WO2005019130A1 - Geopolymers and methods for their production - Google Patents

Geopolymers and methods for their production Download PDF

Info

Publication number
WO2005019130A1
WO2005019130A1 PCT/NZ2004/000193 NZ2004000193W WO2005019130A1 WO 2005019130 A1 WO2005019130 A1 WO 2005019130A1 NZ 2004000193 W NZ2004000193 W NZ 2004000193W WO 2005019130 A1 WO2005019130 A1 WO 2005019130A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
geopolymer
geopolymer composition
metal
boron
Prior art date
Application number
PCT/NZ2004/000193
Other languages
French (fr)
Inventor
Catherine Louise Nicholson
Ross Alan Fletcher
Original Assignee
Industrial Research Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Industrial Research Limited filed Critical Industrial Research Limited
Publication of WO2005019130A1 publication Critical patent/WO2005019130A1/en

Links

Classifications

    • 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
    • C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • 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
    • C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • 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 invention relates to a novel family of geopolymers with controlled set times, containing structurally bound boron and to methods for their production.
  • Geopolymer materials are inorganic polymers synthesised by reaction of a strongly alkaline silicate solution and an aluminosilicate source at near-ambient temperature. The reaction gives rise to a material that exhibits rapid setting and hardening characteristics. Geopolymers have been investigated for use in a number of applications, including as novel cementing systems within the construction industry, as refractory materials and as encapsulants for hazardous and radioactive waste streams.
  • Structural characterisation of geopolymers reveals that these materials do not exhibit long range order and are thus X-ray amorphous. They are based on an aluminosilicate framework in which the aluminium is mainly in tetrahedral coordination and silicon has a variety of coordination geometries. A cation, commonly sodium or potassium, provides charge balance.
  • the structural units include sialate [-Si-O-Al-O-], sialate siloxo [-Si-O-Al-O-Si-O-] and sialate disiloxo [-Si-O-Al-O-Si-O-Si-O-].
  • the Class C material has proven problematic for use in producing a geopolymer product with a setting time sufficiently long enough to enable satisfactory mixing, pouring and moulding of the geopolymer. It has been postulated that the presence of large amounts of calcium is responsible for this fast setting behaviour. This has prevented commercial exploitation of Class C flyash as a raw material for geopolymers both in New Zealand and in other countries.
  • the present invention comprises a geopolymer composition having the following oxide molar ratios:
  • the geopolymer composition of the present invention has a B 2 O 3 / H 2 O molar ratio of between 0.01 and 0.1.
  • the geopolymer composition of the present invention has the following oxide molar ratios:
  • the geopolymer composition is prepared by adding an aluminosilicate source to a reagent mixture comprising boron and/or a boron containing compound and an alkaline Group I metal silicate solution.
  • the geopolymer composition of the present invention is expressed in terms of oxides as follows: (yNa 2 0:zK 2 O):vB 2 O 3 :Al 2 O 3 :xSiO 2 :wH 2 O wherein in the fully hydrated form, w is between about 10 and about 15, v has a value between about 0.5 and about 1.0, x has a value between about 5 and about 8, and y and z have values such that the sum of their values totals 1.
  • the present invention comprises a geopolymer composition expressed in terms of oxides as follows: (yNa 2 0:zK 2 O):vB 2 O 3 :Al 2 O 3 :xSiO 2 :wH 2 O wherein in the fully hydrated form, w is between about 10 and about 20, v has a value between about 0.2 and about 2, x has a value between about 5 and about 10, and y and z have values such that the sum of their values totals 1.
  • the present invention provides a geopolymer composition formed from a reagent mixture comprising or including: (a) a Group I metal silicate; (b) an aluminosilicate; (c) boron and/or a boron containing compound;
  • the invention provides a method of forming a geopolymer composition of the invention, the method comprising or including the steps of: (a) mixing boron and/or a boron containing compound with an alkaline Group I metal silicate solution; (b) adding an aluminosilicate to the alkaline Group I metal silicate solution formed in (a) to produce a geopolymer reagent mixture; and
  • the invention provides a geopolymer composition when produced by a method of the invention.
  • the Group I metal silicate solution may be selected from commercially available Group I metal silicate solutions or a solution of a commercially available Group I metal silicate and water. Alternatively, a Group I metal silicate solution may be produced by the preliminary steps of:
  • the invention provides a method of producing a shaped geopolymer composition comprising or including:
  • the invention provides a shaped geopolymer composition when produced by a method of the invention.
  • Set time The time interval between pouring of the liquid mix into a mould and solidification of the mix.
  • Setting The process of solidification of the mix during which it hardens and gains strength.
  • Curing The process of applying heat and/or moisture to the mix after setting under controlled conditions and for a specific period of time to enhance properties such as compressive strength.
  • Figure 1 is a graph of the relationship between the addition of borax and setting time of a geopolymer of the invention.
  • Figure 2 is an 27 A1 NMR spectrum of a geopolymer of the invention as defined in Example 1;
  • Figure 3 is a 29 Si NMR spectrum of a geopolymer of the invention as defined in Example 1 ;
  • Figure 4 is a 23 Na NMR spectrum of a geopolymer of the invention as defined in Example 1 ;
  • Figure 5 is a n B NMR spectrum of a geopolymer of the invention as defined in Example 1;
  • Figure 6 is a XRD pattern of a geopolymer of the invention as defined in Example 1.
  • Figure 7 is a XRD pattern of a geopolymer of the invention as defined in Example 3.
  • the present invention is broadly directed to a novel family of geopolymers with controlled set times and to methods for their production.
  • the geopolymer of the present invention is novel, particularly as a result of incorporation of boron into its structure.
  • boron or a boron containing compound is added to a typical geopolymer reagent mixture in an amount of 5% to 10% by weight of the reagent mixture.
  • the boron becomes incorporated as an essential part of the geopolymer structure as evidenced by XRD patterns showing no presence of crystalline boron-containing compounds.
  • This is a novel geopolymer structure and can broadly be termed a boroaluminosilicate.
  • the geopolymer composition of the present invention has a B 2 O 3 / H 2 O molar ratio of between 0.01 and 0.1.
  • the geopolymer composition of the present invention has the following oxide molar ratios:
  • the geopolymer composition is prepared by adding an aluminosilicate source to a reagent mixture comprising boron and/or a boron containing compound and an alkaline Group I metal silicate solution.
  • the present invention comprises a geopolymer composition expressed in terms of oxides as follows: (yNa 2 O:zK 2 O):vB 2 O 3 :Al 2 O 3 :xSiO 2 :wH 2 O wherein in the fully hydrated form, w is between about 10 and about 20, v has a value between about 0.2 and about 2, x has a value between about 5 and about 10, and y and z have values such that the sum of their values totals 1.
  • the geopolymer composition of the present invention is expressed in terms of oxides as follows: (yNa 2 O:zK 2 O):vB 2 O 3 :Al 2 O 3 :xSiO 2 :wH 2 O wherein in the fully hydrated form, w is between about 10 and about 15, v has a value between about 0.5 and about 1.0, x has a value between about 5 and about 8, and y and z have values such that the sum of their values totals 1.
  • the present invention provides a geopolymer composition formed from a reagent mixture comprising or including: (a) a Group I metal silicate; (b) an aluminosilicate;
  • Group I metal hydroxides useful in the invention include lithium, sodium, potassium, rubidium and caesium hydroxide.
  • the Group I metal hydroxide is added as a solution which may be formed by a prior step of dissolving a solid hydroxide in water.
  • Group I metal silicates suitable for use in the composition of the invention include sodium and potassium silicate but are not limited thereto.
  • the Group I metal silicate may be used in the form of a commercially available solution.
  • Aluminosilicates useful in the invention include a wide variety of materials characterised in that they are able to provide a source of alumina and a silicate(s) to the geopolymerisation reaction.
  • suitable aluminosilicates include flyash class C (a typical composition of which is set forth in Table 1 herein), flyash class F (a typical composition of which is set forth in Table 2 herein), metakaolin, pumice, allophane, bentonite and ground slag.
  • flyash class C a typical composition of which is set forth in Table 1 herein
  • flyash class F a typical composition of which is set forth in Table 2 herein
  • metakaolin pumice, allophane, bentonite and ground slag.
  • the aluminosilicate is flyash class C.
  • Boron may be used per se or may be provided in the form of a compound.
  • Suitable boron containing compounds include but are not limited to anhydrous or hydrated Group I metal borates, for example borax (hydrated sodium borate), or pure oxides of boron, but are not limited thereto. Borax is currently preferred for use.
  • the oxide of boron is preferably included in a small amount, typically between lwt% and 2wt%, so that the set time of the geopolymer composition is increased. It has been discovered that the addition of higher amounts of oxides of boron may have the effect of decreasing the set time of the geopolymer composition.
