Sulfron in Mechanical Rubber Goods

Transcription

1 Sulfron in Mechanical Rubber Goods Mukund Tiwari, Ko Arts, Gerard van den Hondel Teijin Aramid BV IOM3 Fillers in Rubber Meeting London, March 18, 2011

2 Teijin s business groups Teijin Aramid films & plastics no. 1 in polyester films no. 2 in polycarbonate for optical discs 29% high performance fibers no. 1 in (para-)aramid no. 2 in carbon fiber 29% pharmaceuticals & home health care respiratory, bone & joint and cardiovascular & metabolic diseases 11% 20% 5% trading & retail IT & new business development

3 Teijin Aramid - Twaron Production Delfzijl: Wad denzee Friesland G roning en Monomer and polymer Applications Noord Holland Ijs selmee r Flevoland Dr en the Overijssel Emmen: Twaron Yarn, Staple fiber and pulp Tires Aircraft Zee land Zu id Ho lland U trec ht Noord Bra bant G elde rla nd Limbu rg Arnhem: Pulp, pelletized monomer, purified polymer Defense & law enforcement Marine Off shore Optical fiber cables Plastics Friction parts Protective apparel Mechanical Rubber Goods..and many more

4 What is Sulfron? SULFRON is based on Twaron fibers, which are modified by chemicals to activate the surface of the p-aramid fibers. N N H H O O C C * * n Chemical structure of p-aramid

5 Result of using Sulfron Reduction of tan δ 0,220 0,200 0,180 0,160 CMP1 (Control) CMP2 (1,5 Phr ) CMP3 (2,0 Phr ) CMP4 (3,0 Phr ) loss factor (tan δ) 0,140 0,120 0, 0,080 0,060 0,040 0,020 Dynamic strain: 2 % Frequency: 10 Hz 0, Tempearture ( o C) Lowering of tan δ Improves hysteresis and lowering in the Heat Build up (HBU)

6 SULFRON interacts with filler surface: Results in the reduction in the fillerfiller interaction (Payne effect)); SULFRON improves hysteresis of the vulcanizate Results in lower heat build up; SULFRON CAN also improve: Tear and flex resistance; Modulus without significant damage on elongation at break. Complex shear modulus (G*) Filler-Filler interaction- Payne Effect In-Rubber Structure Hydrodynamic Effects Polymer Network Log (strain)

7 Sulfron 3001 in different rubbercompounds NR compound EPDM compound

8 Sulfron 3001 in NR compound Results from Teijin Aramid lab test

9 NR rubber compound formulations Compounds (in Phr) CMP1 CMP2 CMP3 CMP4 SMR 10 Carbon Black (N234 type) Sulfron ,5 2 3 Nytex 840 (oil) Zinc Oxide Stearic Acid Sunolite 240 (MC wax) 3 2,55* 2,40* 2,10* 6 PPD (Anti-degradant) Total [masterbatch] (Phr) ,05 162,40 163,10 Cure recipe Masterbatch (Phr) ,05 162,40 163,10 Sulphur CBS Total [final compound] (Phr) ,05 165,40 166,10 *correction of micro-crystalline wax

10 Sulfron 3001 in NR: Mixing procedure Mixer: 1,6 L Banbury type Fill-factor: 70% Starting temp.: 50 C Mixing time (mins.) Step 1: 0 1 2½ 4 5 Compounding Rubbers ½ Carbon black + Sulfron 3001 Zinc Oxide + Stearic acid + Oil + ½ Carbon black + rest Sweep Dump ( Temp.: C) Step 2: Addition of curatives on two-roll mill at lower temperature

11 Sulfron 3001 in NR: Mixing cycle (Temperature profile) Mixer Stock temperature ( o C) Control (CMP1) 1,5 Phr S 3001 (CMP2) 2,0 Phr S 3001 (CMP3) 3,0 Phr S 3001 (CMP4) Step 5: Dump Step 4: Sweep Step 3: ZnO + Stearic acid + Oil + 1/2 carbon black + Rest Step 1: Rubber Step 2: 1/2 carbon black + with and without S Mixing time (mins.)

