plastics?

Preliminary tests gavesome indications!

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Polymer melts with CNH

CNH, 2 wt%AA = 2.1% + 0.4%

CNH, 5 wt%AA = 5.2% + 0.4%

CNH can be dispersed better than SWCNT.

ISO 18553

SWCNT, 2 wt%AA = 5.1% + 2.4%

SWCNT, 5 wt%AA = 6.7% + 1,1%

(IPF 2012/ 2013)

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Molding CNH filled Polymer Melts

Dispersion in polymer melts and molding is easier with CNH than with CNT

Mold sample PA6, 10% CNH Mold sample PA6, 10% CNT

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Abbildungsgenauigkeit CNH vs CNT

‐60

‐40

‐20

0

20

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60

‐1000 ‐800 ‐600 ‐400 ‐200 0 200 400 600 800 1000

x [µm]

z [µm

]

CNH CNT

Molding quality with CNH

Much sharper structures were obtained in samples molded with plastics filled with CNH compared to plastics equally filled with CNT.

Mold sample PA6, 1% CNH

Mold sample PA6, 1% CNT

Measurement of the quality of molded structures

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First Conclusions

Potential of CNH as filler to obtain new thermoplastics with improved properties :• Material properties:

• Young‘s modulus, hardness• Strength • Thermal stability, fire resistance

• Easy and good processing properties, such as: • High molding quality• Use for conventional molding• Use for micro molding

• Use for 3D-printers (prototyping)• Environmentally friendly and safe

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(3)Testing of CNH-filled Plastics

Decision for a joint R&D-Prototype Project for CNH filled plastics (PVC, PC, PP, PA, ABS, PEEK)

Co-sponsored by the State of Niedersachsen

and EU

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• Technical objectives: • Improvement of the mechanical properties • Improvement of the thermal stability• Processing in conventional facilities:

• Extruding, molding, micro-molding facilities• Economic objectives:

• Cheap processing Easy Post-processing• Improved material properties• Low fill grades

CNH in PlasticsTI

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Qualification of CNH-Fillers

• Specific surface of CNH higher than for Carbon Black N121:295 m²/g (CNH) vs 119 m²/g (N121)

• Adsorption places of CNH of higher value compared to CB (N121)

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Material / Tmix / r(°C / U/Min.)

2,5% MA CNH

Number ofagglomerates

> 5 (2) µm / mm²

Dave(µm)

A > 5 µm (%)

PP / 220 / 50 247 (1383) 7,98 (3,94) 3,52PP / 220 / 250 137 (814) 9,12 (4,02) 2,49PP / 240 / 50 259 (1347) 8,22 (4,06) 3,57

PP / 240 / 250 199 (1256) 7,69 (3,77) 2,93PP / 260 / 50 245 (1237) 8,03 (4,05) 3,30

PP / 260 / 250 252 (1784) 7,92 (3,69) 4,33ABS / 210 / 50 321 (1629) 8,25 (4,11) 4,35

ABS / 210 / 250 246 (1044) 8,47 (4,33) 3,23ABS / 230 / 50 256 (1204) 8,00 (4,15) 3,19

ABS / 230 / 250 178 (825) 8,95 (4,31) 2,68ABS / 250 / 50 254 (1685) 7,19 (3,70) 3,52

ABS / 250 / 250 219 (999) 8,28 (4,18) 2,88PC / 280 / 50 75 (1068) 6,98 (3,16) 2,19

PC / 280 / 250 35 (812) 6,91 (2,97) 1,73PC / 300 / 50 57 (706) 7,35 (3,23) 1,15

PC / 300 / 250 51 (750) 7,50 (3,18) 1,15PA / 250 / 50 42 (850) 10.3 (3,12) 2,02

PA / 250 / 250 13 (376) 7.55 (2,95) 0,87PA / 270 / 50 48 (909) 8.21 (3,10) 1,85

PA / 270 / 250 16 (782) 8.92 (2,88) 1,45PEEK / 340 / 250 51 (393) 7.35 (3,56) 0,85

CNH-Plastic Melts

PP / 220°C/ 250 rpm

ABS / 230 °C / 250 rpm

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Complex Viscosity

Moderate increase of complex viscosity, Higher for non polar polymers (e.g. ABS) than for polar polymers (e.g. PC)

Complex viscosity forCNH filledthermoplastics

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Thermal Stability (TGA)

The decomposition of CNH-filled plastics tend to occur at higher temperatures (exception PA6), the heat release tend to be also higher.