  • Geopolymer compositions of the invention typically comprise: about 5% to about 25%, preferably 10% to 20%, more preferably 10% to 15% of Group I metal silicates; about 40% to about 70%, preferably 60% to 70% of aluminosilicate; about 1% to about 25%, preferably 5% to 10% of boron; about 1% to about 25%, preferably 1% to 5% of Group I metal hydroxide; and about 5% to about 25%, preferably 5% to 20%, more preferably 5% to 10% of water.
  • the invention provides a method of forming a geopolymer composition of the invention, the method comprising or including the steps of:
  • the alkaline Group I metal silicate solution is preferably provided by mixing a Group I metal silicate solution with an alkaline hydroxide solution.
  • the Group I metal silicate is mixed with an alkaline hydroxide solution wherein the cation in the silicate and the hydroxide are the same.
  • sodium silicate may be mixed with a sodium hydroxide solution.
  • the Group I metal silicate solution may be selected from any one of a number of commercially available Group I metal silicate solutions, for example sodium silicate solution and potassium silicate solution, or a solution of a commercially available
  • Group I metal silicate and water.
  • a Group I metal silicate solution may be produced by the preliminary steps of:
  • the Group I metal silicate is present in a weight % of about 30% to about 55%, preferably 35% to 40% of the solution.
  • a source of same as discussed above, is added to the Group I metal silicate solution with simple mixing.
  • borax is added to a sodium silicate solution with slow mixing.
  • the amount of boron added may be calculated according to the length of setting time required. Greater amounts will lead to longer set times. Such an effect has not been reported previously.
  • Figure 1 shows an amount of boron in the range of about 7% to about 11% by weight of the composition will generally give a set time of between 20 and 45 minutes.
  • the weight % of boron added to the mixture is from about 1% to about 25%, preferably 1 % to 10%, and more preferably 5% to 10%.
  • the aluminosilicate is added to the mixture formed above, with stirring to homogeneity.
  • Aluminosilicate is generally added as a weight % of about 40% to about 70%, preferably 60 % to 70 %.
  • the reaction is carried out at a pH between about 10 and 14, preferably between 12 and 14, and still more preferably between 13 and 14.
  • the geopolymer reagent solution may be left to stand to set for the desired time according to the amount of boron added.
  • Typical set times are between about 10 and about 720 minutes, preferably between 10 and 120 minutes, more preferably between 15 and 45 minutes.
  • the setting occurs at room temperature.
  • the invention provides a method of producing a shaped geopolymer composition comprising or including the steps of:
  • Shaping devices contemplated for use in the present invention include moulds, dies and casts amongst other devices.
  • the geopolymer composition may be cured by dry heating, fan-assisted heating, steam curing or immersion in water or by other means as are known in the art. Most preferably the geopolymer composition is cured by dry heating or steam curing.
  • the geopolymer composition may be cured at a temperature between about 30 and about 120°C, preferably between 50 and 100°C, more preferably between 80 and 100°C, and even more preferably at 90°C.
  • the time taken to cure the geopolymer composition will usually be between about 1 and about 24 hours, preferably between 12 and 24 hours, and more preferably between 12 and 18 hours.
  • the sodium silicate solution has a Na 2 O : SiO 2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm 3 and a viscosity of 400 centipoise,
  • the invention comprises a geopolymer with a set time of 44 minutes and a composition having the following oxide molar ratios:
  • Figure 2 is an Al NMR spectrum of a geopolymer of this embodiment of the invention.
  • Figure 3 is a 29 Si NMR spectrum of a geopolymer of this embodiment of the invention.
  • Figure 4 is an 23 Na NMR spectrum of a geopolymer of this embodiment of the invention.
  • Figure 5 is an ⁇ B NMR spectrum of a geopolymer of this embodiment of the invention.
  • Figure 6 is an XRD pattern of a geopolymer of this embodiment of the invention.
  • the sodium silicate solution has a Na 2 O : SiO 2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm 3 and a viscosity of 400 centipoise,
  • the invention comprises a geopolymer with a set time of 50 minutes and a composition having the following oxide molar ratios:
  • the sodium silicate solution has a Na 2 O : SiO 2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm 3 and a viscosity of 400 centipoise,
  • the invention comprises a geopolymer with a set time of 75 minutes and a composition having the following oxide molar ratios:
  • Figure 7 is an XRD pattern of a geopolymer of this embodiment of the invention.
  • the sodium silicate solution has a Na 2 O : SiO 2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm 3 and a viscosity of 400 centipoise,
  • An example of a further embodiment of the invention comprises the formation of a geopolymer by the steps comprising: (a) Dissolving 1.82 g of sodium hydroxide in 3.69 g of water to form a sodium hydroxide solution,
  • the sodium silicate solution has a Na 2 O : SiO 2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm 3 and a viscosity of 400 centipoise,
  • the sodium silicate solution has a Na O : SiO 2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm 3 and a viscosity of 400 centipoise,
  • the invention comprises a geopolymer with a set time of 160 minutes and a composition having the following oxide molar ratios:
  • the compressive strengths of the geopolymer products were determined using a 100-ton testing machine in accordance with standard cement testing procedures. Samples were characterised by solid state magic angle spinning nuclear magnetic resonance (SS MAS NMR) and X-ray diffraction (XRD) techniques.
  • SS MAS NMR solid state magic angle spinning nuclear magnetic resonance
  • XRD X-ray diffraction
  • Figure 1 illustrates the relationships between the addition of borax and subsequent set time for a geopolymer of the invention.
  • the normal maximum set time achieved for this formulation without addition of borax was found to be 15 minutes. This was extended to 45 minutes by addition of 10% by weight of borax.
  • Table 3 illustrates the interrelationships between the water, sodium and boron concentrations and their effects on the compressive strengths and set times of the
  • geopolymers of the invention Compressive strengths of boron-containing geopolymers comparable to those reported for conventional geopolymers were achieved through reduction of the water and alkali content without compromise of workability. The amount of silicate solution was kept at the same level to ensure enough soluble silica was available for the geopolymerisation reaction to occur. Moreover, extended set times could only be achieved by addition of boron to the formulations.
  • NMR ANALYSIS SS MAS NMR was carried out to determine if and how the boron had been incorporated into the structure of the geopolymer material.
  • Figures 2-5 show the characteristic NMR spectra for the major matrix components, namely aluminium, silicon, sodium and, in this new class of geopolymers, boron.
  • Figure 2 shows that the aluminium is predominantly in tetrahedral sites, as expected.
  • silicon exhibits a range of sites but is predominantly saturated in aluminium.
  • the sodium spectrum indicates that most of the sodium is located within the geopolymer pores rather than within the framework of the structure.
  • the borax starting material exhibits two coordination geometries: trigonal boron (BO 3 structural unit) and tetrahedral (BO structural unit).
  • the ⁇ B NMR spectrum of the hardened geopolymer product exhibits only tetrahedral boron ( Figure 5). This would be expected if the boron formed an integral part of the structure and indicates that it may be in part substituting for tetrahedral aluminium or silicon.
  • the differences in the spectra of the raw material and the final product strongly suggest that the boron is playing a crucial role in the formation of the geopolymer, i.e. the boron has entered the structure and formed a geopolymer based on a boroaluminosilicate framework.
  • a geopolymer with a framework of boroaluminosilicate units conforms to the accepted definition of a geopolymeric material, being amorphous and consisting of a randomly arranged framework of aluminosilicate units charge-balanced by univalent or divalent metal cations. This is therefore a class of geopolymer not previously reported in the literature.
  • the X-ray diffraction pattern of the boron-containing material also shows that this new class of boroaluminosilicate geopolymer conforms to the accepted definition of "geopolymer” in as far as it is an amorphous material based on an aluminosilicate framework.
  • aluminosilicate sources leads to rapid set times, and that the inclusion of boron lengthens this set time. This allows for the first time the use of aluminosilicate sources such as Flyash Class C with acceptable set times. It is further believed that the boron adopts tetrahedral sites in the geopolymer matrix, hence creating a novel family of boroaluminosilicates.
  • compositions of the invention have application in the construction industry, including as novel cementing systems, for example pre-cast product fabrication, as refractory materials, as encapsulants for hazardous, toxic and radioactive waste steams, and as fire resistant materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The present invention relates to novel geopolymer compositions with structurally incorporated boron which have the advantage of a retarded set time. The preferred geopolymer composition has the following oxide molar ratios: (a) SiO2 / Al2O3 = 3.0 - 6.5; (b) M2O / SiO2 = 0.07 - 0.20; (c) H2O / M2O = 8.0 - 19.0; (d) B2O3 / H2O = 0.01 - 0.2; and (e) M2O / B2O3 = 0.5 - 6.0 wherein M is a Group I metal. The present invention also relates to methods of forming these novel geopolymer compositions.

