Industrial minerals in the spotlight:
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1 : optimizing their environmental performance for sustainable development Luca Valentini Università di Padova GNM school physical properties of minerals Bressanone/Brixen, Feb 2018
2 SOME DEFINITIONS MINERAL A mineral substance is defined as a naturally occurring, homogeneous solid, inorganically formed, with a well defined chemical composition (or range of compositions), and an ordered atomic arrangement, that has been formed by geological processes, either on Earth or in extraterrestrial bodies (Mineralogical Society of America)
3 SOME DEFINITIONS NATURAL vs. NON-NATURAL, SYNTHETIC, MAN-MADE (WHAT ELSE?)
4 SOME DEFINITIONS NATURAL vs. NON-NATURAL, SYNTHETIC, MAN-MADE (WHAT ELSE?) not involving anything made or done by people
5 SOME DEFINITIONS NATURAL vs. NON-NATURAL, SYNTHETIC, MAN-MADE (WHAT ELSE?) no chemical substances added and therefore thought to be healthy UNHEALTHY CRUDE OIL (geological/no chemicals added) WTF? WINE (man-induced chemical reactions) HEALTHY
6 SOME DEFINITIONS MINERAL A mineral substance is defined as a naturally occurring, homogeneous solid, inorganically formed, with a well defined chemical composition (or range of compositions), and an ordered atomic arrangement, that has been formed by geological processes, either on Earth or in extraterrestrial bodies (Mineralogical Society of America)
7 SOME DEFINITIONS NATURAL vs. NON-NATURAL, SYNTHETIC, MAN-MADE (WHAT ELSE?)
8 INDUSTRIAL MINERAL SOME DEFINITIONS A geological material obtained by mining (in its broadest sense) which represents a non-metallic, non-fuel raw material of commercial value (An Introduction to Industrial Minerals)
9 EXAMPLES OF INDUSTRIAL MINERALS Some metal ores are also used as industrial minerals Rutile (TiO 2 ) Extraction of Ti and use as Ti-oxide TioCem Chromite (FeCr 2 O 4 ) Extraction of Cr and use as Cr-oxide
10 EXAMPLES OF INDUSTRIAL MINERALS Industrial minerals may be obtained as by-products of ore mining Galena (PbS) Baryte (BaSO 4 ) Sfalerite (ZnS) Fluorite (CaF 2 )
11 EXAMPLES OF INDUSTRIAL MINERALS Asbestos Baryte Calcite Clays Corundum Diamond Dolomite Feldspar Graphite Gypsum Magnesite Mica Quartz Talc Zeolite Zircon
12 EXAMPLES OF INDUSTRIAL MINERALS Clay minerals distribution in soils CAOLINITE ILLITE SMECTITE Worldwide kaolinite production (USGS, 2017) 37,000,000 T
13 EXAMPLES OF INDUSTRIAL MINERALS Clay distribution in marine sediments
14 EXAMPLES OF INDUSTRIAL MINERALS Worldwide limestone production (USGS, 2017) 350,000,000 T
15 Properties of materials made from industrial minerals
16 BULK PROPERTIES Microstructural features Microstructure = set of spatial and geometrical relationships among the different phases present in a heterogeneous material A heterogeneous material is made of domains of different phases, or of a single phase in different states of aggregation Colloids Gels Foams Emulsions Soils Earth s crust Bones Blood TYNDALL EFFECT Solution Colloid
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18 BULK PROPERTIES Microstructural features: optical methods Optical scan of concrete microstructure
19 BULK PROPERTIES Microstructural features: optical methods Optical micrograph of clinker microstructure
20 BULK PROPERTIES Microstructural features: electron microscopy SEM-BSE image of cement powder
21 ANGULAR POSITION ATTENUATION BULK PROPERTIES Microstructural features: X-ray tomography n th raw of pixels RADIOGRAPH x x
22 BULK PROPERTIES Microstructural features: X-ray tomography
23 BULK PROPERTIES micropores Porosity mesopores macropores 2 nm 50 nm GAS ADSORPTION MIP TOMOGRAPHIC METHODS
24 BULK PROPERTIES Porosity: Mercury Intrusion Prorosimetry D = 4γcosθ/P
25 BULK PROPERTIES Porosity: Mercury Intrusion Prorosimetry
26 BULK PROPERTIES Relationship between microstructure and mechanical properties
27 Gallery of 3D rendered Tomographic images
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36 SURFACE PROPERTIES
37 SURFACE PROPERTIES SURFACE FREE ENERGY dg = SdT + VdP + μ i dn i + σ k da k i k Surfaces behave differently compared to the bulk!
38 SURFACE PROPERTIES Surfaces behave differently compared to the bulk!
39 SURFACE PROPERTIES Surfaces behave differently compared to the bulk!
40 SURFACE PROPERTIES Residual surface charge H 2 O adsorption (wetting) Surface protonation Surfaces behave differently compared to the bulk!