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350 400 450 500 550

Temperature (°C)

PP-PUR.001––––––– PP-0,1%(Nanohorns).001––––––– PP-2,5%(Nanohorns).001––––––– PP-5%(Nanohorns).001–––––––

Universal V4.5A TA Instruments

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Temperature (°C)

ABS Pur.001––––––– ABS-0,1%(Nanohorns).001––––––– ABS-2,5%(Nanohorns).001––––––– ABS-5%(Nanohorns).001–––––––


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Temperature (°C)

PC-PUR.001––––––– PC-0,1%(Nanohorns).001––––––– PC-2,5%(Nanohorns).001––––––– PC-5%(Nanohorns).001–––––––


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Temperature (°C)

PA6-Pur.001––––––– PA6-0,1%(Nanohorns).001––––––– PA6-2,5%(Nanohorns).001––––––– PA6-5%(Nanohorns).001–––––––


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0 100 200 300 400 500 600 700 800

Temperature (°C)

PEEK-PUR.001PEEK+0,1%NH.001PEEK+2,5%NH.001PEEK+5%NH.001


TGA for CNH filledplastics:

Schwarz: 0%Red: 0,1%Blue: 2,5%Green: 5%

PEEK

ABS

PC PA6

PP

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Bending Module / Strength

CNH-Filler increases strength (exception PEEK)CNH-Filler increases bending Modulus (exception PP)

Mechanical properties forCNH-filled plastics:

Red: StrengthBlue: Bending

Modulus

PEEK

ABS

PC PA6

PP

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Hardness / Scott‘s Modulus

CNH Filler increase hardness / Scott‘s modulus.

ABS

PA6PC PEEK

PP

Hardness / Scott‘smodulus for CNH-filled plastics

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Flexural Modulus & Temperature

The increased flexural modulus of elasticity is maintained also withrising temperature (blue 0%, red 1%, green 5%).

Temperaturedependent bendingModulus

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Conclusions for CNH-filled Thermoplastics

• CNH-Fillers are easy to disperse in polymer melts.• CNH-Fillers improve the crystallinity (in cristalline polymers). • CNH-Fillers improve the Young-Modulus.• CNH-Fillers improve the break resistance.• CNH-Fillers improve hardness.• CNH-Fillers improve the fire resistance.• CNH-Fillers improve the thermal stability.• Molding quality with CNH filled plastics is high.• Molding with CNH filled plastics is easy and efficient.

→ Prototypes for CNH filled plastics: • Granulates for molding• Thread for 3D-Printing

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(4) CNH-plastic-Prototypes

Based on the obtained results CNH-plastic-prototypes were produced for processing (molding) tests.

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Molding Test Tool

Tool for Test rod

(rectangular) Test rod (circular) Tensile test bar Pattern shape

(structured chip)

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CNHK-Molding-Demonstration

Molding of different samples (different patterns) were successfully demonstrated with the test tool

Circular rod

Tensile bar

Rectangular rodChip

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(5) Prototypes for 3D-Printing

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CNH filled thread samples (3 mm diameter, 10 % CNH) have been produced with PA6, PP, ABS and PC for 3D printing

(6) Outlook

CNH-filled Thermoplastics can be used for:• Small high quality pieces with exact geometry

(e.g. plug casing, gear wheel, non-magnetic components for watches)• Small /miniaturized mechanical pieces with low deformation

(e.g. plastic chassis, lever, rods, plastic -metal/-ceramic/-glass joints)• Small /miniaturized mechanical pieces with low abrasion

(e.g. friction wheel, joint balls, articulation, friction coupling) • Pieces which are temperature resistant (fire resistant)

(e.g. battery packages, heat treathened components) • Prototyping with 3D printing with high performing plastics

(e.g. CNH reinforced ABS, combined composite 3-D printing)• As new type of reinforced plastics (e.g. alternative to GFRP)

(e.g. where molding, machining, recycling is easy and efficient)

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Questions are welcome!Thank you very much for your attention !

Norbert Molitor, TIE GmbH, www.t-i-e.euJosef Ludwig, LNP GmbH, www.lnp-northeim.de

Werner Ternka, TPK GmbH, www.tpk-kunststofftechnik.de

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