WO2017105961A1 - Ciment hybride à base de magnésium et son procédé de fabrication - Google Patents

Ciment hybride à base de magnésium et son procédé de fabrication Download PDF

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WO2017105961A1
WO2017105961A1 PCT/US2016/065372 US2016065372W WO2017105961A1 WO 2017105961 A1 WO2017105961 A1 WO 2017105961A1 US 2016065372 W US2016065372 W US 2016065372W WO 2017105961 A1 WO2017105961 A1 WO 2017105961A1
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Prior art keywords
magnesium
composition
containing material
hybrid
oxide
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Hwai-Chung Wu
Kraig WARNEMUENDE
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Wayne State University
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Wayne State University
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Priority claimed from US14/968,214 external-priority patent/US10150700B2/en
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B9/00—Magnesium cements or similar cements
    • C04B9/20—Manufacture, e.g. preparing the batches
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/10—Lime cements or magnesium oxide cements
    • C04B28/105—Magnesium oxide or magnesium carbonate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B9/00—Magnesium cements or similar cements
    • C04B9/11—Mixtures thereof with other inorganic cementitious materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • This application relates to a hybrid magnesium cement and a method of manufacture of same.
  • Portland cement has been used in concrete for nearly two centuries. But, Portland cement generally requires energy -intensive production facilities sufficient to process limestone at 2,000 °F in mammoth kilns. About one pound of carbon dioxide is released to the atmosphere for every pound of Portland cement produced. While Portland cement is used in many concrete structures, Portland cement also contributes significantly to decay of installed infrastructure as Portland cement deteriorates, especially due to attack from chloride ions.
  • Magnesium cement is suitable as a substitute for Portland cement.
  • magnesium cements are derived from magnesium oxide and are therefore relatively costly and relatively complicated products.
  • Marketed products involving magnesium cement are primarily limited to the interior wall applications, such as magnesium oxychloride cement boards.
  • Magnesium oxychloride cement experiences a strength loss when wet as a result of leaching of magnesium chloride and other chloride components.
  • Another magnesium cement, magnesium oxysulfate cement also loses strength when wet because it still has a relatively significant magnesium chloride component. Such strength reduction is a major obstacle to other structural uses of magnesium cement.
  • Other magnesium cements provide high performance, but have limited raw material supplies, cannot be wet-cured, and are otherwise ten-fold more expensive than Portland cement.
  • a more sustainable material is needed to replace Portland cement, especially a material has superior mechanical properties and duty life, especially in wet duty service, while being reasonably priced.
  • a hybrid magnesium cement composition comprising a mixture of a first composition and a second composition.
  • the first composition comprises a first component including a magnesium-containing material and a second component including a salt having a non-metallic oxide anion.
  • the first composition is partially cured (e.g.) by reacting with water.
  • the second composition includes a metal silicate polymer which is also partially cured (e.g, by reacting with water).
  • the hybrid magnesium cement composition is formed by combining the first composition with the second composition.
  • the hybrid magnesium cement composition includes inorganic polymer chains having at least 60 units of a silicon phosphate (e.g., S1P 2 O 7 ).
  • a hybrid magnesium cement composition is formed of an A-side having an Al -component including a light-burn grade magnesium- containing material, and an A2-component including a salt having a non-metallic oxide anion.
  • a B-side having a metal silicate polymer is included.
  • a magnesium-containing material composition in another embodiment, includes calcium carbonate, calcium oxide, magnesium carbonate, and magnesium oxide.
  • the magnesium-containing material composition includes inorganic polymer chains having at least 60 repeat units of SiP 2 0 7 .
  • a method of manufacture of a hybrid magnesium cement composition includes calcining a magnesium-containing material at a temperature in a range of 770 °C to 1, 100 °C for a time period ranging from 0.2 hr to 2.5 hr to form a light- burn grade magnesium-containing material (LGBM).
  • the method also includes mixing the LGBM with a non-metallic oxide salt to form a magnesium-oxide-non-metallic oxide salt (MONMO) inorganic polymer.
  • a non-metallic oxide salt is a salt having a non-metallic oxide anion.
  • the MONMO is mixed with a metal silicate polymer to form a dry hybrid magnesium-containing composition.
  • a light-burn grade magnesium-containing material (LGBM) composition includes calcium carbonate present in the range of 0 wt.% to 70 wt.% of the LGBM, calcium oxide in an amount less than 10 wt.% of the LGBM, magnesium carbonate in an amount less than 25 wt.% of the LGBM, and magnesium oxide present in an amount ranging from 18 wt.% to 70 wt.% of the LGBM.
