WO2006079875A1 - Improved microsilica, its application like pozzolanic material and methods for its obtaining - Google Patents
Improved microsilica, its application like pozzolanic material and methods for its obtaining Download PDFInfo
- Publication number
- WO2006079875A1 WO2006079875A1 PCT/IB2005/002161 IB2005002161W WO2006079875A1 WO 2006079875 A1 WO2006079875 A1 WO 2006079875A1 IB 2005002161 W IB2005002161 W IB 2005002161W WO 2006079875 A1 WO2006079875 A1 WO 2006079875A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- microsilica
- pozzolanic
- silica
- cristobalite
- cement
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 181
- 229910021487 silica fume Inorganic materials 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 248
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 57
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims description 34
- 230000000694 effects Effects 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 238000003801 milling Methods 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 68
- 239000004568 cement Substances 0.000 abstract description 54
- 239000004567 concrete Substances 0.000 abstract description 39
- 239000010453 quartz Substances 0.000 abstract description 35
- 235000012239 silicon dioxide Nutrition 0.000 description 35
- 239000011398 Portland cement Substances 0.000 description 27
- 230000008569 process Effects 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 13
- 239000000654 additive Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 7
- 239000000920 calcium hydroxide Substances 0.000 description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 229910021653 sulphate ion Inorganic materials 0.000 description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 6
- 235000011941 Tilia x europaea Nutrition 0.000 description 6
- 239000004571 lime Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000003993 interaction Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000002956 ash Substances 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- -1 calcium aluminate silicates Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000004574 high-performance concrete Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- UTPYTEWRMXITIN-YDWXAUTNSA-N 1-methyl-3-[(e)-[(3e)-3-(methylcarbamothioylhydrazinylidene)butan-2-ylidene]amino]thiourea Chemical compound CNC(=S)N\N=C(/C)\C(\C)=N\NC(=S)NC UTPYTEWRMXITIN-YDWXAUTNSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 208000020442 loss of weight Diseases 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical class [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920008716 Darex Polymers 0.000 description 1
- 229920002774 Maltodextrin Polymers 0.000 description 1
- 241001441728 Molidae Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 235000015076 Shorea robusta Nutrition 0.000 description 1
- 244000166071 Shorea robusta Species 0.000 description 1
- 229910020169 SiOa Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010316 high energy milling Methods 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052646 quartz group Inorganic materials 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
Definitions
- microsilica its application like pozzolanic material and methods for its obtaining.
- the actual invention is related to the field of the development of pozzolanic materials for construction, specifically to microsilicas that exhibit high pozzolanic indexes and methods for their obtaining.
- the Portland cement is one of the most important materials in the construction industry due to its multiple applications and its advisable physical and chemical characteristics that present. Nevertheless, the costs associated to their obtaining as well as the high amounts that they must be produced to cover the necessities of cement for construction, have been important factors for the generation of new materials that allow to replace part of the cement used for the manufacture of concrete or products derived from concrete, without causing a decrement in their mechanical properties and resistance.
- the pozzolans are siliceous or siliceous and aluminous materials which in itself possesses little or no cementitious value but will, in finely divided form and in the presence of moisture, chemically react with calcium hydroxide at ordinary temperature to form compounds possessing cementitious properties.
- the application of the pozzolans in concrete allows to increase its durability in function of the increase in its diverse properties, such as impermeability, resistance to sulphate attack, handling, mechanical resistance in advanced ages and reduction in the alkali aggregate reactivity among others; these generates minor cement consumptions and the obtaining of construction materials with better mechanical properties and durability.
- the synthetic pozzolans generated like byproducts from diverse industrial processes, have quickly become the primary source of artificial pozzolans used at the moment.
- the electrical power stations using rice husks or coal as fuel, and metallurgical furnaces producing iron, silicon and ferrosilicon alloys are the main source of artificial pozzolans like fly ashes, rice husk ash, blast furnace slag, silica fume, etc.
