Nippon Shokubai Co., Ltd. · TSE:4114

Nippon Shokubai — 3rd International Conference on Polycarboxylate Superplasticizers PCE 2019

21 slides from Nippon Shokubai's conference presentation, Sep 25, 2019

1. Slide 1: Improved Air-void Quality and Rheology with Novel Amphiphilic Polycarboxylate-based Superplasticizer

   3rd International Conference on Polycarboxylate Superplasticizers PCE 2019 25th, September 2019 Improved Air-void Quality and Rheology with Novel Amphiphilic Polycarboxylate-based Superplasticizer Nippon Shokubai Co., Ltd. Yuya Akao Copyright NIPPON SHOKUBAI CO., LTD. All rights reserved. 1

2. Slide 2: Index

   Index 1. Introduction 2. Concept of Amphiphilic PCE 3. Fundamental results 4. Results of mortar/concrete test 5. Summary Copyright NIPPON SHOKUBAI CO., LTD. All rights reserved. 2

3. Slide 3: Introduction

   Introduction 1981 The first patent application of MPEG PC-type WRA in the world 2000~ Patent application of IPEG(TPEG), HPEG, VPEG type WRA MPEG type PCE structure invented by NSCL, IPEG(TPEG), HPEG, VPEG type PCE structure Patent JPS5918338B2 invented by NSCL, Akashi bridge pier (Japan) Tokyo-bay h

4. Slide 4: Patent applications of IPEG, HPEG type PCEs

   Patent applications of IPEG, HPEG type PCEs United States Patents EP Patents US6727315B2,US6569234B2,US9212094B2, EP1103570B1,EP1179517B1,EP1390317B1, US7125944B2,US8058328B2,US7030282B2, EP2263984B1,EP1680377B1,EP1213315B1, US7026442B2,US9850378B2,US10208203B2, EP1229005B1,EP2623528B1,EP2152771B1,

5. Slide 5: Concept of “Amphiphilic PCE”

   Concept of “Amphiphilic PCE” Copyright NIPPON SHOKUBAI CO., LTD. All rights reserved. 5

6. Slide 6: Concept of Amphiphilic PCE

   Concept of Amphiphilic PCE “Amphiphilic molecules“ contains both hydrophilic and hydrophobic components. Conventional PCE Amphiphilic PCE Drawbacks Improvement Rough entrained air Fine entrained air Increase viscosity Better rheology Estimated Mechanism Adsorbed on cement particle and also on air bu

7. Slide 7: Design of Amphiphilic PCEs

   Design of Amphiphilic PCEs Chemical composition Hydrophobic Dispersing Acid Mw group group Conventional PCE STD STD STD STD [CP] a low similar Amphiphilic PCE b Slightly same [AP] c high d High lower Copyright NIPPON SHOKUBAI CO., LTD. All rights reserved. 7

8. Slide 8: Fundamental results

   Fundamental results Copyright NIPPON SHOKUBAI CO., LTD. All rights reserved. 8

9. Slide 9: Adsorption ratio on cement

   Adsorption ratio on cement W/C=100, OPC(JP)=100g, W=100g, Dosage of PCE 0.05wt%/C, Analyzed by TOC Adsorption ratio [%] 100% 80% 60% 40% CP 20% AP-d 0% 0 50 100 150 200 Time [min] AP-d has moderate adsorption rate Copyright NIPPON SHOKUBAI CO., LTD. All rights reserved. 9

10. Slide 10: MD simulation

    MD simulation Modeling conditions 1) Scientific Reports , 7, 16599 (2017) ・MD simulations: Gromacs package1) ・Cement pore solution1): 1.72 g/L CaSO4 2H2O, 6.959 g/L Na2SO4, 4.757 g/L K2SO4 and 7.12 g/L KOH * Replace “acid” to “hydrophobic group” CP-model Rg (all) = 4.2 nm AP-model Rg (all) = 3.71 nm

11. Slide 11: Polymer analysis

    Polymer analysis Wilhelmy method Result 80 100% 70 84% γ (mN/m) 60 50 64% γ：Statistic surface tension L：2d + 2W 40 Water CP CP AP-d AP-d 0.1wt%aq. 0.1wt%aq 0.1wt%aq. 0.1wt%aq 𝑭 𝜸= 𝑳 ∗ 𝒄𝒐𝒔𝜽 AP-d is stronger to foam than CP Copyright NIPPON SHOKUBAI CO., LTD. All rights reserved. 11