12 Filler-filler interaction: Payne effect G`(1% - 20%) Measured on the masterbatch 1 st day 260 G' (1% - 20%) kpa Control S 3001; 1,5 Phr S 3001; 2 Phr S 3001; 3 Phr CMP1 CMP2 CMP3 CMP4 Sample code Lower the filler-filler interaction Lower the Payne effect

13 Filler-filler interaction: After cure G`(3% - 10%) Freq 1Hz - Measured on the cured sample G'(3% - 10%) kpa Control S 3001; 1,5 Phr S 3001; 2 Phr Shear mode: Temp.: o C Freq.: 1 Hz S 3001; 3 Phr 40 0 CMP1 CMP2 CMP3 CMP4 Sample code Lowering in the difference of Shear modulus Reduction in the filler-filler interaction

14 Filler-filler interaction: After cure G`(3% - 10%) Freq 10Hz - Measured on the cured sample Shear mode: Temp.: o C Freq.: 10 Hz G'(3% - 10%) kpa Control S 3001; 1,5 Phr S 3001; 2 Phr S 3001; 3 Phr 40 0 CMP1 CMP2 CMP3 CMP4 Sample code Lowering in the difference of Shear modulus Reduction in the filler-filler interaction

15 Cure characteristics Cure temperature: 150 C Compounds CMP1 CMP2 CMP3 CMP4 Properties Control 1,5 Phr 2 Phr 3 Phr t s2 (mins.) 3,85 4,12 4,23 4,37 t 90 (mins.) 9,11 9,98 9,77 9,63 M L (Nm) 0,17 0,16 0,15 0,14 M H (Nm) 1,5 1,43 1,41 1,41 S (M H M L ) (Nm) 1,33 1,27 1,26 1,26

16 Hardness (Shore A type) Shore A Control S 3001; 1,5 Phr S 3001; 2 Phr S 3001; 3 Phr CMP1 CMP2 CMP3 CMP4 Sample code

17 Mechanical properties (Tensile) Compounds CMP1 CMP2 CMP3 CMP4 Properties Control 1,5 Phr 2 Phr 3 Phr Tensile strength (MPa) 30,2 28,2 28,3 26,9 Elongation (%) Mod 25% (MPa) 0,8 0,8 0,9 0,9 Mod 50% (MPa) 1,2 1,3 1,4 1,4 Mod % (MPa) 2,2 2,3 2,5 2,6 Mod 200% (MPa) 6,1 6,3 6,7 6,8 Mod 300% (MPa) 11,9 12,4 13,2 13,5

18 Tensile behaviour (Stress-Strain curves) Stress (MPa) Control [CMP1-Y3064-1] 1.5 phr [CMP2-Y3064-6] 2 phr [CMP3-Y3064-7] 3 phr [CMP4-Y3064-8] Strain (%)

19 Dynamic properties: Hysteresis Gabo Eplexor 150 N tan δ values measured at different temperatures 0,220 0,200 0,180 0,160 CMP1 (Control) CMP2 (1,5 Phr ) CMP3 (2,0 Phr ) CMP4 (3,0 Phr ) loss factor (tan δ) 0,140 0,120 0, 0,080 0,060 0,040 Reduction of tan δ 0,020 Dynamic strain: 2 % Frequency: 10 Hz 0, Tempearture ( o C) Improves hysteresis and lowering in the Heat Build up (HBU)

20 Heat Build Up (HBU):Microwave method Microwave power: 800 W Compounds CMP1 CMP2 CMP3 CMP4 Properties* Control 1,5 Phr 2 Phr 3 Phr Time [sec.] Temperature rise [ C] Blowout (Burning) 137 (No blowout) 122 (No blowout) 108 (No blowout) DUPLO CMP1 CMP2 CMP3 CMP4 Temperature rise [ C] Blowout (Burning) 149 (No blowout) 111 (No blowout) 120 (No blowout) Sample dimensions: Diameter: 17,8 mm Height: 25 mm

21 Conclusions Sulfron 3001 in NR model compound shows: a significant decrease in the carbon black-carbon black interactions (Payne effect) in the uncured and cured state; As a result of this improves: Hysteresis (tan δ ); Heat build up (in correlation with tan δ). a slight effect on cure, processing and mechanical properties. Heat Build up test by Microwave method: shows a decrease in the temp. rise for the samples with ; could be used as a fast screening method.