41 CONFOCAL MICROSCOPY SURFACE PROPERTIES Observing surfaces ATOMIC FORCE MICROSCOPY
42 SURFACE PROPERTIES Surfaces are where things happen
43 SURFACE PROPERTIES Surface of NaCl crystal after partial dissolution
44 SURFACE PROPERTIES link to video: Surfaces are where things happen
45 SURFACE PROPERTIES Adsorption is the attachment of species in solution at the interface with a pre-existing solid surface, without formation of a new crystal structure fractional coverage Θ = number of occupied adsorption sites number of available adsorption sites
46 SURFACE PROPERTIES The specific surface area can be measured by controlled adsorption of N 2 (or other gas phases as Ar, Kr, CO 2 ) V Monolayer volume calculated based on BET theory (Brunauer-Emmer-Teller) p/p 0
47 SURFACE PROPERTIES Activated carbon 1 mm
48 SURFACE PROPERTIES Electrical double layer Electrostatic interaction (long range) Electrostatic interaction Covalent bonding
49 SURFACE PROPERTIES Electrical double layer The electric potential of the double layer is defined zeta potential (z)
50 SURFACE PROPERTIES Electrical double layer ζ potential[mv] Colloidal stability 0 to ±5 Rapid coagulation or flocculation ±10 to ±30 Incipient instability ±30 to ±40 Moderate stability ±40 to ±60 Good stability > ±61 Excellent stability
51 SURFACE PROPERTIES Zeta-potential measurement: dynamic light scattering SPECKLE PATTERN The intensity fluctuation is proportional to the electrophoretic mobility within an applied electric field: U = f(ζ, ε, η)
52 Portland cement and other binders
53 ORDINARY PORTLAND CEMENT (OPC) RAW MATERIALS: LIMESTONE + CLAY + GYPSUM 1450 C CLINKER MINERALOGY C 3 S Ca 3 SiO 5 Alite C 2 S Ca 2 SiO 4 Belite C 3 A Ca 3 Al 2 O 6 Aluminate C 4 AF Ca 4 Al 2 Fe 2 O 10 Ferrite C = CaO A = Al2O3 F = Fe2O3 S = SiO2 S = SO3
54 PORTLAND CEMENT CEMENT HYDRATION MIXING WORKABLE PASTE SET HARDENING MAIN HYDRATION PRODUCTS C-S-H (CaO) 1.7 (SiO 2 )(H 2 O) 4 Silicato di calcio idrato CH Ca(OH) 2 Portlandite C 3 ASH 32 Ca 6 Al 2 (SO 4 ) 3 (OH) 12 26H 2 O Ettringite C = CaO A = Al2O3 F = Fe2O3 S = SiO2 S = SO3
55 PORTLAND CEMENT OPC Hydration Ca 3 SiO H 2 O (CaO) 1.7 (SiO 2 ) 4H 2 O Ca(OH) 2 Hydraulic binder! Slaked lime Ca(OH) 2 + CO 2 CaCO 3 + H 2 O Non-Hydraulic Roman (pozzolanic) cement x Ca(OH) 2 + y SiO 2(am) + z H 2 O (CaO) x (SiO 2 ) y zh 2 O
56 ROMAN CEMENT Caesarea Maritima (Israel)
57 ROMAN CEMENT Alcantara bridge (Spain)
58 ROMAN CEMENT Alcantara bridge (Spain) Ponte Pietra (Italy)
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60 PORTLAND CEMENT C-S-H: CEMENT HYDRATION PRODUCT SEM AFM
61 PORTLAND CEMENT CEMENT HYDRATION PRODUCT: PORTLANDITE
62 PORTLAND CEMENT CEMENT HYDRATION PRODUCT: ETTRINGITE
63 CEMENT POROSITY micropores mesopores macropores 2 nm 50 nm GAS ADSORPTION MIP TOMOGRAPHIC METHODS
64 CEMENT POROSITY Air voids
65 CEMENT POROSITY Air voids Size distribution by tomographic imaging Freeze-thaw degradation
66 CEMENT POROSITY Modulating the pore network tortuosity by the use of nano-seeds
67 CEMENT POROSITY Modulating the pore network tortuosity by the use of nano-seeds
68 CEMENT POROSITY Modulating the pore network tortuosity by the use of nano-seeds
69 CEMENT POROSITY Modulating the pore network tortuosity by the use of nano-seeds
70 CEMENT WORKABILITY
71 CEMENT WORKABILITY
72 CEMENT WORKABILITY
73 CEMENT WORKABILITY Link to video:
74 CEMENT WORKABILITY Controlling cement workability by adsorbed organic macromolecules Carboxylic acid (COOH) COO- Polyethylene glycol (C 2 H 6 O 2 ) PEG
75 CEMENT WORKABILITY Controlling cement workability by adsorbed organic macromolecules CLINKER SURFACE (NEGATIVELY CHARGED) Ca CATION Steric hindrance suppresses flocculation
76 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT 5% 7% GLOBAL ANTHROPOGENIC EMISSIONS
77 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT
78 United Nations Human Settlements Programme
79 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT
80 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT
81 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT Currently one billion people are living in slums
82 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT
83 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT
84 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT CaCO 3 CaO + CO 2 Al 2 Si 2 O 5 (OH) 4 Al 2 Si 2 O 7 + 2H 2 O
85 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT CLAY MINERALS CONCENTRATION IN SOILS GDP GROWTH (DATA FROM IMF)
86 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT
87 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT
88 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT Thermal activation of smectite clay BASAL REFLECTIONS TRIOCTAHEDRAL CONTRIBUTION DIOCTAHEDRAL CONTRIBUTION RAW CLAY 750 C * NEWLY FORMED PHASE 850 C
89 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT Thermal activation of smectite clay DTA-TG ANALYSIS 29 Si{ 1 H} CP/MAS NMR
90 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT Alkali activation of calcined clays Common alkaline activators: Sodium hydroxide Sodium silicate Sodium carbonate ph
91 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT Reaction product of alkali-activated blend of calcined smectite and waste marble slurry
92 BUILDING MATERIALS AND SUSTAINABLE DEVELOPMENT Reaction product of alkali-activated blend of calcined smectite and waste marble slurry
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