- the silica fume is manufactured by electric arc furnaces as a byproduct of the production of metallic silicon or ferrosilicon alloys.
- the gaseous SiO oxidizes to SiO 2 and condenses in the form of special fine particles consisting of amorphous silica.
- the silica fume is removed by filtration of salient gases in filter devices.
- the pozzolanic activity of the silica fume occurs substantially by the non-crystalline character of the silica and by its great specific superficial area (10 to 30 m 2 /g), that it depends on its particle size (lower than 1 ⁇ m). Nevertheless, the silica fume has a relatively low bulk density, so that the costs for their shipment and storage are relatively high. On the other hand, the silica fume form a great amount of dust and is difficult to make it flow; also it cannot be transferred into storage silos by pneumatic lines, bucket elevator or screen conveyor as easily as the cement can be.
- the natural pozzolans are crude or calcined natural materials that have pozzolanic characteristics.
- Some natural pozzolans include volcanic ashes, pumicites, opaline cherts and shales, tuffs and some diatomaceous earths.
- natural pozzolans vary considerably, depending on their origin. This is caused by variable proportions of the active materials and their mineralogical and physical characteristics. Most of the natural pozzolans contain important amounts of silica, alumina, iron oxide and alkaline agents, which also react with calcium hydroxide and alkalis (sodium and potassium) to form more complex compounds. The molecular structure as well as the amount of silica present in pozzolans is also very important. Generally, the amorphous silica reacts more quickly with calcium hydroxide and alkalis than does silica in the crystalline form (quartz, for example).
- the shape, fineness, particle size distribution, density, and composition of natural pozzolan particles influence in the characteristics of freshly mixed and hardened concrete, and the strength development of hardened concrete.
- any pozzolan when it is used in sufficient quantity is capable of preventing the excessive expansion resulting from the alkali-silica reaction.
- This reaction implies the interaction of hydroxyl ions associated with alkalis in Portland cement with certain siliceous components of the aggregates in concrete. The reaction products can cause excessive expansion, cracking, and the general deterioration of the concrete.
- the natural pozzolans are generally more effective than fly ashes to controlling the alkali-silica reaction.
- the use of natural pozzolans with Portland cement for the concrete obtaining generally increases its resistance to aggressive attack by seawater, to sulphate solutions from soil, and to natural acid waters. The relative improvement is greater for concrete with low cement content.
- the particle size is one of the most important; by this way those materials with very reduced particle sizes are distinguished, which are called microsilicas.
- the synthetic silicas the silica fume and natural silicas being these the most common in the market.
- the silica fume is recognized like the main ingredient for high performance concrete, nevertheless, presents some disadvantages, such as: A) The actual production is limited by smeltings of silica,
- the suitably processed natural microsilicas compete in quality with the silica fume at lower costs.
- the microsilica allow to improve the cement characteristics, contributing to the improvement of a greater abrasion resistance, greater resistance to the chemical attack and a very low diffusion of chlorine ions. This allows that the resulting cements can properly be used in adverse environments, such as soils with high humidity or high sulphate contents, or marine environments.
- silica mixtures with an ample distribution of different particle sizes 1 ' 2 , hydrofobic silicas obtained from silicone oil precipitation 3 , silica mixtures with CaC ⁇ 3 4 , colloidal silicas 5 ' 6 , silicas obtained like reaction products between bauxite and acids 7 , silica fume humidified dusts to improve their fluidity 8 , resulting silicas from the magnetic metal separation from rocky wastes 9 , synthetic microsilicas with high reflectivity 10 , stable watery dispersions of microsilica mixed with metal oxides 11 , microsilicas with bulk controlled densities 12 , microsilica dispersions that do not present thixotropic effect 13 , spherical silicas with specific diameters 14 , microsilicas mixed with chelating agents 15 or treated with acids 16 , as well as silicas with tertiary structures from
- the mentioned siliceous materials previously are obtained from processes that involve the addition of multiple substances that can provide negative or undesirable effects when making contact with the cement. Also, the processes for their obtaining tend to be complex and to use great amounts of energy and infrastructure, which can increase considerably their costs.