  • the composition totals 100 wt.% of the LGBM, excluding other components.
  • LGBM light-burn grade magnesium- containing material
  • a light-burn grade magnesium- containing material (LGBM) composition includes calcium carbonate present in the range of 30 wt.%) to 70 wt.%) of the LGBM, calcium oxide in an amount less than 10 wt.%> of the LGBM, magnesium carbonate in an amount less than 25 wt.%> of the LGBM, and magnesium oxide present in an amount ranging from 18 wt.%> to 70 wt.%> of the LGBM.
  • a method of manufacture of a hybrid magnesium cement composition includes steps of calcining a magnesium- containing material at a temperature in a range of 770 °C to 1, 100 °C for a first time period, mixing the magnesium-containing material with a first salt to form a magnesium oxide- containing inorganic polymer composition, partially curing the magnesium oxide-containing inorganic polymer composition, and mixing the magnesium oxide-containing inorganic polymer with a metal silicate polymer to form a hybrid magnesium-containing composition.
  • the hybrid magnesium cement composition includes inorganic polymer chains having at least 60 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ).
  • FIGURE 1 graphically illustrates a time versus temperature graph of calcining of magnesium-containing materials according to at least one embodiment
  • FIGURE 2 diagrammatically illustrates a method of making a hybrid magnesium- containing cement according to at least one embodiment
  • FIGURE 3 provides plots of ultimate strain for the samples of Table 5.
  • FIGURE 4 shows the 29 Si magic-angle spinning (MAS) spectra acquired for a regular Portland cement (OPC) mortar and the ductile cement mortar (inorganic cement) of an embodiment of the present invention.
  • a hybrid magnesium cement composition comprising a mixture of a first composition and a second composition.
  • the first composition includes a first component including a magnesium-containing material and a second component including a salt having a non-metallic oxide anion.
  • salts include, but are not limited to, phosphate salts, sulfate salts, chlorate salts, or nitrate salts.
  • magnesium-containing material include, but are not limited to, dolomite, magnesite, and the like.
  • the first composition is partially cured by reacting with water.
  • the second composition includes a metal silicate polymer and is partially cured by reacting with water.
  • the hybrid magnesium cement composition is formed by combining the first composition with the second composition.
  • the hybrid magnesium cement composition includes inorganic polymer chains having at least 60 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ). In a variation, the hybrid magnesium cement composition includes inorganic polymer chains having from about 60 to 1000 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ). In a variation, the hybrid magnesium cement composition includes inorganic polymer chains having from about 60 to 120 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ). In another variation, the hybrid magnesium cement composition includes inorganic polymer chains having from about 80 to 100 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ).
  • a hybrid magnesium cement in at least one embodiment, is formed by mixing a Part A: a magnesium-containing material that includes magnesium oxide with a Part B: a metal silicate polymer. Before mixing to form the hybrid magnesium cement, the magnesium-containing material and the metal silicate polymer are each partially reacted separately, forming a partially-cured magnesium-containing material and a partially-cured metal silicate polymer.
  • Part A is a mixture of a Part Al : a light-burn grade magnesium- containing material, and a Part A2: a non-metallic oxide salt.
  • the term "light burn grade magnesium-containing material” is a magnesium-containing material or composition that has been calcined at temperatures ranging from 700°C - 1100°C.
  • a time versus weight loss graph is shown of calcining of the magnesium-containing material according to at least one embodiment.
  • a dolomite is the magnesium-containing material.
  • At line 10 is the weight loss trace of calcining the dolomite at 900 °C.
  • the weight loss equivalent to the stoichiometric amount of carbon dioxide from the decomposition of magnesium carbonate in the dolomite to magnesium oxide is reached in approximately 45 minutes.
  • At line 12 is the weight loss trace of calcining the dolomite at 850 °C. The loss of the stoichiometric amount of carbon dioxide from the decomposition of magnesium carbonate in the dolomite to magnesium oxide is reached in approximately 1 15 minutes.
  • At line 16 is the weight loss trace of calcining the dolomite at 750 °C. The loss of the stoichiometric amount of carbon dioxide from the decomposition of magnesium carbonate in the dolomite to magnesium oxide is not achieved.
  • At line 18 is the weight loss trace of calcining the dolomite at 600 °C. The loss of the stoichiometric amount of carbon dioxide from the decomposition of magnesium carbonate in the dolomite to magnesium oxide is never achieved.
  • the light-burn grade magnesium-material has a composition as shown in Table 1 A, where the composition accumulates to 100%.
