Strength Enhancement for Portland Limestone Cements

Steve FarringtonPrincipal Scientist, Admixture Systems Development

PCA Manufacturing Committee Fall Technical Session

August 25, 2014

Presentation synopsis

M ti tiMotivation

Approach

Testing

Results

Summary

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Company overviewCompany overviewBASF – The Chemical Company

• The world’s leading chemical company• Serves all major industries

380 d i f ili i 6 V b d i• 380 production facilities; 6 Verbund sites• World-class, innovative, high-value

products• Intelligent, sustainable system solutions• 2013 Sales: €74 Billion• Employees: 112 000Employees: 112,000

“We create chemistry for a sustainable future”

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We create chemistry for a sustainable future

BASF: a global supplier of cementBASF: a global supplier of cement additives

Why?

existing global presence, infrastructure, coverage and customer access

innovation focus and R&D capacity to drive new technologies

technological competence in mineralogy, materials, cement hydration

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global access to technologies and chemistries throughout BASF

From request to product: 8-step approach q p p ppto a tailored solution

3. Formulation f dditi1. Materials to BASF

2. Milling in lab ball millof additives

4. Mortar testing(additives w/ mix H2O)

6. Mortar and/or t t ti

8. Mortar and/or concrete testing

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5. Milling in lab(with additives)

concrete testing7. Plant trial(plant and/or BASF)

Why focus on Portland LimestoneWhy focus on Portland Limestone Cement?

Sustainable development

Regulation

Climate change legislation

Portland limestone cements (5-15% limestone) recognized by Canadian standards in 2008

Type IL Portland–limestone cement category included in 2013 version of ASTM C595

C t d h d li t t d ASTM C1157Cement producers have made limestone cements under ASTM C1157

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PLC and additive formulation approach

General approach for production of PLC is to grind the cement to a higher Blaine fineness to try to match the early strength of OPC

longer grinding time = lower mill production longer grinding time = higher energy requirement focus on early-age strength can reduce late-age strength

Formulation target: efficient grinding aid improve hydration process to improve early strength development with improve hydration process to improve early strength development with

innovative chemistry include chemistry for late strength development

Allow for higher mill production by achieving the early strength without a large Blaine fineness increase

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Summary of tests done with a PCASummary of tests done with a PCA member company

New MasterCem performance enhancing cement additive was tested on three different days in one of the finish mills producing Type IL cement

Type IL, MasterCem @ 0.09% by mass cementcement

Production increase >15% compared to Type IL with amine acetate grinding aidyp g g

Cement properties also compared to Type I with amine acetate as grinding aid

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Finish mill production

Date Time Type Limestone Additive -325, % Blaine, cm2/g

Production, tph

1-day cube strength, psi

28-day cube strength, psi

6/19/2013 13:30 IL 14.2% MasterCem 94.4 3805 74.3 2536 6200

6/19/2013 10:30 IL 14.1% MasterCem 96.0 4022 63.4 2523 6200

6/19/2013 16:00 IL 15 0% MasterCem 97 8 4253 62 3 2878 63806/19/2013 16:00 IL 15.0% MasterCem 97.8 4253 62.3 2878 6380

6/19/2013 18:30 IL 13.9% amineacetate 96.4 4229 58.3 2567 5560

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Cement testing results: cube strength

Type IL Blaine target: 4400

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Results from concrete tests: ASTM C465Results from concrete tests: ASTM C465 certification of MasterCem

Concrete data Type IL (sample 1) Type IL (sample 2) ASTM Type IL (sample 1) Type IL (sample 2) ASTM

MasterCem 0 0.09% difference 0 0.09% difference C465

w/c 0.59 0.56 -0.03 0.58 0.56 -0.02 Slump (in) 2 75 2 5 -0 25 2 5 2 75 0 25Slump (in) 2.75 2.5 0.25 2.5 2.75 0.25

Air (%) 1.6 2.4 0.8 1.7 2.2 0.5

Concrete compressive strength testing T IL ( l 1) T IL ( l 2) ASTM Type IL (sample 1) Type IL (sample 2) ASTM

MasterCem 0 0.09% difference % 0 0.09% difference % C465

3-day 3195 3918 723 123 3218 3881 663 121 7-day 4000 4904 904 123 4037 4895 858 1217-day 4000 4904 904 123 4037 4895 858 12128-day 5026 6119 1093 122 5296 6006 710 113 Average 123 118 90% min.

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Conclusions from first industrial trials ofConclusions from first industrial trials of MasterCem

Use of MasterCem performance enhancing additive allowed for 15% improvement of finish mill production of Type IL cement

U f M t C f h i t dditi ll d TUse of MasterCem performance enhancing cement additive allowed Type IL cement to have a similar strength profile to Type I cement

During one of the trials samples were collected for certification of theDuring one of the trials, samples were collected for certification of the MasterCem additive under ASTM C465

ASTM C465 certification (plant-specific) of a MasterCem product was S C 65 ce ca o (p a spec c) o a as e Ce p oduc asachieved

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BASF Cement Additives teamMatt McGlone: Business Segment Manager, Cement AdditivesJulissa Hidalgo: Product Manager Cement AdditivesJulissa Hidalgo: Product Manager, Cement AdditivesBryan Patterson: Market Development Manager, Cement Additives

Questions?

CEMENTIUM®. Cementing a better future.13

14INTERN13.03.2011

C3S Alite 70.6

Phase [ma.-%] Klinker Aug08 Mergelstetten

-C2S Belite 10.5C3A total 10.0C3A cub. : orthor. 90 : 10C4(A,F) Ferrite 7.1K2SO4 Arcanite 0.0K3Na(SO4)2 Aphthitalite 0.5K2Ca2(SO4)3 Ca-Langbeinite 0.0CaO Free Lime 0.0MgO Periclase 1.0CaCO3 Calcite 0.3SiO2 Quartz 0.1Ca(OH)2 Portlandite 0.0

density (total) 3.16220

Solid state chemistry (XRF, fused bead): Klinker Aug08 Mergelstetten

Sulfate SO3 [wt.-%] 0.44

Calcium CaO [wt.-%] 67.34

Potassium K2O [wt.-%] 0.36

Sodium Na2O [wt.-%] 0.03

Silicon SiO2 [wt.-%] 21.54

Iron Fe2O3 [wt.-%] 2.80

Aluminium Al O [wt %] 5 40

Mergelstetten

Aluminium Al2O3 [wt.-%] 5.40

Magnesium MgO [wt.-%] 0.96

Manganese Mn3O4 [ppm] 529

Chromium Cr2O3 [ppm] 127

Titanum TiO2 [ppm] 2959

Tin SnO [ppm] 26

Chlorine Cl [ppm] <NWG

Phosphorus P2O5 [ppm] 1880

L.O.I. (1050°C) [wt.-%] 0.38

Trocknungsverlust (120°C) [wt.-%] 0.28

Moduli:

Natriumequivalent 0.27

Kalkstandard (not relevant in cement) 98

Sulfatisierungsgrad (not relevant in cement) 127

Silicatmodul 2 63

Klinker Aug08 Mergelstetten

Silicatmodul 2.63Tonerdemodul 1.93

Summ Silicates 81.12ratio C3S/C2S 6.71Summ Aluminates 17.07ratio C3A/C4AF 1.41ratio Silicates/Aluminates 4.75