Description

GEOPOLYMERS AND METHODS FOR THEIR PRODUCTION
FIELD OF THE INVENTION
This invention relates to a novel family of geopolymers with controlled set times, containing structurally bound boron and to methods for their production.
BACKGROUND TO THE INVENTION
Geopolymer materials (also known as alkali-activated flyash-based cements) are inorganic polymers synthesised by reaction of a strongly alkaline silicate solution and an aluminosilicate source at near-ambient temperature. The reaction gives rise to a material that exhibits rapid setting and hardening characteristics. Geopolymers have been investigated for use in a number of applications, including as novel cementing systems within the construction industry, as refractory materials and as encapsulants for hazardous and radioactive waste streams.
Structural characterisation of geopolymers reveals that these materials do not exhibit long range order and are thus X-ray amorphous. They are based on an aluminosilicate framework in which the aluminium is mainly in tetrahedral coordination and silicon has a variety of coordination geometries. A cation, commonly sodium or potassium, provides charge balance. The structural units include sialate [-Si-O-Al-O-], sialate siloxo [-Si-O-Al-O-Si-O-] and sialate disiloxo [-Si-O-Al-O-Si-O-Si-O-].
Much interest has centred on the types of aluminosilicate sources that can be used successfully in the geopolymerisation reaction. Naturally occurring minerals including clays and pumice as well as industrial wastes such as flyash and slag have been investigated. There is considerable advantage in being able to utilise the latter types of waste materials and much effort has been put into developing geopolymers synthesised from the flyash obtained as a by-product of coal combustion. Flyash may be divided into two types - Class C and Class F. New Zealand flyash contains very high levels of lime (CaO) and is termed "Class C" flyash, in contrast to the low-lime content, "Class F" flyash. The Class C material has proven problematic for use in producing a geopolymer product with a setting time sufficiently long enough to enable satisfactory mixing, pouring and moulding of the geopolymer. It has been postulated that the presence of large amounts of calcium is responsible for this fast setting behaviour. This has prevented commercial exploitation of Class C flyash as a raw material for geopolymers both in New Zealand and in other countries.
The effect of adding a variety of inorganic salts of potassium, calcium and magnesium to several alkali-activated fly ash-based cement reagent mixtures has been investigated (W.K.W. Lee & J.SJ. van Deventer, "The effect of ionic contaminants on the early-age properties of alkali-activated fly ash-based cements", Cement and Concrete Research, 32 (2002), 577-584). Generally, the addition of Ca and Mg salts was found to accelerate the set time of the mixture, while the addition of K salts was found to retard the set time. However, the effects were also dependant upon the composition of the reagent mixture.
It would be desirable to produce geopolymers from fast set flyash which have controlled set times. It is therefore an object of the invention to provide a geopolymer having a controlled set time or to at least provide the public with a useful choice.
SUMMARY OF THE INVENTION
In a first aspect the present invention comprises a geopolymer composition having the following oxide molar ratios:
(a) SiO2 / Al2O3 = 3.0 - 6.5;
(b) M2O / SiO2 = 0.07 - 0.20; (c) H2O / M2O = 8.0 - 19.0;
(d) B2O3 / H2O = 0.01 - 0.2; and
(e) M2O / B2O3 = 0.5 - 6.0 wherein M is a Group I metal. Desirably, the geopolymer composition of the present invention has a B2O3 / H2O molar ratio of between 0.01 and 0.1.
Preferably the geopolymer composition of the present invention has the following oxide molar ratios:
(a) SiO2 / Al2O3 = 4.0 - 5.0;
(b) M2O / SiO2 = 0.10 - 0.15;
(c) H2O / M2O = 10.0 - 17.0; (d) B2O3 / H2O = 0.02 - 0.06; and (e) M2O / B2O3 = 1.0 - 4.0. wherein M is a Group I metal.
Preferably, the geopolymer composition is prepared by adding an aluminosilicate source to a reagent mixture comprising boron and/or a boron containing compound and an alkaline Group I metal silicate solution.
Preferably the geopolymer composition of the present invention is expressed in terms of oxides as follows: (yNa20:zK2O):vB2O3:Al2O3:xSiO2:wH2O wherein in the fully hydrated form, w is between about 10 and about 15, v has a value between about 0.5 and about 1.0, x has a value between about 5 and about 8, and y and z have values such that the sum of their values totals 1.
In a further aspect the present invention comprises a geopolymer composition expressed in terms of oxides as follows: (yNa20:zK2O):vB2O3:Al2O3:xSiO2:wH2O wherein in the fully hydrated form, w is between about 10 and about 20, v has a value between about 0.2 and about 2, x has a value between about 5 and about 10, and y and z have values such that the sum of their values totals 1.
In a yet a further aspect the present invention provides a geopolymer composition formed from a reagent mixture comprising or including: (a) a Group I metal silicate; (b) an aluminosilicate; (c) boron and/or a boron containing compound;
(d) a Group I metal hydroxide; and
(e) water.
In another aspect the invention provides a method of forming a geopolymer composition of the invention, the method comprising or including the steps of: (a) mixing boron and/or a boron containing compound with an alkaline Group I metal silicate solution; (b) adding an aluminosilicate to the alkaline Group I metal silicate solution formed in (a) to produce a geopolymer reagent mixture; and
(c) allowing the geopolymer reagent mixture formed in (b) to set and thereby form a geopolymer composition.
In another aspect the invention provides a geopolymer composition when produced by a method of the invention.
The Group I metal silicate solution may be selected from commercially available Group I metal silicate solutions or a solution of a commercially available Group I metal silicate and water. Alternatively, a Group I metal silicate solution may be produced by the preliminary steps of:
(a) adding a Group I metal compound to water to form a Group I metal ion solution; and
(b) dissolving a silicate in the Group I metal ion solution to form a Group I metal silicate solution.
In broad terms in another aspect the invention provides a method of producing a shaped geopolymer composition comprising or including:
(a) carrying out the method of the invention described above to obtain a geopolymer reagent mixture;
(b) prior to setting, transferring the geopolymer reagent mixture to a shaping device;
(c) allowing the geopolymer reagent mixture to set to form a shaped geopolymer composition; and
(d) curing the shaped geopolymer composition. In another aspect the invention provides a shaped geopolymer composition when produced by a method of the invention.
To those skilled in the art to which the invention relates, many changes in construction and widely differing embodiments and applications of the invention will suggest themselves without departing from the scope of the invention as defined in the appended claims. The disclosures and the descriptions herein are purely illustrative and are not intended to be in any sense limiting.
DEFINITIONS
Where in the specification the following terms are used they have the following meanings:
Flyash - Fine ash recovered from the flue gas on combustion of a hydrocarbon fuel, for example from coal in thermal power stations.
Set time - The time interval between pouring of the liquid mix into a mould and solidification of the mix. Setting - The process of solidification of the mix during which it hardens and gains strength.
Curing - The process of applying heat and/or moisture to the mix after setting under controlled conditions and for a specific period of time to enhance properties such as compressive strength.
BRIEF DESCRIPTION OF THE FIGURES