  • the light-burn grade magnesium-material has a composition as shown in Table IB, where the composition accumulates to 100%.
  • the light-burn grade magnesium-material has a composition as shown in Table 1C, where the composition accumulates to 100%.
  • the weight ratio in the light-burn grade magnesium-containing material of MgC0 3 to MgO ranges from 0 to 0.71. In another embodiment, the weight ratio of the light-burn grade magnesium-containing material MgC0 3 to MgO ranges from 0.01 to 0.55. In yet another embodiment, the weight ratio of the light- burn grade magnesium-containing material MgC0 3 to MgO ranges from 0.05 to 0.20.
  • essentially all MgC0 3 in the raw material is transformed by calcining into MgO as measured by weight between the initial dried material and the after-calcining, cooled dried material.
  • in forming light-burn grade magnesium- containing material essentially all MgC0 3 in the raw material is transformed by calcining into MgO and essentially none of the CaC0 3 in the raw material is converted into CaO.
  • in forming light-burn grade magnesium-containing material essentially all MgC0 3 in the raw material is transformed by calcining into MgO and less than 20 rel.% of the CaC0 3 in the raw material is converted into CaO.
  • in forming light-burn grade magnesium-containing material essentially all MgC0 3 in the raw material is transformed by calcining into MgO and less than 10 rel.% of the CaC0 3 in the raw material is converted into CaO. In another embodiment, in forming light-burn grade magnesium- containing material at least 80 rel.% of MgC0 3 in the raw material is transformed by calcining into MgO and less than 20 rel.% of the CaC0 3 in the raw material is converted into CaO. In another embodiment, in forming light-burn grade magnesium-containing material at least 90 rel.% of MgC0 3 in the raw material is transformed by calcining into MgO and less than 20 rel.% of the CaC0 3 in the raw material is converted into CaO.
  • the magnesium-containing material is the dolomite that is calcined to form a light-burn grade dolomite.
  • the light-burn grade dolomite is calcined at temperature for a time period ranging from 0.2 hours to 2.5 hours.
  • the light-burn grade dolomite is calcined at temperature for a time period ranging from 0.5 hours to 2 hours.
  • the light-burn grade dolomite is calcined at temperature for a time period ranging from 0.75 hours to 1.5 hours.
  • the magnesium-containing material in at least one embodiment, is the light- burn grade dolomite formed by calcining a dolomite at a temperature ranging from 770°C to 1, 100°C.
  • the light-burn grade dolomite is formed by calcining the dolomite at a temperature ranging from 800°C to 950°C.
  • the light-burn grade dolomite is formed by calcining the dolomite at a temperature ranging from 850°C to 900°C. It was surprising that an exceptionally and unacceptably violent reaction occurs when the light-burn grade dolomite is calcined at temperatures at or above 1,100°C and subsequently mixed with a non-metallic oxide salt.
  • the mixture of light-burn grade dolomite with the non-metallic oxide salt forms a magnesium-oxide-non-metallic oxide salt inorganic polymer (MO MO).
  • non-metallic oxide salt refers to the anion part of the salt.
  • MO MO is reactable with the metal silicate polymer to form the hybrid cement in certain embodiments.
  • the non-metallic oxide salt is a sulfate salt. In another embodiment, the non-metallic oxide salt is a phosphate salt. In at least one embodiment, the phosphate salt is a soluble phosphate. In another embodiment, the phosphate is a crystalline phosphate. Non-limiting examples of the phosphate salt include metal dihydrogen phosphate, dimetal hydrogen phosphate, metal phosphate, where the metal is a monovalent metal cation, such as potassium. In another embodiment, the phosphate salt may include phosphate compositions having ammonium, alkaline earth, and/or di- and/or trivalent metal cations.
  • the weight ratio of the non-metallic oxide salt to the magnesium oxide in the light-burned grade dolomite ranges from 0.1 to 1.2. In another embodiment, the weight ratio of the non-metallic oxide salt to the magnesium oxide in the light-burned grade dolomite ranges from 0.3 to 1.1. In yet another embodiment, the weight ratio of the non-metallic oxide salt to the magnesium oxide in the light-burned grade dolomite ranges from 0.5 to 0.95. It is unexpected that the weight ratio of non-metallic oxide salt to magnesium oxide is significantly different from the stoichiometric ratio. Without being tied to any one theory, this unexpected result may arise from the broad distribution of particles sizes of the light-burn grade dolomite, where the large particle sizes do not receive all of the reactants during the relative short reaction time period.