- Figure 1 Show a comparative graphic of density for raw (A) and calcined (B) silica samples from ignimbrite silica deposit.
- Figure 2. Show a comparative graphic of compressive strength (ASTM C-311) for , ignimbrite mixtures pairs from figure 1 with Portland cement, using Portland cement as witness (first column of each series) at 1 , 3, 7 and 28 days.
- Figure 3. Show a comparative graphic of pozzolanic index at 28 days for sample pairs of raw silica (A) and treated silica at 600-620°C (B) from figure 1.
- Figure 4. Show an X ray diffraction spectrum of the sample 1 from ignimbrite deposit of figure 1. Quartz crystalline phase can be distinguished (Q).
- Figure 5. Show an X ray diffraction spectrum of the sample 2 from the ignimbrite deposit from figure 1. It can be distinguished the crystalline phases of quartz (Q), cristobalite (C) and tridimite (T).
- Figure 6 Show an X ray diffraction spectrum of the sample 3 from the ignimbrite deposit from figure 1. It can be distinguished the crystalline phases of quartz
- Figure 7 Show an X ray diffraction spectrum of the sample 4 from the ignimbrite deposit from figure 1. It can be distinguished the crystalline phases of quartz
- FIG. 10 Show an X ray diffraction spectrum of the sample 8 from the ignimbrite deposit from figure 1. It can be distinguished the crystalline phases of quartz (Q), cristobalite (C) and tridimite (T).
- Figure 11 Show an X ray diffraction spectrum of the sample 10 from the ignimbrite deposit from figure 1. It can be distinguished the crystalline phases of quartz
- Figure 12 Show an X ray diffraction spectrum of a semi-quantitative determination of the sample 1 from the ignimbrite deposit from figure 1. It can be distinguished the crystalline phases of quartz (Q), cristobalite (C) and tridimite (T).
- Figure 13 Show an X ray diffraction spectrum of a semi-quantitative determination of the sample 2 from the ignimbrite deposit from figure 1. It can be distinguished the crystalline phases of quartz (Q), cristobalite (C) and tridimite (T).
- Figure 14 Show an X ray diffraction spectrum of a semi-quantitative determination of the sample 8 from the ignimbrite deposit from figure 1.
- FIG. 15 Show a comparative graphic of compressive strength (ATSM C-31 1) in concrete mixtures with the microsilica of the invention (series A to D) and silica fume (series E to G) at 3, 7 and 28 days, using Portland cement as witness (T). The used proportions of the materials were 5% (A and E), 10%
- Figure 16 Show a comparative graphic of flexion strength in concrete mixtures with the microsilica of the invention (series A to D) and silica fume (E to G) at 7 and ⁇ 28 days, using Portland cement as witness (T). The used proportions of the materials were 5% (A and E), 10% (B and F), 15% (C and G) y 20% (D).
- Figure 17. Show a comparative graphic of abrasion index in concrete mixtures with the microsilica of the invention (series A, C and E) and silica fume (series B, D and F) at 1 , 3, 7 and 28 days, using concrete 300 as witness (T). The values are expressed in material weight loss by cycle (g).
- Figure 18 Show a comparative graphic of chloride ion penetrability (ASTM C-1202) in concrete mixtures with the microsilica of the invention (series A) and silica fume (B), using Portland cement as witness (T). The low, very low and moderate permeability zones can be distinguished.
- FIG. 19 Show a comparative graphic of sulphate attack resistance (ATSM C-1012) in concrete mixtures with the microsilica of the invention (series A to C) and
- FIG. 21 Show a comparative graphic of resistance to attack by alkali aggregate reaction (ASTM C-1260) in concrete mixtures with the microsilica of the invention (Series A, D and E), silica fume (B series), flying ashes (C series) and low alkali Portland cement as witness (T series) at 16 days.