The invention is further described with reference to the accompanying figures in which:
Figure 1 is a graph of the relationship between the addition of borax and setting time of a geopolymer of the invention.
Figure 2 is an 27A1 NMR spectrum of a geopolymer of the invention as defined in Example 1; Figure 3 is a 29Si NMR spectrum of a geopolymer of the invention as defined in Example 1 ;
Figure 4 is a 23Na NMR spectrum of a geopolymer of the invention as defined in Example 1 ;
Figure 5 is a nB NMR spectrum of a geopolymer of the invention as defined in Example 1;
Figure 6 is a XRD pattern of a geopolymer of the invention as defined in Example 1; and
Figure 7 is a XRD pattern of a geopolymer of the invention as defined in Example 3.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention is broadly directed to a novel family of geopolymers with controlled set times and to methods for their production.
The geopolymer of the present invention is novel, particularly as a result of incorporation of boron into its structure. In the present invention boron or a boron containing compound is added to a typical geopolymer reagent mixture in an amount of 5% to 10% by weight of the reagent mixture. The boron becomes incorporated as an essential part of the geopolymer structure as evidenced by XRD patterns showing no presence of crystalline boron-containing compounds. This is a novel geopolymer structure and can broadly be termed a boroaluminosilicate.
The addition of boron or a boron containing compound to the geopolymer reagent mixture has the effect of slowing the set time of the geopolymer composition. This is a particularly desirable effect as previously the use of geopolymers has been restricted by their rapid set times. As discussed above in one aspect the present invention comprises a geopolymer composition having the following oxide molar ratios: (a) SiO2 / Al2O3 = 3.0 - 6.5; (b) M2O / SiO2 = 0.07 - 0.20;
(c) H2O /M2O = 8.0 - 19.0;
(d) B2O3 / H2O = 0.01 - 0.2; and
(e) M2O / B2O3 = 0.5 - 6.0. wherein M is a Group I metal.
Desirably, the geopolymer composition of the present invention has a B2O3 / H2O molar ratio of between 0.01 and 0.1.
Preferably the geopolymer composition of the present invention has the following oxide molar ratios:
(a) SiO2 / Al2O3 = 4.0 - 5.0;
(b) M2O / SiO2 = 0.10 - 0.15;
(c) H2O / M2O = 10.0 - 17.0;
(d) B2O3 / H2O = 0.02 - 0.06; and (e) M2O / B2O3 = 1.0 - 4.0. wherein M is a Group I metal.
Preferably, the geopolymer composition is prepared by adding an aluminosilicate source to a reagent mixture comprising boron and/or a boron containing compound and an alkaline Group I metal silicate solution.
In a further aspect the present invention comprises a geopolymer composition expressed in terms of oxides as follows: (yNa2O:zK2O):vB2O3:Al2O3:xSiO2:wH2O wherein in the fully hydrated form, w is between about 10 and about 20, v has a value between about 0.2 and about 2, x has a value between about 5 and about 10, and y and z have values such that the sum of their values totals 1.
Preferably the geopolymer composition of the present invention is expressed in terms of oxides as follows: (yNa2O:zK2O):vB2O3:Al2O3:xSiO2:wH2O wherein in the fully hydrated form, w is between about 10 and about 15, v has a value between about 0.5 and about 1.0, x has a value between about 5 and about 8, and y and z have values such that the sum of their values totals 1.
In a yet further aspect the present invention provides a geopolymer composition formed from a reagent mixture comprising or including: (a) a Group I metal silicate; (b) an aluminosilicate;
(c) boron and/or a boron containing compound;
(d) a Group I metal hydroxide; and
(e) water.
Group I metal hydroxides useful in the invention include lithium, sodium, potassium, rubidium and caesium hydroxide. The Group I metal hydroxide is added as a solution which may be formed by a prior step of dissolving a solid hydroxide in water.
Group I metal silicates suitable for use in the composition of the invention include sodium and potassium silicate but are not limited thereto.
Desirably, the Group I metal silicate may be used in the form of a commercially available solution.
Aluminosilicates useful in the invention include a wide variety of materials characterised in that they are able to provide a source of alumina and a silicate(s) to the geopolymerisation reaction. Non-limiting examples of suitable aluminosilicates include flyash class C (a typical composition of which is set forth in Table 1 herein), flyash class F (a typical composition of which is set forth in Table 2 herein), metakaolin, pumice, allophane, bentonite and ground slag. Preferably the aluminosilicate is flyash class C.
Boron may be used per se or may be provided in the form of a compound. Suitable boron containing compounds include but are not limited to anhydrous or hydrated Group I metal borates, for example borax (hydrated sodium borate), or pure oxides of boron, but are not limited thereto. Borax is currently preferred for use.
Where the source of boron is an oxide of boron, the oxide of boron is preferably included in a small amount, typically between lwt% and 2wt%, so that the set time of the geopolymer composition is increased. It has been discovered that the addition of higher amounts of oxides of boron may have the effect of decreasing the set time of the geopolymer composition.
Geopolymer compositions of the invention typically comprise: about 5% to about 25%, preferably 10% to 20%, more preferably 10% to 15% of Group I metal silicates; about 40% to about 70%, preferably 60% to 70% of aluminosilicate; about 1% to about 25%, preferably 5% to 10% of boron; about 1% to about 25%, preferably 1% to 5% of Group I metal hydroxide; and about 5% to about 25%, preferably 5% to 20%, more preferably 5% to 10% of water.
In one embodiment the geopolymer composition has a composition expressed in terms of molar oxide ratios as follows:
(a) SiO2 / Al2O3 - 3.0 - 6.5;
(b) Na2O / SiO2 = 0.07 - 0.20;
(c) H2O / Na2O = 8.0 - 19.0;
(d) B2O3 / H2O = 0.01 - 0.2; and (e) Na2O / B2O3 = 0.5 - 6.0.
In another aspect the invention provides a method of forming a geopolymer composition of the invention, the method comprising or including the steps of:
(a) mixing boron and/or a boron containing compound with an alkaline Group I metal silicate solution;
(b) adding an aluminosilicate to the alkaline Group I metal silicate solution formed in (a) to produce a geopolymer reagent mixture; and
(c) allowing the geopolymer reagent mixture formed in (b) to set and thereby form a geopolymer composition. The alkaline Group I metal silicate solution is preferably provided by mixing a Group I metal silicate solution with an alkaline hydroxide solution. Preferably the Group I metal silicate is mixed with an alkaline hydroxide solution wherein the cation in the silicate and the hydroxide are the same. For example sodium silicate may be mixed with a sodium hydroxide solution.
The Group I metal silicate solution may be selected from any one of a number of commercially available Group I metal silicate solutions, for example sodium silicate solution and potassium silicate solution, or a solution of a commercially available
Group I metal silicate and water. Alternatively, a Group I metal silicate solution may be produced by the preliminary steps of:
(i) adding a Group I metal compound to water to form a Group I metal ion solution; and (ii) dissolving a silicate in the Group I metal ion solution to form a Group I metal silicate solution.
The Group I metal silicate is present in a weight % of about 30% to about 55%, preferably 35% to 40% of the solution.
A source of same as discussed above, is added to the Group I metal silicate solution with simple mixing. For example, borax is added to a sodium silicate solution with slow mixing. Surprisingly, the amount of boron added may be calculated according to the length of setting time required. Greater amounts will lead to longer set times. Such an effect has not been reported previously. For example, Figure 1 shows an amount of boron in the range of about 7% to about 11% by weight of the composition will generally give a set time of between 20 and 45 minutes.