22 Sulfron 3001 in EPDM compound Results from Teijin Aramid lab test

23 EPDM Rubber compound formulations Compounds EP1 EP2 EP3 EP4 EP5 EP6 Keltan 578 Z Corax N Corax N S Sunpar ZMMBI Naugard Total Cure recipe Sulphur Perkadox 14-40pd Total

24 Sulfron 3001 in EPDM: Mixing procedures Mixer: 1.6 L Banbury type Fill-factor: 70% Starting temp.: 50 C Mixer: 1.6 L Banbury type Fill-factor: 70% Starting temp.: 50 C Mixing time (min) Step 1: 0 1 2½ 4 5 Step 2: Rubbers ½ N660 + with or without Sulfron 3001 Oil + ½ N660 + rest Sweep Compounding Dump ( Temp.: C) Addition of curatives on two-roll mill at lower temperature Mixing time (min) Step 1: 0 1 2½ 4 5 Step 2: Rubbers ½ N660 + ½ N326 + with or without Sulfron 3001 Oil + ½ N660 + ½ N326 + rest Sweep Compounding Dump ( Temp.: C) Addition of curatives on two-roll mill at lower temperature

25 Sulfron 3001 in EPDM: Mixing cycle (Temperature Profile) Mixer stock temperature ( o C) Temperature profile during Sulfron () mixing 1/2 CB + Rest 1/2 CB + with or without Polymer Sweep Dump EP1 [N660] EP2 [N phr ] EP3 [N phr ] EP4 [N660 + N326] EP5 [N660 + N phr ] EP6 [N660 + N phr ] Mixing time (min)

26 Filler-filler interaction: Payne effect Measured on the masterbatch 1 st day Control [N660] 2 phr S phr S 3001 Control [N660 + N326] 2 phr S phr S G' (1% - 20%) kpa 50 0 EP1 EP2 EP3 EP4 EP5 EP6 Sample code Lower the filler-filler interaction Lower the Payne effect

27 Filler-filler interaction: After cure Measured on the cured sample: Strain sweep at C G'(3%-10%) kpa Control [N660] 2 phr S phr S 3001 Control [N660 + N326] Shear mode: Temp.: o C Freq.: 0.5 Hz 2 phr S phr S EP1 EP2 EP3 EP4 EP5 EP6 Sample code Lowering in the difference of Shear modulus Reduction in the filler-filler interaction

28 Cure characteristics Cure temperature: 170 C Compounds EP1 EP2 EP3 EP4 EP5 EP6 Properties Control 2 phr 3 phr Control 2 phr 3 phr t s2 (min) t 90 (min) M L (Nm) M H (Nm) Delta S (Nm)

29 Hardness (Shore A type) Hardness (Shore A type) Control [N660] 2 phr S phr S 3001 Control [N660 + N326] 2 phr S phr S EP1 EP2 EP3 EP4 EP5 EP6 Sample code

30 Mechanical properties (Tensile behaviour) Compounds EP1 EP2 EP3 EP4 EP5 EP6 Properties Control 2 phr 3 phr Control 2 phr 3 phr Tensile strength (MPa) Elongation (%) Mod 25% (MPa) Mod 50% (MPa) Mod % (MPa) Mod 200% (MPa)

31 Dynamic properties: Hysteresis Rubber Process Analyzer (RPA) tan δ values measured at different temperatures loss factor (tan δ) Shear measurements: Dynamic strain amplitude: 2% Frequency: 1 Hz EP1 (Control: N660) EP2 (N phr ) EP3 (N phr ) EP4 (Control: N326 + N660) EP5 (N326 + N phr ) EP6 (N326 + N phr ) Temperature ( o C) Lowering of tan δ Improves hysteresis and lowering in the Heat Build up (HBU)

32 Conclusions Sulfron 3001 in EPDM based model belt compound shows: a significant decrease in the carbon black-carbon black interaction (Payne effect) both in the uncured and cured state; As a result of this improves: Hysteresis (tan δ ); Heat build up (in correlation with tan δ). a slight effect on cure, processing and mechanical properties.