- the proportions of used materials were 10% (A and B), 15% (D), 20 (E) and 25% (C).
- Another one of the objectives of the present invention is to provide a simple and low consumption energy method for the obtaining of natural microsilicas composed mainly of cristobalite and tridimite with high pozzolanic indexes, from geologic deposits.
- the invention is based on the discovery that the best characteristics as pozzolanic material in the microsilica are directly related with the presence of greater percentage of cristobalite and tridimite in the silica (SiOa) of the material, in comparison with those silicas composed mainly by quartz. This allows to obtain microsilicas like improved pozzolanic materials that contains greater amounts of cristobalite and tridimite in the silica.
- the cristobalite and tridimite are quartz polymorphs, which means that they are composed of the same chemical elements (SiO 2 ), but they have a different crystalline structure. Within the polymorphic members of the quartz group, the coesite and the stishovite are also included, which appear depending of pressure and temperature conditions of which the quartz is exposed. Table 1 shows the different polymorphic modifications from the quartz. Table 1
- the cristobalite is only metastable at normal surface temperatures; meaning that, if it were possible, it would slowly convert to the quartz structure. But this is a slow and complicated process taking thousands of years if it happens at all. It is a slow process mostly because the transformation implies the breaking of bonds and the rearrangement of atoms.
- microsilicas that they contain above of 85% in weight of silica (SiO 2 ) has advisable pozzolanic activity for construction materials
- the microsilicas of the invention contain a greater pozzolanic activity in comparison with the microsilicas known actually.
- the microsilicas of the invention have a pozzolanic activity at least of 40% greater than the microsilicas composed only by quartz or which those in which the quartz is in an equal or greater percentage of 50% in weight with respect to the total weight of silica.
- the joint amount of cristobalite and tridimite are from 55 to 90% in weight with respect to the total weight of silica, preferably from 70 to 90% in weight.
- the crystal size of cristobalite and tridimite can be from 5 to 12 nm, preferably from 6 to 11 nm, with which these elements are criptocrystalline.
- microsilicas of the invention have smaller densities (from 5 to 10%) that those microsilicas composed by high amounts of quartz, which allows to reduce the material weight in similar volumes.
- the materials of the invention can increase their pozzolanic activity by calcination means and to react in an advisable way with cementitious materials to increase and to improve the physical characteristics of these.
- microsilicas of the invention have advisable particle sizes to mix themselves with cementitious materials, allowing an intimate interaction with the cementitious material, without need to use high energy milling processes to diminish more the particle size.
- the microsilicas of the invention generally have a particle size distribution equal or smaller to 40 ⁇ m at 98%, similar sizes than the reported for another type of microsilicas.
- the high percentages of cristobalite and tridimite in the pozzolanic material of the invention allow to increase the pozzolanic activity of the material without need to reduce even more their particle size.
- the greater percentages of cristobalite and tridimite in the microsilicas of the invention do not alter their physical properties like pozzolanic material to be used in cementitious materials, as well do not alter either the typical properties of the cementitious material with which they can be combined.
- the high percentages of cristobalite and tridimite allow to improve in a surprising way the pozzolanic characteristics of the microsilicas, without need to put the material under posterior chemical transformation processes or calcination at high temperatures.
- the pozzolanic index of the materials of the invention reaches greater values than 120% with respect to cement witness at 28 days in a consistent way, similar values than the values reached by highly processed microsilicas.
- the microsilica 600 an extracted product from a natural deposit of white geosilica found in New Zealand, contains an average percentage of SiO 2 of 87.9%, a pozzolanic index of 119% and a particle size of 20 ⁇ m at 97.9%. Also, the physical and chemical characteristics of the material place it like a high reactivity pozzolanic material, that allows to improve many of the cement characteristics. Nevertheless, for its obtaining, it is necessary to watch continuously the material milling process to obtain the mentioned particle sizes 18 . Unlike the mentioned above, the pozzolanic material of the present invention has pozzolanic indexes greater than 120% with a particle size of 40 ⁇ m at 98%, a greater particle size value than the mentioned previously.