Typically, the weight % of boron added to the mixture is from about 1% to about 25%, preferably 1 % to 10%, and more preferably 5% to 10%.
The aluminosilicate is added to the mixture formed above, with stirring to homogeneity. Aluminosilicate is generally added as a weight % of about 40% to about 70%, preferably 60 % to 70 %. The reaction is carried out at a pH between about 10 and 14, preferably between 12 and 14, and still more preferably between 13 and 14.
Once formed, the geopolymer reagent solution may be left to stand to set for the desired time according to the amount of boron added. Typical set times are between about 10 and about 720 minutes, preferably between 10 and 120 minutes, more preferably between 15 and 45 minutes.
Desirably, the setting occurs at room temperature.
In broad terms in another aspect the invention provides a method of producing a shaped geopolymer composition comprising or including the steps of:
(a) carrying out the method of the invention described above to obtain a geopolymer reagent mixture;
(b) prior to setting, transferring the geopolymer reagent mixture to a shaping device;
(c) allowing the geopolymer reagent mixture to set to form a shaped geopolymer composition; and
(d) curing the shaped geopolymer composition.
Shaping devices contemplated for use in the present invention include moulds, dies and casts amongst other devices.
The geopolymer composition may be cured by dry heating, fan-assisted heating, steam curing or immersion in water or by other means as are known in the art. Most preferably the geopolymer composition is cured by dry heating or steam curing. The geopolymer composition may be cured at a temperature between about 30 and about 120°C, preferably between 50 and 100°C, more preferably between 80 and 100°C, and even more preferably at 90°C. The time taken to cure the geopolymer composition will usually be between about 1 and about 24 hours, preferably between 12 and 24 hours, and more preferably between 12 and 18 hours.
The present invention will now be described in more detail with reference to the following non-limiting experimental section. EXPERIMENTAL:
EXAMPLE 1
An example of one preferred embodiment of the invention comprises the formation of a geopolymer by the steps comprising:
(a) Dissolving 1.86 g of sodium hydroxide in 7.41 g of water to form a sodium hydroxide solution, (b) Slowly adding 7.02 g of sodium silicate solution to the sodium hydroxide solution with constant stirring to form an alkaline sodium silicate solution. The sodium silicate solution has a Na2O : SiO2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm3 and a viscosity of 400 centipoise,
(c) Adding 5.91 grams of borax to the sodium silicate solution with continuous stirring, and
(d) Adding 35.57 g of New Zealand flyash to the sodium silicate solution with continuous stirring to form the reagent solution. Table 1 below provides a typical composition for New Zealand flyash.
(e) Pouring the reagent solution into a mould and allowing it to set at ambient temperature, and
(f) Curing the solution at 90°C for 16 hours in a drying oven
In this embodiment the invention comprises a geopolymer with a set time of 44 minutes and a composition having the following oxide molar ratios:
SiO2 / Al2O3 = 4.5; Na2O / SiO2 = 0.1;
H2O / Na20 = 17;
B2O3 / H20 = 0.04; and
Na2O / B2O3 = 1.67
Figure 2 is an Al NMR spectrum of a geopolymer of this embodiment of the invention.
Figure 3 is a 29Si NMR spectrum of a geopolymer of this embodiment of the invention.
Figure 4 is an 23Na NMR spectrum of a geopolymer of this embodiment of the invention.
Figure 5 is an πB NMR spectrum of a geopolymer of this embodiment of the invention. Figure 6 is an XRD pattern of a geopolymer of this embodiment of the invention. EXAMPLE 2
An example of another embodiment of the invention comprises the formation of a geopolymer by the steps comprising:
(a) Dissolving 1.86 g of sodium hydroxide in 2.47 g of water to form a sodium hydroxide solution,
(b) Slowly adding 7.02 g of sodium silicate solution to the sodium hydroxide solution with constant stirring to form an alkaline sodium silicate solution. The sodium silicate solution has a Na2O : SiO2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm3 and a viscosity of 400 centipoise,
(c) Adding 2.0 grams of borax to the sodium silicate solution with continuous stirring, and (d) Adding 35.57 g of New Zealand flyash to the sodium silicate solution with continuous stirring to form the reagent solution. Table 1 below provides a typical composition for New Zealand flyash.
(e) Pouring the reagent solution into a mould and allowing it to set at ambient temperature, and (f) Curing the resultant solid at 90°C for 16 hours in a drying oven.
In this embodiment the invention comprises a geopolymer with a set time of 50 minutes and a composition having the following oxide molar ratios:
SiO2 / Al2O3 = 4.5;
Na2O / SiO2 = 0.15; H2O / Na2O = 10.5;
B2O3 / H2O = 0.02; and
Na2O / B2O3 = 4
EXAMPLE 3
An example of a further embodiment of the invention comprises the formation of a geopolymer by the steps comprising:
(a) Dissolving 1.82 g of sodium hydroxide in 3.69 g of water to form a sodium hydroxide solution, (b) Slowly adding 7.02 g of sodium silicate solution to the sodium hydroxide solution with constant stirring to form an alkaline sodium silicate solution. The sodium silicate solution has a Na2O : SiO2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm3 and a viscosity of 400 centipoise,
(c) Adding 2.0 grams of lithium pyroborate to the sodium silicate solution with continuous stirring, and
(d) Adding 35.57 g of New Zealand flyash to the sodium silicate solution with continuous stirring to form the reagent solution. Table 1 below provides a typical composition for New Zealand flyash.
(e) Pouring the reagent solution into a mould and allowing it to set at ambient temperature, and
(f) Curing the resultant solid at 90°C for 16 hours in a drying oven.
In this embodiment the invention comprises a geopolymer with a set time of 75 minutes and a composition having the following oxide molar ratios:
SiO2 / Al2O3 = 4.5;
Na2O / SiO2 = 0.12;
H2O / Na2O = 14.5;
B2O3 / H2O = 0.03; and Na2O / B2O3 = 2.2
Figure 7 is an XRD pattern of a geopolymer of this embodiment of the invention.
EXAMPLE 4
An example of a further embodiment of the invention comprises the formation of a geopolymer by the steps comprising:
(a) Dissolving 1.86 g of sodium hydroxide in 3.70 g of water to form a sodium hydroxide solution,
(b) Slowly adding 7.02 g of sodium silicate solution to the sodium hydroxide solution with constant stirring to form an alkaline sodium silicate solution. The sodium silicate solution has a Na2O : SiO2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm3 and a viscosity of 400 centipoise,
(c) Adding 6.0 grams of borax to the sodium silicate solution with continuous stirring, and (d) Adding 35.57 g of New Zealand flyash to the sodium silicate solution with continuous stirring to form the reagent solution. Table 1 below provides a typical composition for New Zealand flyash. (e) Pouring the reagent solution into a mould and allowing it to set at ambient temperature for 1 hour, and
(f) Curing the resultant solid at 90°C for 16 hours in a drying oven. In this embodiment the invention comprises a geopolymer with a set time of 120 minutes and a composition having the following oxide molar ratios: SiO2 / Al2O3 = 4.5; Na2O / SiO2 - 0.15; H2O / Na2O - 12.6; B2O3 / H2O = 0.05; and Na2O / B2O3 = 1.7
EXAMPLE 5
An example of a further embodiment of the invention comprises the formation of a geopolymer by the steps comprising: (a) Dissolving 1.82 g of sodium hydroxide in 3.69 g of water to form a sodium hydroxide solution,