  • the particle size may contribute to the magnesium-containing material's effectiveness in the hybrid cement.
  • the particle size distribution of the dolomite in at least one embodiment, has more than 85 wt.% being less than a Tyler Equivalent 100-mesh screen and less than 15 wt.% being less than a 4.8 ⁇ particle size when measured according to ASTM D422-07.
  • the particle size distribution of the dolomite has a particle size distribution with more than 90 wt.% being less than a Tyler Equivalent 100-mesh screen and less than 15 wt.% being less than a 15.8 ⁇ particle size.
  • particle size distribution of the dolomite has a particle size distribution with more than 95 wt.% being less than a Tyler Equivalent 100-mesh screen and less than 15 wt.% being less than a 36.2 ⁇ particle size.
  • the light-burn grade dolomite experiences a weight loss ranging from 23-28 dry weight percentage relative to an uncalcined dolomite. In another embodiment, the light-burn grade dolomite experiences a weight loss ranging from 24-27 dry weight percentage relative to an uncalcined dolomite. In yet another embodiment, the light-burn grade dolomite experiences a weight loss ranging from 25-26 dry weight percentage relative to an uncalcined dolomite. It is preferable that the weight loss measured be weight lost from magnesium- containing materials releasing carbon dioxide while forming magnesium oxide.
  • the carbon dioxide amount released from magnesium-containing materials ranges from 60 wt.% of the total weight loss to 95 wt.% of the total weight loss. In another embodiment, the carbon dioxide amount released from magnesium-containing materials ranges from 70 wt.% of the total weight loss to 90 wt.% of the total weight loss. In another embodiment, the carbon dioxide amount released from magnesium-containing materials ranges from 75 wt.% of the total weight loss to 85 wt.% of the total weight loss. In another embodiment, the carbon dioxide amount released from magnesium- containing materials ranges from 70 wt.% to 120 wt.% of the stoichiometric maximum weight loss of magnesium carbonate.
  • a dolomite blend includes 51 wt.%) calcium carbonate (CaC0 3 ) and 42 wt.%> magnesium carbonate (MgC0 3 ).
  • the molar mass of CaC0 3 is 100 g and CaO is 56 g.
  • the molar mass of MgC0 3 is 84.5 g and MgO is 40 g.
  • the dolomite magnesium theoretically decomposes only MgC0 3 to only MgO, the sample would weigh 40/84.5 of the original amount 47.3% of the original MgC0 3 mass or 19.9 g MgO.
  • the resultant weight of light-burn grade dolomite is, therefore, only (51+19.9)/(51+42) or 76% of the original weight. Stated as the stoichiometric loss of carbon dioxide, i.e. 100 wt.%-76 wt.%, that is 24 wt.% loss.
  • the carbon dioxide amount released from magnesium-containing materials ranges from 80 wt.%) to 110 wt.%) of the stoichiometric maximum mass loss of magnesium carbonate. In another embodiment, the carbon dioxide amount released from magnesium-containing materials ranges from 90 wt.% to 105 wt.% of the stoichiometric maximum mass loss of magnesium carbonate.
  • Calcining of the dolomite may occur using heating techniques known in the art.
  • Heating techniques include a static oven method, a static oven method with preheating, a calciner method, a calciner process with preheating, a dielectrically-heated method, and a microwave-heated method.
  • magnesium-containing minerals are suitable for use in certain other embodiments without exceeding the scope and limitations of the contemplated invention.
  • Non-limiting examples of other magnesium-containing materials include magnesite, pyroxenite, amphibolite, serpentine, dunite, and chlorite.
  • the reaction of the calcium oxide with the metal silicate polymer can be hazardously exothermic.
  • the excess calcium oxide can be retarded with a preliminary addition of water to form a hydrated lime (Ca(OH) 2 ) prior to mixing with the metal silicate polymer.
  • the magnesium-containing material has chloride present in a maximum amount of 10 wt.% chloride content. In another embodiment, the magnesium-containing material has chloride present in a maximum amount of 5 wt.% chloride content. In another embodiment, the magnesium-containing material has chloride present in a maximum amount of 2 wt.%.
  • the magnesium-containing material may be retarded using a set retarder such as boric acid or borax.
  • the retarded magnesium-containing material may be also un-retarded by addition of materials to neutralize or sequester the boron-containing compounds.
  • a dolomite cement mortar is formed from the light-burn grade dolomite, phosphate salt, a first latent hydraulic additive, a second latent hydraulic additive, water, and sand.
  • the dolomite cement mortar is reacted with the metal silicate polymer to form the hybrid cement in at least one embodiment.