- the pozzolanic indexes developed by the pozzolanic material depend of the crystalline composition of the silica. Due to this it is evident that when diminishing the particle size of material of the invention at levels of the microsilica 600, the pozzolanic properties of the material are even increased more due to the increase in the superficial exposed area of the material; this allows to a greater interaction and reactivity with the components of the cement.
- the microsilica of the invention can be obtained from materials with high silica, like for example from ignimbrite.
- the pozzolanic material described here is obtained in a general way by means of the following process: a) Obtaining the siliceous material from natural deposits, preferably from ignimbrite deposits, b) Selecting those parts of the deposit that contain SiO 2 in an equal or greater amounts than 85% in weight with respect to the total weight of the material, c) From the parts obtained in b), to select those that have a density smaller than 2.4 g/cm 3 , d) Crushing the parts obtained in c) until obtaining a particle size smaller than 1/2", e) Calcination of the obtained material previously, at 590 to 620 0 C, and f) Milling the calcined material until obtaining a mesh particle size of 325 at 96% like minimum.
- the method of the invention allows to obtain pozzolanic materials with a pozzolanic index equal or greater to 120%; nevertheless, eliminating calcination step of the process previously described, the obtained material develops pozzolanic indexes from 110 to 120%, which also can be used for certain applications than the pozzolanic material with a greater pozzolanic index.
- the pozzolanic activity of materials with high silica content can recover with a heat treatment at temperatures of 500 to 750 0 C and later milling of the material during a time of 30 to 60 minutes 19 .
- the process of the invention allows to obtain pozzolanic materials with high silica content and greater proportions of cristobalite and tridimita in the silica of the material, in comparison with other pozzolanic materials.
- the obtained pozzolanic material exhibits pozzolanic indexes at least of 40% greater than those pozzolanic materials that contain predominantly quartz in the silica, independently of the percentage of silica that contains the pozzolanic material.
- the existence of a greater proportion of cristobalite and tridimite in the pozzolanic material of the invention does not affect negatively the behavior of the material in common tests of resistance and durability of concrete and mortars, developing similar physical and chemical properties or inclusive better properties than the observed for other similar pozzolanic materials.
- the pozzolanic material of the invention can be obtained from the calcination and milling of raw materials such as the ignimbrite, this can be process with the same procedures and equipment used for the ordinary cement production (rotatory furnace and mill with separator, for example), allowing to use the common infrastructure that can be found in industrial plants for producing and processing cement.
- the pozzolanic material of the invention can be obtained with the common procedures to obtain cement, is desirable that the material is ground to obtaining a particle size smaller to 20 microns to increase even more the pozzolanic activity of the material of the invention.
- the particle size of the microsilica described here is greater than the observed for the silica fume or microsilica 600, the observed superficial area of the material (BET) is similar than the superficial area of microsiiica fume (see table 10); this characteristic was obtained in the microsilica of the invention without need to grind the material in excess.
- Eriksson describes the obtaining of a fine active aggregate like pozzolanic material that consists of a mixture of an inactive dry component like quartz or lime and a substance who contain abundant amorphous silicon oxide. This mixture is ground with the purpose of activating the inactive material so that this it reacts in an advisable way with the lime of the cement 20 . Nevertheless, this material involves the addition of elements that increase their costs of obtaining and which they can react in an undesirable way with other elements of the cement.
- cement additives that use siliceous materials to increase the cement chemical resistance are known.
- the cement additive described by Vsevolod 24 constituted by a mixture of finely divided quartz with a surface area from 1 ,000 to 5,000 cm 2 /g in a proportion in weight from 30 to 80%, and cristobalite and/or tridimite in a proportion in weight from 20 to 70%, allows to increase the cement water resistance in comparison with additives conformed solely by quartz.