(b) Slowly adding 7.02 g of sodium silicate solution to the sodium hydroxide solution with constant stirring to form an alkaline sodium silicate solution. The sodium silicate solution has a Na2O : SiO2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm3 and a viscosity of 400 centipoise,
(c) Adding 4.0 grams of lithium pyroborate to the sodium silicate solution with continuous stirring, and
(d) Adding 35.57 g of New Zealand flyash to the sodium silicate solution with continuous stirring to form the reagent solution. Table 1 below provides a typical composition for New Zealand flyash.
(e) Pouring the reagent solution into a mould and allowing it to set at ambient temperature for 1 hour, and
(f) Curing the resultant solid at 90°C for 16 hours in a drying oven.
In this embodiment the invention comprises a geopolymer with a set time of 225 minutes and a composition having the following oxide molar ratios: SiO2 / Al2O3 = 4.5; Na2O / SiO2 = 0.12; H2O /Na2O = 14.5; B203 / H2O = 0.06; and Na2O / B2O3 = l.l
EXAMPLE 6
An example of a further embodiment of the invention comprises the formation of a geopolymer by the steps comprising:
(a) Dissolving 1.86 g of sodium hydroxide in 2.47 g of water to form a sodium hydroxide solution,
(b) Slowly adding 7.02 g of sodium silicate solution to the sodium hydroxide solution with constant stirring to form an alkaline sodium silicate solution. The sodium silicate solution has a Na O : SiO2 ratio of 3.22, a solids weight % of 40, a density of 1.41 g/cm3 and a viscosity of 400 centipoise,
(c) Adding 10.0 grams of borax to the sodium silicate solution with continuous stirring, and (d) Adding 35.57 g of New Zealand flyash to the sodium silicate solution with continuous stirring to form the reagent solution. Table 1 below provides a typical composition for New Zealand flyash.
(e) Pouring the reagent solution into a mould and allowing it to set at ambient temperature, and (f) Curing the resultant solid at 90°C for 16 hours in a drying oven.
In this embodiment the invention comprises a geopolymer with a set time of 160 minutes and a composition having the following oxide molar ratios:
SiO2 / Al2O3 = 4.5;
Na2O / SiO2 = 0.2; H2O / Na2O = 10.7;
B2O3 / H2O = 0.08; and
Na2O / B2O3 = l.l
Figure imgf000019_0001
Figure imgf000019_0002
COMPRESSIVE STRENGTH TESTING:
The compressive strengths of the geopolymer products were determined using a 100-ton testing machine in accordance with standard cement testing procedures. Samples were characterised by solid state magic angle spinning nuclear magnetic resonance (SS MAS NMR) and X-ray diffraction (XRD) techniques.
Figure 1 illustrates the relationships between the addition of borax and subsequent set time for a geopolymer of the invention. The normal maximum set time achieved for this formulation without addition of borax was found to be 15 minutes. This was extended to 45 minutes by addition of 10% by weight of borax.
Table 3 illustrates the interrelationships between the water, sodium and boron concentrations and their effects on the compressive strengths and set times of the
Figure imgf000020_0001
geopolymers of the invention. Compressive strengths of boron-containing geopolymers comparable to those reported for conventional geopolymers were achieved through reduction of the water and alkali content without compromise of workability. The amount of silicate solution was kept at the same level to ensure enough soluble silica was available for the geopolymerisation reaction to occur. Moreover, extended set times could only be achieved by addition of boron to the formulations.
The examples above describe a method of preparing geopolymer materials based on New Zealand flyash, the setting times of which can be controlled, thereby enabling New Zealand flyash to be utilised as a viable feedstock for geopolymer synthesis. However, it will be appreciated by one skilled in the art that other flyashes and other aluminosilicate sources may also be used. In addition to control of set time, this method also produces a new family of geopolymers not previously described.
NMR ANALYSIS: SS MAS NMR was carried out to determine if and how the boron had been incorporated into the structure of the geopolymer material. Figures 2-5 show the characteristic NMR spectra for the major matrix components, namely aluminium, silicon, sodium and, in this new class of geopolymers, boron.
Figure 2 shows that the aluminium is predominantly in tetrahedral sites, as expected. In figure 3, silicon exhibits a range of sites but is predominantly saturated in aluminium. In figure 4, the sodium spectrum indicates that most of the sodium is located within the geopolymer pores rather than within the framework of the structure.
The borax starting material exhibits two coordination geometries: trigonal boron (BO3 structural unit) and tetrahedral (BO structural unit). In contrast, the πB NMR spectrum of the hardened geopolymer product exhibits only tetrahedral boron (Figure 5). This would be expected if the boron formed an integral part of the structure and indicates that it may be in part substituting for tetrahedral aluminium or silicon. The differences in the spectra of the raw material and the final product strongly suggest that the boron is playing a crucial role in the formation of the geopolymer, i.e. the boron has entered the structure and formed a geopolymer based on a boroaluminosilicate framework.
A geopolymer with a framework of boroaluminosilicate units conforms to the accepted definition of a geopolymeric material, being amorphous and consisting of a randomly arranged framework of aluminosilicate units charge-balanced by univalent or divalent metal cations. This is therefore a class of geopolymer not previously reported in the literature.
XRD ANALYSIS:
Since geopolymers do not exhibit long-range order, the X-ray diffraction pattern of these materials is typically amorphous. Figures 6 and 7 show that the same is true of the boron-containing geopolymers. Some residual unreacted quartz from the flyash is apparent as the strong peaks in the spectrum. The lack of evidence for any crystalline boron-containing compounds in conjunction with the NMR results also strongly indicates that the boron has been incorporated as an essential part of the geopolymer structure. The X-ray diffraction pattern of the boron-containing material also shows that this new class of boroaluminosilicate geopolymer conforms to the accepted definition of "geopolymer" in as far as it is an amorphous material based on an aluminosilicate framework.
INDUSTRIAL APPLICATION
Without wishing to be bound by any particular theory it is believed that the presence of calcium oxide in aluminosilicate sources leads to rapid set times, and that the inclusion of boron lengthens this set time. This allows for the first time the use of aluminosilicate sources such as Flyash Class C with acceptable set times. It is further believed that the boron adopts tetrahedral sites in the geopolymer matrix, hence creating a novel family of boroaluminosilicates.
These compositions of the invention have application in the construction industry, including as novel cementing systems, for example pre-cast product fabrication, as refractory materials, as encapsulants for hazardous, toxic and radioactive waste steams, and as fire resistant materials.
Where in the foregoing description reference has been made to elements or integers having known equivalents, then such equivalents are included as if they were individually set forth.
Although the invention has been described by way of example and with reference to particular embodiments, it is to be understood that modifications and/or improvements may be made without departing from the scope or spirit of the invention.
In addition, where features or aspects of the invention are described in terms of Markush groups, those skilled in the art will recognise that the invention is also thereby described in terms of any individual member or subgroup of members of the Markush group.