  • the dolomite cement mortar composition in at least one embodiment, includes the formulation in Table 2, as follows, where the composition totals 100 wt.%: Table 2
  • the reaction of the magnesium-containing material with the metal silicate is too rapid for good mixing.
  • the rapid reaction results in damage to the molds, relatively poor workability, relatively low hardened strength, and relatively large granularity of the dolomite cement mortar.
  • the addition of the GGBFS to the magnesium-containing material results in a relatively slower reaction rate, in at least one embodiment.
  • having the GGBFS in the composition lowers the heat of hydration and lower temperature increases during the mixing of the dolomite cement mortar in certain embodiments.
  • GGBFS in certain embodiments, also reduces the occurrence of microcracking in the dolomite cement mortar because of reduced thermal gradients during the curing of the dolomite cement mortar.
  • the metal silicate polymer is formed by an inorganic polymerization reaction at the nano-structure condition in a gelled state using a relatively low temperature regime of less than 100 °C. Such a condition leads to formation of longer inorganic chains and loosely cross-linked chains in acidic regimes with elevated reagent concentrations. Rings, cluster networks, and cages are included in the basic regimes with relatively low reagent concentrations.
  • a silica-containing compound is reacted with a hydroxide anion using a water glass reaction at relatively high reagent concentrations in a very basic pH regime defined by 3.7 wt. % anhydrous sodium hydroxide anion to form an aluminum silicate inorganic polymer.
  • the silica-containing compounds include silicates known in the art to be wastes without many current use applications.
  • Non-limiting examples of silicate-containing compounds include a municipal incineration ash, a biomass ash, a silicate glass, a ground glass, mine tailings, and mixtures thereof.
  • Non-limiting examples of biomass ash include ash from combustion of rice, husks, straw, algae, or switchgrass.
  • Non-limiting examples of the silicate glass include sodium silicate, fly ash, class C fly ash, class F fly ash, silica fume, high-reactivity metakaolin, blast furnace slag, and bottom ash, especially bottom ash ground to an average particle size ranging from less than 100 Tyler mesh to 4.8 ⁇ .
  • the unexpected ability to use bottom ash is advantageous despite its relative inertness, especially because of the large amount of essentially unusable bottom ash waste material that is available.
  • the hydroxide anion is present in an amount ranging from 7 weight percent in solution to a saturated hydroxide anion solution.
  • hydroxide anion include sodium hydroxide anion, ammonium hydroxide anion, magnesium hydroxide anion and calcium hydroxide anion, preferably calcium hydroxide formed by hydration of calcium oxide in the magnesium-containing material.
  • Use of calcium oxide or hydroxide anion from the magnesium-containing material is unexpectedly advantageous in reducing cost and the use of low-value materials in forming the metal silicate polymer when the polymer is combined with the magnesium-containing material.
  • calcium oxide in the light-burn grade dolomite is present at less than 5 wt.% of the light-burn grade dolomite. In another embodiment, calcium oxide in the light-burn grade dolomite is present at less than 9.5 wt.% of the light-burn grade dolomite. In at least one embodiment, the metal silicate polymer is present in an amount ranging from 65 wt.% to 97 wt.% of the metal silicate polymer composition.
  • the metal silicate polymer is present in an amount ranging from 75 wt.% to 93 wt.%) of the metal silicate polymer composition. In yet another embodiment, the metal silicate polymer is present in an amount ranging from 80 wt.%> to 90 wt.%> of the metal silicate polymer composition.
  • a non-limiting example of the metal silicate polymer includes an aluminosilicate inorganic polymer.
  • the metal silicate polymer composition is given in the range in Table 3, as follows, where the composition totals 100 wt.%>: : Table 3
  • an additive is included in the hybrid magnesium cement composition or components thereof.
  • the additive include a supplemental oxide, such as an iron oxide; a chemical activator, such as sodium sulfate; a superplasticizer, such as a sulfonated composition; a lightening agent, such as cenospheres; a foaming agent, such as an inorganic foaming agent; a stabilization agent; a fiber reinforcement, such as a short fiber or a continuous fiber; and a filler, such as a sand and/or an aggregate filler forming a hybrid magnesium concrete.
  • a supplemental oxide such as an iron oxide
  • a chemical activator such as sodium sulfate
  • a superplasticizer such as a sulfonated composition
  • a lightening agent such as cenospheres
  • a foaming agent such as an inorganic foaming agent
  • a stabilization agent such as a fiber reinforcement, such as a short fiber or a continuous fiber
  • a filler such
  • a silicon phosphate when MOP (magnesium-oxide phosphate inorganic polymer) is reacted with a metal silicate polymer to form a silicon phosphate.