12. Slide 12: Dosage efficiency

    Dosage efficiency Concrete Test Mix design: W/C=0.45 s/a=0.47 OPC(JP)=382.2kg/m3, Slump 22±1, Air<2.0% Mixing protcol : C+W+S+G ⇒90sec (60rpm.) 0.16 ▲20% 0.14 PCE dosage ▲10% ▲15% 0.12 0.10 0.08 0.06 CP AP-a AP-b AP-c AP-d (wt%/C) PCE 0.1 05 0.1 1 5 0.1 20 0.1 20 0.1 30 Defoamer 0.0 0.0 0.001 2 0.00

13. Slide 13: Results of mortar/concrete test

    Results of mortar/concrete test Copyright NIPPON SHOKUBAI CO., LTD. All rights reserved. 13

14. Slide 14: Features of Amphiphilic PCE①

    Features of Amphiphilic PCE① Images in hardened concrete With PCE as is With Defoamer Defoamer (& AEA) Air ~ 10 vol% ~2 vol% ~5 vol% Conventional PCE Amphipilic PCE Copyright NIPPON SHOKUBAI CO., LTD. All rights reserved. 14

15. Slide 15: Entrained air property

    Entrained air property Air Void Measurement Concrete Test Mix design: W/C=0.45, s/a=0.47, OPC(JP)=382.2kg/m3 Refer to ASTM C457-98. Mixing protocol: C+W+S+G ⇒90sec (60rpm.) 800 air < 2% Spacing Factor (μm) 700 600 500 air 5-6% 400 300 200 CP AP-a AP-b AP-c AP-d More hydrophobic group, smaller spacin

16. Slide 16: Entrained air property

    Entrained air property Concrete Test W/C=0.45, s/a=0.47, OPC(JP)=382.2kg/m3, Slump=23±1cm, Air=5-6% C+W+S+G ⇒90sec (60rpm.) 400 Spacing Factor (μm) 350 344 300 293 250 271 200 (wt%/C) CP CP AP-d ・All met ASTM freezing PCE 0.1 1 5 0.1 2 0.1 35 thawing resistance criteria Defoamer 0.001 7 none 0.001 6

17. Slide 17: Features of Amphiphilic PCE②

    Features of Amphiphilic PCE② Fresh concrete Conventional PCE Amphiphilic PCE contact point cement Air ■Stronger bubble may show stronger bearing effect. ■More of contact points to cement particles may increase yield point. Copyright NIPPON SHOKUBAI CO., LTD. All rights reserved. 17

18. Slide 18: Rheological property

    Rheological property RST Rheometer (BROOKFIELD) Hysteresis curve ★𝒀𝒊𝒆𝒍𝒅 𝒑𝒐𝒊𝒏𝒕 = 𝑴𝒂𝒙𝒊𝒎𝒖𝒎 𝒀𝒊 [𝑷𝒂] 𝒀𝒎 −𝒀𝒍 Vane spindle ●𝑷𝒍𝒂𝒔𝒕𝒊𝒄 𝒗𝒊𝒔𝒄𝒐𝒔𝒊𝒕𝒚 = [𝑷𝒂 ∗ 𝑺] 𝑿𝒎 −𝑿𝒍 𝑿 𝒂𝒙𝒊𝒔 = 𝑺𝒉𝒂𝒓𝒆 𝒓𝒂𝒕𝒆 [𝟏/𝒔] 𝒀 𝒂𝒙𝒊𝒔 = 𝑺𝒉𝒂𝒓𝒆 𝑺𝒕𝒓𝒆𝒔𝒔 [𝑷𝒂] 1200 ★…

19. Slide 19: Rheological property

    Rheological property Mortar conditions W/C=0.45, OPC(JP)=525g, Sand=1350g, W=188.8g, Temp.=20℃, Flow 190±10mm, air 3±0.5% Mixing procedure : S+C+W (9min), Hobart mixer (speed 1) 600 30 CP ↑ 500 Share stress [Pa] Worse AP-d 25 Plastic viscosity (1-4 1/s ) [Pa*S] 400 25% 300 20 Decrease 200 15 Better

20. Slide 20: Summary

    Summary Amphiphilic PCE Features Smaller spacing factor Adapted freezing thawing criteria Better plastic viscosity & yield point Prospective applications ・Contribute to better pumpability with Lower plastic viscosity ・Simplify admixture system ex) Amphiphilic PCE with defoamer instead of conventiona

21. Slide 21: Thank you for your kind attention

    Thank you for your kind attention ・NSCL are ready for supplying sample ・It is possible to provide this PPT file 21

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