Claims

CLAIMS:
1. A geopolymer composition comprising the oxide molar ratios: (a) SiO2/Al2O3 = 3.0-6.5;
(b) M2O/SiO2 = 0.07 -0.20;
(c) H2O/M2O = 8.0 -19.0;
(d) B2O3/H2O = 0.01 -0.2; and
(e) M2O/B2O3 = 0.5-6.0 wherein M is a Group I metal.
2. A geopolymer composition as claimed in claim 1 wherein the B2O3 / H2O molar ratio is between 0.01 and 0.1.
3. A geopolymer composition as claimed in claims 1 or 2 comprising the oxide molar ratios:
(a) SiO2/Al2O3 = 4.0-5.0;
(b) M2O/SiO2 = 0.10 -0.15;
(c) H2O/M2O = 10.0 -17.0; (d) B2O3 / H2O = 0.02 - 0.06; and
(e) M2O/B2O3 = 1.0-4.0. wherein M is a Group I metal.
4. A geopolymer composition as claimed in any of the preceding claims wherein M is selected from one or more of Li, Na, K, Rb and Cs.
5. A geopolymer composition of formula (I) (yNa2O:zK2O):vB2O3:Al2O3:xSiO2:wH2O Formula (I) wherein in the fully hydrated form, w is between about 10 and about 20, v has a value between about 0.2 and about 2, x has a value between about 5 and about 10, and y and z have values such that the sum of their values totals 1.
6. A geopolymer composition as claimed in claim 5, wherein in the fully hydrated form, w is between about 10 and about 15, v has a value between about 0.5 and about
1.0, x has a value between about 5 and about 8, and y and z have values such that the sum of their values totals 1.
7. A geopolymer composition formed from a reagent mixture comprising or including: a Group I metal silicate; an aluminosilicate; boron and/or a boron containing compound; a Group I metal hydroxide; and water.
8. A geopolymer composition as claimed in claim 7, wherein the Group I metal hydroxide is in solution and is selected from one or more of LiOH, NaOH, KOH, RbOH and CsOH.
9. A geopolymer composition as claimed in claim 7, wherein the Group I metal silicate is sodium silicate or potassium silicate.
10. A geopolymer composition as claimed in claim 7, wherein the aluminosilicate is selected from the group comprising flyash class C, flyash class F, metakaolin, pumice, allophane, bentonite and ground slag.
11. A geopolymer composition as claimed in claim 10, wherein the aluminosilicate is flyash class C.
12. A geopolymer composition as claimed in claim 7, wherein the boron containing compound is selected from an anhydrous or hydrated Group I metal borates, or a pure oxides of boron.
13. A geopolymer composition as claimed in claim 12, wherein the boron containing compound is borax (hydrated sodium borate).
14. A geopolymer composition as claimed in any preceding claim comprising: about 5% to about 25% of Group I metal silicates; about 40% to about 70% of aluminosilicate; about 1% to about 25% of boron; about 1% to about 25% of Group I metal hydroxide; and about 5% to about 25% of water.
15. A geopolymer composition as claimed in claim 14 comprising: 10% to
20% of Group I metal silicates; 60% to 70% of aluminosilicate; 5% to 10% of boron; 1% to 5% of Group I metal hydroxide; and 5% to 20% of water.
16. A geopolymer composition as claimed in claim 15 including: 10% to 15% of Group I metal silicates; and 5% to 10% of water.
17. A method of forming a geopolymer composition comprising or including the steps of: adding an aluminosilicate source to a reagent mixture comprising or including boron and/or a boron containing compound and an alkaline Group I metal silicate solution.
18. A method of forming a geopolymer composition of the invention, the method comprising or including the steps of: a. mixing boron and/or a boron containing compound with an alkaline Group I metal silicate solution; b. adding an aluminosilicate to the alkaline Group I metal silicate solution formed in (a) to produce a geopolymer reagent mixture; and c. allowing the geopolymer reagent mixture formed in (b) to set and thereby form a geopolymer composition.
19. A method as claimed in claims 17 or 18, wherein the Group I metal silicate is sodium silicate or potassium silicate.
20. A method as claimed in claims 17 or 18, wherein the aluminosilicate is selected from the group comprising flyash class C, flyash class F, metakaolin, pumice, allophane, bentonite and ground slag.
21. A method as claimed claim 20, wherein the aluminosilicate is flyash class C.
22. A method as claimed in claims 17 or 18, wherein the boron containing compound is selected from an anhydrous or hydrated Group I metal borate or a pure oxide of boron.
23. A method as claimed in claim 22, wherein the boron containing compound is borax (hydrated sodium borate).
24. A method as claimed in claims 17 or 18, wherein the Group I metal silicate solution is selected from commercially available Group I metal silicate solutions or solutions of a commercially available Group I metal silicate and water.
25. A method as claimed in claims 17 or 18, wherein the Group I metal silicate solution is provided by mixing a Group I metal silicate solution with an alkaline hydroxide solution.
26. A method as claimed in claim 25, wherein the Group I metal silicate and the alkaline hydroxide solution have the same cation.
27. A method as claimed in claim 26 wherein the cation is selected from the group comprising Li, Na, K, Rb and Cs.
28. A method as claimed in claims 17 or 18, wherein the Group I metal silicate is present in a weight % of about 30% to about 55% of the solution.
29. A method as claimed in claim 28 wherein the Group I metal silicate is present in a weight % of 35% to 40% of the solution.
30. A method as claimed in claims 17 or 18, wherein the weight % of boron added to the mixture is from about 1% to about 25%.
31. A method as claimed in claim 30, wherein the weight % of boron added to the mixture is from 1% to 10%.
32. A method as claimed in claim 31, wherein the weight % of boron added to the mixture is from 5% to 10%.
33. A method as claimed in claims 17 or 18, wherein the aluminosilicate is added as a weight % of about 40% to about 70%).
34. A method as claimed in claim 33, wherein the aluminosilicate is added as a weight % of 60 % to 70 %.
35. A method as claimed in claims 17 or 18, wherein the method is carried out at a pH between about 10 and 14.
36. A method as claimed in claims 17 or 18, further including the preliminary steps of preparing a Group I metal silicate solution by the steps of: i. adding a Group I metal compound to water to form a Group I metal ion solution; and ii. dissolving a silicate in the Group I metal ion solution to form a Group I metal silicate solution.
37. A method as claimed in claims 17 or 18, further including the subsequent step of: d. leaving the geopolymer composition to stand to set for a desired time according to the amount of boron added.
38. A method as claimed in claim 37, wherein the set time is between about 10 and about 720 minutes.
39. A method as claimed in claim 38, wherein the set time is between 10 and 120 minutes.
40. A method as claimed in claim 39, wherein the set time is between 15 and 45 minutes.
41. A method as claimed in claim 37, wherein the setting occurs at room temperature.
42. In another aspect the invention provides a geopolymer composition when produced by a method of any one of claims 17 to 40.
43. A method of producing a shaped geopolymer composition comprising or including the steps of: a. carrying out the method of any one of claims 17 to 36 to obtain a geopolymer reagent mixture; b. prior to setting, transferring the geopolymer reagent mixture to a shaping device; c. allowing the geopolymer reagent mixture to set to form a shaped geopolymer composition; and d. curing the shaped geopolymer composition.
44. A method as claimed in claim 43, wherein the shaping device is selected from the group comprising moulds, dies and casts.
45. A method as claimed in claim 43, wherein the geopolymer composition is cured by dry heating, fan-assisted heating, steam curing or immersion in water.
46. A method as claimed in claim 45, wherein the geopolymer composition is cured by dry heating or steam curing.
47. A method as claimed in claim 43, wherein the geopolymer composition is cured at a temperature between about 30 and about 120°C.
48. A method as claimed in claim 47, wherein the geopolymer composition is cured at a temperature between 50 and 100°C.
49. A method as claimed in claim 48, wherein the geopolymer composition is cured at a temperature between 80 and 100°C.
50. A method as claimed in claim 49, wherein the geopolymer composition is cured at 90°C.
51. A method as claimed in claim 43, wherein time taken to cure the geopolymer composition is between about 1 and about 24 hours.
52. A method as claimed in claim 51, wherein time taken to cure the geopolymer composition is between 12 and 24 hours.
53. A method as claimed in claim 52, wherein time taken to cure the geopolymer composition is between 12 and 18 hours.
54. In another aspect the invention provides a shaped geopolymer composition when produced by a method of the invention.
55. A geopolymer composition substantially as herein described with reference to any one or more of the examples and with or without reference to the accompanying drawings.
56. A method substantially as herein described with reference to any one or more of the examples and with or without reference to the accompanying drawings.
PCT/NZ2004/000193 2003-08-22 2004-08-20 Geopolymers and methods for their production WO2005019130A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NZ527772A NZ527772A (en) 2003-08-22 2003-08-22 Alkali activated fly ash based geopolymer cements and methods for their production
NZ527772 2003-08-22