  • a silicon phosphate includes SiP 2 0 7 , and in particular, crystalline SiP 2 0 7 .
  • the crystalline silicon phosphate includes needle-shaped crystals having a relatively long chain length.
  • the silicon phosphate includes inorganic polymer chains having at least 60 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ).
  • the silicon phosphate includes inorganic polymer chains having from about 60 to 1000 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ). In another refinement, the silicon phosphate includes inorganic polymer chains having from about 60 to 120 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ).
  • the malleability of MOP with the needle-shaped crystal significantly exceeds the malleability observed in the art with relatively short chain crystals of a silicon phosphate (e.g., SiP 2 0 7 ).
  • the silicon phosphate allows slippage along the inorganic polymer chain, advantageously improving the malleability of the hybrid cement relative to Portland cement's ultimate compressive strain capacity of less than 0.3%.
  • the hybrid cement i.e., silicon phosphate
  • the hybrid cement has an ultimate compressive strain capacity ranging from 0.5% to 3 %.
  • the hybrid cement has an ultimate strain capacity ranging from 0.8% to 2.5%.
  • a soluble phosphate salt may be ground and mixed in with the dry hybrid magnesium-containing cement composition, forming shotcrete-dry mix, in at least one embodiment.
  • the soluble phosphate salt may be dissolved in water which is then mixed with the dry hybrid magnesium cement composition forming shotcrete- wet mix. It is surprising that the soluble phosphate salt accelerates the polymerization of the hybrid magnesium cement composition to a point where the mixture is unworkable after a time period ranging from 30 seconds to 5 minutes.
  • the amount of phosphate salt in at least one embodiment ranges from 0.5 weight percent to 20 weight percent of the hybrid magnesium cement composition.
  • the phosphate salt is present in an amount ranging from 2 weight percent to 15 weight percent of the hybrid magnesium cement composition.
  • the phosphate salt is present in an amount ranging from 5 weight percent to 10 weight percent of the hybrid magnesium cement composition.
  • the reinforcement includes a short fiber having a length ranging from 0.06 inches to 1 inch. In another embodiment, the short fiber has a length ranging from 0.25 inch to 0.75 inch. In another embodiment, reinforcement includes a continuous fiber including a woven reinforcement and/or a nonwoven reinforcement.
  • the reinforcement includes a fiber having a metal composition.
  • the reinforcement includes a fiber having a ceramic composition, such as a glass fiber.
  • the reinforcement includes a fiber having an organic composition, such as a natural fiber, an aramid fiber, a carbon fiber, a polypropylene fiber or a nanotube.
  • the reinforcement includes a crenulated fiber. In another embodiment, reinforcement includes a milled fiber. In yet another embodiment, the reinforcement includes an extruded fiber.
  • aggregate is added with the sand to form a magnesium concrete.
  • the aggregate is gravel.
  • the aggregate in at least one embodiment, is added to the magnesium cement composition in an amount ranging from 25 volume percent to 50 volume percent of the magnesium cement composition before the sand and aggregate is added. In another embodiment, the aggregate is added to the magnesium cement composition in an amount ranging from 35 volume percent to 45 volume percent.
  • the ratio of sand to gravel in the magnesium cement composition ranges from 0.5 to 0.75. In another embodiment, the ratio of sand and gravel in the magnesium cement composition ranges from 0.6 to 0.7. In at least one embodiment, when the magnesium cement composition, sand, and gravel are mixed the magnesium concrete is formed.
  • a method of manufacture of a hybrid magnesium cement composition includes steps of calcining a magnesium- containing material at a temperature in a range of 770 °C to 1, 100 °C for a first time period, mixing the magnesium-containing material with a first salt to form a magnesium oxide- containing inorganic polymer composition, partially curing the magnesium oxide-containing inorganic polymer composition, and mixing the magnesium oxide-containing inorganic polymer with a metal silicate polymer to form a hybrid magnesium-containing composition.
  • the hybrid magnesium cement composition includes inorganic polymer chains having at least 60 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ).
  • the hybrid magnesium cement composition includes inorganic polymer chains having from about 60 to 1000 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ). In a variation, the hybrid magnesium cement composition includes inorganic polymer chains having from about 60 to 120 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ). In another variation, the hybrid magnesium cement composition includes inorganic polymer chains having from about 80 to 100 repeat units of a silicon phosphate (e.g., SiP 2 0 7 ).