- the process described for the obtaining of this additive involves the mixture of siliceous material with different catalysts, such as NaOH, KOH, NaCO 3 , KCO 3 or mixtures of such, with a subsequent heat treatment at very high temperature (1 ,000 to 1 ,550 0 C). Nevertheless, the mentioned additive does not increase in a consistent manner the cement compressive strength in all cases and not all of the mixture material conserve a homogenous particle size, since only the cristobalite and/or tridimite crystals have a particle size smaller to 1 mm, which can cause problems in its interaction with cement particles.
- catalysts such as NaOH, KOH, NaCO 3 , KCO 3 or mixtures of such
- the cristobalite and/or tridimite crystals contain in their surface important amounts of sodium or potassium oxides, characteristic that results of vital importance to observed the improvement effect in the cement; these important amounts of oxides can be negative for a better chemical interaction between the siliceous material and the cement components.
- the pozzolanic material of the invention not contains a significant amount of sodium and potassium oxides, the particle size is smaller to 1 mm in an homogenous way (crystals smaller to 20 nm) and, in addition, in all the cases increases the cement compressive strength at 28 days.
- the pozzolanic effect of the material of the invention is not associated to the alkaline metal oxide presence, but to the own characteristics of the material, mainly to cristobalite and tridimite content.
- the process of obtaining of the present invention allows to use much lower temperatures to process the pozzolanic material, and without need to use additional siliceous materials previously treated.
- the present invention demonstrates that the amount of cristobalite and tridimite that it is conforming the silica of the pozzolanic material, is determining for the increase in the pozzolanic properties of the material, reaching pozzolanic indexes greater to 120%, superior value to which develop well- known pozzolanic materials with percentage of silica near or even greater to 90%.
- the microsilica samples that contain only quartz or high proportions of the same have a poor performance in the pozzolanic indexes that they develop, in comparison with the microsilica of the invention.
- the addition of cristobalite and tridimite to high performance microsilicas as it is the case of the silica fume in the same proportions that they exists in the material of the invention, did not improve its pozzolanic properties.
- the microsilica of the invention does not have cementitious properties of union by itself. Nevertheless, it can react with the lime of the cement at room temperature in the presence of water, when it gets to form mixtures with the cement that is tried to improve.
- the concretes formed from cement mixtures and the pozzolanic material of the invention develop a very advisable impermeability as well as high compressive strengths, comparable to the developed by other pozzolanic materials, as for example silica fume.
- the material of the invention improves the cement abrasion indexes from 10 to 70% with respect to cements that use silica fume in the same proportions, and allows to diminish in a dramatic way the expansion caused by the sulphate attack in a 2,800% at 28 weeks.
- microsilica of the invention With the microsilica of the invention, significant improvements in all cement properties can be obtained using low proportions of this material in the cementitious mixtures, generally using at least 5% in weight of the material.
- the use of the material of the invention provides an important economic advantage in the generation of cement with improved properties, since it allows reductions in the used amount of Portland cement in the generated mixtures.
- the pozzolanic material of the invention can be used as substitute of the commercial silica fume as well as other pozzolanic materials in the production of high performance concretes.
- Example 1 Obtaining of raw material.
- Example 2 Obtaining of the pozzolanic material.
- Example 1 The material samples obtained in example 1 were transported from quarry to a cement processing plant. The samples were crushed later separately in a crushing jaw machine until obtaining a size smaller to 1/2" and later they were put under calcination at 590 to 62O 0 C in a rotatory furnace during 1 hr. Later, the resulting materials along with a milling additive as for example Darex or triethanolamine, were worn out separately in a ball mill with separator during 30 minutes until obtaining a mesh particle size of 325 at 96% as minimum. The treated materials were placed in containers or plastic bags until their use.
- Example 3 Determination of the pozzoianic material density.
