Neue CNH-Kunststoffe für neue Anwendungen Vortrag 15. Werkstoff-Forum, Hannover Messe 2015 Dr. Norbert Molitor, Josef Ludwig, Werner Ternka

Transcription

1 Neue CNH-Kunststoffe für neue Anwendungen Vortrag 15. Werkstoff-Forum, Hannover Messe 2015 Dr. Norbert Molitor, Josef Ludwig, Werner Ternka April 2015

2 New Plastic for New Applications 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 Page 2 of 23

3 (1) Characterization of Carbon Nanohorns Description: Carbon Nanohorns (CNH) Spheroidal aggregates of hornlike single-walled nanostructures: Length nm, Diameter 3 25 nm In Bulk-Material: agglomerates up to some µm size Bulk density: Specific Surface: Typical Pore-Ø: Purity: g/l > 200 m²/g (raw material), with treatment > m²/g nm > 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) Page 3 of 23

4 (2) Motivation What could CNH contribute to improve plastics? Preliminary tests gave some indications! Page 4 of 23

5 Polymer melts with CNH CNH, 2 wt% A A = 2.1% + 0.4% SWCNT, 2 wt% A A = 5.1% + 2.4% CNH, 5 wt% A A = 5.2% + 0.4% SWCNT, 5 wt% A A = 6.7% + 1,1% ISO CNH can be dispersed better than SWCNT. (IPF 2012/ 2013) Page 5 of 23

6 Molding CNH filled Polymer Melts Mold sample PA6, 10% CNH Mold sample PA6, 10% CNT Dispersion in polymer melts and molding is easier with CNH than with CNT Page 6 of 23

7 Molding quality with CNH Measurement Abbildungsgenauigkeit of the quality CNH vs of CNTmolded structures 60 Mold sample PA6, 1% CNH z [µm] Mold sample PA6, 1% CNT x [µm] CNH CNT Much sharper structures were obtained in samples molded with plastics filled with CNH compared to plastics equally filled with CNT. Page 7 of 23

8 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 Page 8 of 23

9 (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 Page 9 of 23

10 CNH in Plastics 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 Page 10 of 23

11 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) Page 11 of 23

12 CNH-Plastic Melts Material / T mix / r ( C / U/Min.) 2,5% MA CNH Number of agglomerates > 5 (2) µm / mm² D ave (µm) A > 5 µm (%) PP / 220 C/ 250 rpm ABS / 230 C / 250 rpm PP / 220 / (1383) 7,98 (3,94) 3,52 PP / 220 / (814) 9,12 (4,02) 2,49 PP / 240 / (1347) 8,22 (4,06) 3,57 PP / 240 / (1256) 7,69 (3,77) 2,93 PP / 260 / (1237) 8,03 (4,05) 3,30 PP / 260 / (1784) 7,92 (3,69) 4,33 ABS / 210 / (1629) 8,25 (4,11) 4,35 ABS / 210 / (1044) 8,47 (4,33) 3,23 ABS / 230 / (1204) 8,00 (4,15) 3,19 ABS / 230 / (825) 8,95 (4,31) 2,68 ABS / 250 / (1685) 7,19 (3,70) 3,52 ABS / 250 / (999) 8,28 (4,18) 2,88 PC / 280 / (1068) 6,98 (3,16) 2,19 PC / 280 / (812) 6,91 (2,97) 1,73 PC / 300 / (706) 7,35 (3,23) 1,15 PC / 300 / (750) 7,50 (3,18) 1,15 PA / 250 / (850) 10.3 (3,12) 2,02 PA / 250 / (376) 7.55 (2,95) 0,87 PA / 270 / (909) 8.21 (3,10) 1,85 PA / 270 / (782) 8.92 (2,88) 1,45 PEEK / 340 / (393) 7.35 (3,56) 0,85 Page 12 of 23

13 Complex Viscosity Complex viscosity for CNH filled thermoplastics Moderate increase of complex viscosity, Higher for non polar polymers (e.g. ABS) than for polar polymers (e.g. PC) Page 13 of 23

14 Thermal Stability (TGA) Weight (%) PP-PUR.001 PP-0,1%(Nanohorns).001 PP-2,5%(Nanohorns).001 PP-5%(Nanohorns).001 PP 4 2 Deriv. Weight (%/ C) Weight (%) ABS Pur.001 ABS-0,1%(Nanohorns).001 ABS-2,5%(Nanohorns).001 ABS-5%(Nanohorns).001 ABS Deriv. Weight (%/ C) TGA for CNH filled plastics: Schwarz: 0% Red: 0,1% Blue: 2,5% Green: 5% Temperature ( C) Universal V4.5A TA Instruments Temperature ( C) Universal V4.5A TA Instruments PEEK-PUR.001 PEEK+0,1%NH.001 PEEK+2,5%NH.001 PEEK+5%NH Weight (%) PC-PUR.001 PC-0,1%(Nanohorns).001 PC-2,5%(Nanohorns).001 PC-5%(Nanohorns) Deriv. Weight (%/ C) Weight (%) PA6-Pur.001 PA6-0,1%(Nanohorns).001 PA6-2,5%(Nanohorns).001 PA6-5%(Nanohorns) Deriv. Weight (%/ C) [ ] Weight (%) [ ] Deriv. Weight (%/ C) PC PA PEEK Temperature ( C) Universal V4.5A TA Instruments Temperature ( C) Universal V4.5A TA Instruments Temperature ( C) Universal V4.5A TA Instruments The decomposition of CNH-filled plastics tend to occur at higher temperatures (exception PA6), the heat release tend to be also higher. Page 14 of 23

15 Bending Module / Strength PP ABS Mechanical properties for CNH-filled plastics: Red: Strength Blue: Bending Modulus PC PA6 PEEK CNH-Filler increases strength (exception PEEK) CNH-Filler increases bending Modulus (exception PP) Page 15 of 23

16 Hardness / Scott s Modulus Hardness / Scott s modulus for CNHfilled plastics PP ABS PC PA6 PEEK CNH Filler increase hardness / Scott s modulus. Page 16 of 23

17 Flexural Modulus & Temperature Temperature dependent bending Modulus The increased flexural modulus of elasticity is maintained also with rising temperature (blue 0%, red 1%, green 5%). Page 17 of 23

18 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 Page 18 of 23

19 (4) CNH-plastic-Prototypes Based on the obtained results CNHplastic-prototypes were produced for processing (molding) tests. Page 19 of 23

20 Molding Test Tool Tool for Test rod (rectangular) Test rod (circular) Tensile test bar Pattern shape (structured chip) Page 20 of 23

21 CNHK-Molding-Demonstration Chip Rectangular rod Circular rod Tensile bar Molding of different samples (different patterns) were successfully demonstrated with the test tool Page 21 of 23

22 (5) Prototypes for 3D-Printing CNH filled thread samples (3 mm diameter, 10 % CNH) have been produced with PA6, PP, ABS and PC for 3D printing Page 22 of 23

23 (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) Page 23 of 23

24 Questions are welcome! Thank you very much for your attention! Norbert Molitor, TIE GmbH, Josef Ludwig, LNP GmbH, Werner Ternka, TPK GmbH,