  • the metal silicate polymer composition includes a base, an accelerator, a hydraulic additive, sand, and a silicate selected from the group consisting of flyash, slag, biomass ash and bottom ash.
  • the method further includes a step of adding water to form a wetted hybrid magnesium-containing cement composition.
  • a second salt is mixed with the wetted hybrid magnesium-containing cement composition to form a magnesium- containing shotcrete wet mix.
  • the method includes a step of mixing a second salt to the hybrid magnesium-containing composition forming a magnesium-containing shotcrete dry mix.
  • the first and second salts independently include an anion that is a non-metallic metal oxide.
  • the first and second salt being selected from the group consisting of phosphate salts, sulfate salts, chlorate salts, or nitrate salts.
  • the method further includes steps of mixing a first hydraulic additive in the magnesium oxide-containing inorganic polymer composition; and mixing a sand with the magnesium oxide-containing inorganic polymer composition and the first hydraulic additive.
  • the method further includes a step of mixing a second hydraulic additive in the magnesium oxide-containing inorganic polymer composition.
  • step 100 the magnesium-containing material, such as the dolomite, is provided.
  • step 102 the magnesium-containing material is calcined at 770°C to 1, 100° C for 0.2 hours to 2.5 hours forming the light-burn grade magnesium-containing material.
  • step 104 the light-burn grade magnesium-containing material is mixed with the soluble phosphate salt forming the MOP.
  • step 106 the MOP is mixed with a silicate to form the magnesium-containing cement mortar without water.
  • step 108 magnesium-containing cement mortar is partially cured as result of mixing with water forming a partially-cured magnesium-containing cement mortar.
  • an uncured metal silicate polymer precursor is provided, such as the formulation in Table 3 without the water.
  • the metal silicate polymer precursor partially cures forming a partially- cured metal silicate polymer.
  • the partially-cured magnesium-containing cement mortar and the partially-cured metal silicate polymer are mixed to form the hybrid magnesium-containing cement.
  • a sample magnesium-containing cement mortar is prepared with 1 part magnesium oxide in a light-burn grade dolomite, 1 part GGBFS, and 0.1 part tripotassium phosphate.
  • a sample of a metal silicate polymer is prepared with 1 part Class F fly ash, and 0.13 parts sodium hydroxide anion. Between the magnesium-containing cement mortar and the metal silicate polymer, 1.9 parts of sand, 0.15 parts of silica, and 0.73 parts of water are dispersed. The mixture is mixed thoroughly forming a hybrid magnesium-containing cement sample composition.
  • the hydration mechanism is not fully understood in this case, but is known to be different than the hydration mechanism of Portland cement.
  • Example 1 The composition of Example 1 is cast into 40 mm x 40 mm x 40 mm molds. The samples are demolded after 24 hours. After three days, the compressive strength is measured at 35 MPa when tested to failure at a constant cross-head speed of 0.001 mm/sec according to test method ASTM C773-88 (2011). After two weeks, the compressive strength achieves 50 MPa with a variability of +/- 15%.
  • the ultimate strain of the samples ranges from l .o% to 2.o%, which is at least three times the ultimate strain of Portland cement. While not wishing to be bound by any one theory, the increase in ultimate strain, i.e. the malleability, is believed to be the result of the formation of needle-like crystals of SiP 2 0 7 having unexpectedly long polymeric chains.
  • Example 1 The composition of Example 1 is cast as a 3 mm plate. Short fibers, having an average length ranging from 1.6 mm to 60 mm, are added to Example 1 and are present in an amount ranging from 0.1 vol.% to 2 vol.%.
  • Example 1 The composition of Example 1 is cast as a 3 mm plate. Continuous fibers, having an average length ranging greater than 60 mm, are added to Example 1 and are present in an amount ranging from 0.1 vol.% to 5 vol.%.
  • Example 3 i.e. magnesium-containing hybrid cements made with fibers unexpectedly show an ability to sustain increasing loads beyond the first crack strength, thereby failing progressively rather than catastrophically. The failure appears to be more like the yielding of steel and is classified as pseudo-strain hardening. Catastrophic failure is typically expected of ceramics like the hybrid magnesium-containing cement.
  • Example 6 i.e. magnesium-containing hybrid cements made with fibers unexpectedly show an ability to sustain increasing loads beyond the first crack strength, thereby failing progressively rather than catastrophically. The failure appears to be more like the yielding of steel and is classified as pseudo-strain hardening. Catastrophic failure is typically expected of ceramics like the hybrid magnesium-containing cement.