- the density of the samples obtained in example 2 was determined using an Accupyc picnometer model 1330. The obtained results were compared with the density of the same samples but without calcination (crude samples). As it is observed in table 4 and in figure 1 , in all cases the density of the samples of the pozzoianic material subject to calcination at 61O 0 C, was greater than the density value of the corresponding sample without calcination; also substantial differences between the density values from different crude samples (from 2.23 to 2.59 g/cm 3 ) and calcined samples were observed (from 2.27 to 2.63 g/cm 3 ).
- Example 4 Pozzoianic index evaluation from pozzoianic material.
- the treated samples from pozzoianic material obtained in example 2 were evaluated in their pozzoianic index according to ASTM C-311 and compared their developed compressive strengths in cements with these materials and silica fume.
- This method establishes in a general way, that the pozzoianic material must be mixed with Portland cement in a relation in weight of 20:80 respectively and make compressive strength tests according to ASTM C-109 to this mixture, comparing the obtained results with the compressive strength of the Portland cement used like witness; the pozzoianic index of the proven material, turns out to divide the compressive strength mixture of this material by the compressive strength of the cement witness and to multiply it by 100.
- Diverse microsilica samples of the invention were mixed with Portland cement to measure the resulting compressive strength in buckets according to ASTM C-109, for which 20% in weight of Portland cement were replaced by the pozzolanic material under test.
- the obtained pozzolanic indexes for the materials of the invention are show in table 5 and figure 3.
- all the pozzolanic materials of the invention without calcination exhibited pozzolanic indexes from 86 to 115%, whereas for calcined materials the resulting pozzolanic indexes were from 88 to 123% (see figure 3).
- Example 5 X-ray diffraction from pozzoianic material.
- the samples of pozzoianic material of example 2 were analyzed by x-ray diffraction. As it can be observed in figures 4 to 11 , the samples with a density smaller to 2.4 g/cm 3 showed a substantially greater amount of cristobalite and tridimite than those samples that exhibited densities greater to 2.4 g/cm 3 , where the amounts of cristobalite and tridimite were minimum or not exist, appearing solely quartz crystals (see sample 1 and figure 4).
- the amount of cristobalite, tridimite and quartz was determined in 3 representative samples of the material extracted from the deposit, after obtaining the mentioned results previously, as well the crystallite size for each one of these crystalline phases.
- the samples with densities smaller to 2.4 g/cm 3 presented a percentage in weight of cristobalite and tridimite at least of 56% with respect to the total weight of silica and with a crystallite size equal or smaller to 12 nm.
- the sample with a density greater to 2.4 g/cm 3 exhibited a percentage in weight much greater of quartz than cristobalite and tridimite in the silica.
- the table 6 also shows some of the differences in the performance like pozzoianic material of these materials; as it can be observed, the samples with a percentage in weight greater or equal to 56% of cristobalite and tridimite in the silica of the material present the best performance. Table 6
- Example 6 Composition and particle size of the pozzolanic material of the invention.
- the pozzolanic material with a density smaller to 2.4 g/cm 3 was analyzed in its particle size and its chemical composition using conventional methods, after being processed at industrial level as it indicates the example 1.
- the obtained pozzolanic material has a particle size of 40 ⁇ m at 98% (see table 7), a percentage of silica near to 90% and a density of 2.33 g/cm 3 (see table 8). Also, the pozzolanic index of the material is greater to 120% (see table 9).
- Example 7 Preparation of mixtures with the pozzolanic material for resistance and durability tests.
- Example 8 Compressive strength of mixtures of cement and the microsilica of the invention.
- the pozzolanic material of example 6 was mixed with Portland cement in different proportions and compared with similar mixtures but with silica fume like comparison material according to ASTM C-192. As it can be observed in figure 15, the mixtures containing the material of the invention develop similar compressive strength values at 28 days to the obtained for mixtures containing silica fume in the same proportions. In anyone of the proportions of the material of the invention under test, superior values of compressive strength were obtained in reference to the sample witness.
- Example 9 Resistance to the flexion.
- the pozzolanic material of the invention was mixed with sand and Portland cement in diverse proportions to obtain concrete mortar mixtures according to ASTM C-192.
- the mixtures containing the pozzolanic material developed greater values of flexion resistance at 28 days in comparison with mixtures containing silica fume in the same proportions, as well as with a witness (see figure 16).
- the values of flexion resistance in mixtures with 5 to 15% of the pozzolanic material were very similar to each other.
- Example 10 Resistance to the abrasion.
- Example 11 Resistance to the chlorine ions penetration.
- a concrete mixture containing the pozzolanic material of the invention was prepared according to ASTM C-1202, in comparison with Portland cement and a mixture elaborated with silica fume.
- the tried samples developed the electrical charge values observed in figure 18.
- the mixture with the pozzolanic material developed a value near to 1 ,000 coulombs, which allows to classified the mixture with very low permeability; also, this value was near to the reached value of mixture with silica fume (near to 500 coulombs, very low permeability) and a 55% minor to the observed for the ordinary cement (with moderate permeability).
- Example 13 Potential resistance to alkali aggregate reactivity.
- Mortar mixtures with pozzolanic material were tried under conditions according to ASTM C-227. As it can be observed in figure 20, the mixtures with percentage from 10 to 20% of pozzolanic material conserved an expansion value smaller to 0.01% during the test, whereas the sample with 5% reached a value of 0.03% at 6 months. Nevertheless, all the previous values were 90% lower in all ages compared with the observed values for witness.
- Example 14 Resistance to attack by alkali aggregate reactivity with diverse pozzolanic materials.
- Example 15 Comparative physical and chemical characteristics of material of the invention.
- microsilica of the invention exhibits similar characteristics of performance to the high performance silica fume, but with superior pozzolanic indexes to this one. Also, the pozzolanic indexes of the material of the invention are superior to the observed for microsilica 600. Table 10
Abstract
Description
Claims
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CA002596302A CA2596302A1 (en) | 2005-01-31 | 2005-07-06 | Improved microsilica, its application like pozzolanic material and methods for its obtaining |
US10/599,441 US7537653B2 (en) | 2005-01-31 | 2005-07-06 | Microsilica materials with improved pozzolanic activity |
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MXPA05001211A MXPA05001211A (en) | 2005-01-31 | 2005-01-31 | Improved microsilica, its application like pozzolanic material and methods for its obtaining. |
MXPA/A/2005/001211 | 2005-01-31 |
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US (1) | US7537653B2 (en) |
CA (1) | CA2596302A1 (en) |
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WO (1) | WO2006079875A1 (en) |
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MXPA05003691A (en) | 2002-10-07 | 2005-11-17 | James Hardie Int Finance Bv | Durable medium-density fibre cement composite. |
US7998571B2 (en) | 2004-07-09 | 2011-08-16 | James Hardie Technology Limited | Composite cement article incorporating a powder coating and methods of making same |
NZ571874A (en) | 2006-04-12 | 2010-11-26 | Hardie James Technology Ltd | A surface sealed reinforced building element |
NZ584799A (en) * | 2007-10-02 | 2012-08-31 | Hardie James Technology Ltd | Cementitious formulations comprising silicon dioxide and calcium oxide |
US20100192474A1 (en) * | 2009-01-30 | 2010-08-05 | Lehigh University | Ultrahard stishovite nanoparticles and methods of manufacture |
US7792250B1 (en) | 2009-04-30 | 2010-09-07 | Halliburton Energy Services Inc. | Method of selecting a wellbore cement having desirable characteristics |
US20130239652A1 (en) * | 2009-12-18 | 2013-09-19 | Varel Europe S.A.S | Variable frequency impact test |
US8887806B2 (en) | 2011-05-26 | 2014-11-18 | Halliburton Energy Services, Inc. | Method for quantifying cement blend components |
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US7537653B2 (en) | 2009-05-26 |
US20070209554A1 (en) | 2007-09-13 |
CA2596302A1 (en) | 2006-08-03 |
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