  • Example 6 i.e. magnesium-containing hybrid cements made with fibers unexpectedly show an ability to sustain increasing loads beyond the first crack strength, thereby failing progressively rather than catastrophically. The failure appears to be more like the yielding of steel and is classified as pseudo-strain hardening. Catastrophic failure is typically expected of ceramics
  • Specimens were demolded after 24 hours and stored in air under standard laboratory conditions until testing. Each cube specimen was instrumented with strain gages and ramped to failure at a constant crosshead speed of 0.001 mm/sec by a high-capacity MTS testing machine. The 3-day compressive strength was 35 MPa and reached 50 MPa after 2 weeks; the strength variation was within 15%. The most significant finding was the substantial gain in ductility. As shown in Figure 3, the ultimate strain (strain at the peak load) is around 1.5%, which is more than 3 times higher than that of regular portland concrete. When the test was terminated right after exceeding the maximum load, the specimen still retained its structural integrity. A highly ductile failure was observed.
  • Part A mix and Part B mix were cast into the same cubic molds separately. Therefore, Part A alone and Part B alone samples were prepared and tested following the same procedure described above.
  • the 3 -day compressive strength was 22 MPa and 20 MPa for Part A and Part B sample, respectively.
  • the corresponding ultimate strain was 0.3% for both types of samples.
  • FIG. 4 shows the Si magic-angle spinning (MAS) spectra acquired for a regular Portland cement (OPC) mortar and the ductile cement mortar (inorganic cement) discussed above.
  • 29 Si MAS NMR is a well known spectroscopic method for the characterization of the silicon species with different number of bridging oxygens (Q n ).
  • Q 4 the majority of the silicon species exist as Q 4 (74%) and the rest as Q 2 (26%).
  • Q 4 bridging oxygens

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

La présente invention concerne une composition de ciment hybride à base de magnésium ayant un composant côté A et un composant côté B. Le composant côté A comprend un composant A1 comprenant un matériau contenant du magnésium de qualité à brûlage léger, et un composant A2 comprenant un sel d'oxyde non métallique. Le composant côté B comprend un polymère de silicate métallique.
PCT/US2016/065372 2015-12-14 2016-12-07 Ciment hybride à base de magnésium et son procédé de fabrication Ceased WO2017105961A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN113956017A (zh) * 2021-12-03 2022-01-21 昌吉市飞鸿新材料技术有限公司 聚能防火保温板浆料
CN114525079A (zh) * 2022-01-19 2022-05-24 北京林业大学 一种无醛阻燃氯氧镁水泥基木材胶黏剂及其制备方法

Citations (5)

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US6458423B1 (en) * 1999-08-03 2002-10-01 David M. Goodson Sprayable phosphate cementitious coatings and a method and apparatus for the production thereof
US20050016421A1 (en) * 2001-02-14 2005-01-27 Shinsaku Fujimori Cement composition
US20050160946A1 (en) * 2003-01-31 2005-07-28 Comrie Douglas C. Cementitious materials including stainless steel slag and geopolymers
JP2009007202A (ja) * 2007-06-28 2009-01-15 Denki Kagaku Kogyo Kk セメント混和材及びセメント組成物
US20130000520A1 (en) * 2011-06-30 2013-01-03 NTH Consultants, Ltd. Hybrid magnesium cement and method of manufacture

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Publication number Priority date Publication date Assignee Title
US6458423B1 (en) * 1999-08-03 2002-10-01 David M. Goodson Sprayable phosphate cementitious coatings and a method and apparatus for the production thereof
US20050016421A1 (en) * 2001-02-14 2005-01-27 Shinsaku Fujimori Cement composition
US20050160946A1 (en) * 2003-01-31 2005-07-28 Comrie Douglas C. Cementitious materials including stainless steel slag and geopolymers
JP2009007202A (ja) * 2007-06-28 2009-01-15 Denki Kagaku Kogyo Kk セメント混和材及びセメント組成物
US20130000520A1 (en) * 2011-06-30 2013-01-03 NTH Consultants, Ltd. Hybrid magnesium cement and method of manufacture

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113956017A (zh) * 2021-12-03 2022-01-21 昌吉市飞鸿新材料技术有限公司 聚能防火保温板浆料
CN114525079A (zh) * 2022-01-19 2022-05-24 北京林业大学 一种无醛阻燃氯氧镁水泥基木材胶黏剂及其制备方法
CN114525079B (zh) * 2022-01-19 2023-12-29 北京林业大学 一种无醛阻燃氯氧镁水泥基木材胶黏剂及其制备方法

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