Publications (1)

Publication Number Publication Date
WO2005019130A1 true WO2005019130A1 (en) 2005-03-03

Family

ID=34214935

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NZ2004/000193 WO2005019130A1 (en) 2003-08-22 2004-08-20 Geopolymers and methods for their production

Country Status (2)

Country Link
NZ (1) NZ527772A (en)
WO (1) WO2005019130A1 (en)

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1801084A1 (en) * 2005-12-20 2007-06-27 Pavel Svoboda Fly-ash concrete compositon, method of preparation by geo-polymeric reaction of activated fly-ash and its use.
WO2008012438A2 (en) * 2006-07-28 2008-01-31 Red Lion Cement Technology Limited Geopolymeric cement based on fly ash and harmless to use
EP1887064A1 (en) * 2006-08-07 2008-02-13 Services Pétroliers Schlumberger Geopolymer composition and application for carbon dioxide storage
EP1887065A1 (en) * 2006-08-07 2008-02-13 Services Pétroliers Schlumberger Geopolymer composition and application in oilfield industry
WO2008017414A1 (en) * 2006-08-07 2008-02-14 Services Petroliers Schlumberger Pumpable geopolymer formulation for oilfield application
WO2008017109A1 (en) * 2006-08-07 2008-02-14 Alcoa Of Australia Limited Method for management of contaminants in alkaline process liquors
WO2006121823A3 (en) * 2005-05-09 2008-08-21 Corning Inc Geopolymer composites and structures formed therefrom
EP2093200A1 (en) 2008-02-19 2009-08-26 Services Petroliers Schlumberger Pumpable geopolymer formulation for oilfield application
US7794537B2 (en) 2006-08-07 2010-09-14 Schlumberger Technology Corporation Geopolymer composition and application in oilfield industry
WO2011020975A2 (en) 2009-08-21 2011-02-24 Laboratoire Central Des Ponts Et Chaussees Geopolymer cement and use thereof
WO2011072784A1 (en) 2009-12-17 2011-06-23 Services Petroliers Schlumberger Pumpable geopolymers comprising a mixing aid and dispersing agent
WO2011072786A1 (en) 2009-12-17 2011-06-23 Services Petroliers Schlumberger (Sps) Pumpable geopolymers comprising a setting accelerator
WO2011072785A1 (en) 2009-12-17 2011-06-23 Services Petroliers Schlumberger (Sps) Pumpable geopolymers comprising a fluid-loss agent
EP2385029A1 (en) 2010-05-03 2011-11-09 Services Pétroliers Schlumberger Compositions and method for well cementing
EP2389345A2 (en) * 2009-01-22 2011-11-30 The Catholic University Of America Tailored geopolymer composite binders for cement and concrete applications
CN102491658A (en) * 2011-12-08 2012-06-13 湖南科技大学 Method for preparing geopolymeric material from bentonite
WO2013044016A3 (en) * 2011-09-21 2013-05-30 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Geopolymer resin materials, geopolymer materials, and materials produced thereby
WO2014028792A1 (en) * 2012-08-16 2014-02-20 Halliburton Energy Services, Inc. Geopolymer cement compositions and methods of use
EP2727894A1 (en) 2012-10-30 2014-05-07 Sociedad Anónima Minera Catalano-Aragonesa Forming of ceramic materials made with inorganic polymers
EP1971562B1 (en) 2005-12-06 2015-03-18 James Hardie Technology Limited Method of manufacture of shaped geopolymeric particles
US9242900B2 (en) 2009-12-01 2016-01-26 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Porous geopolymer materials
CZ305657B6 (en) * 2009-11-05 2016-01-27 Unipetrol Výzkumně Vzdělávací Centrum, A. S. Liquid geopolymeric resin for producing volume-stable reinforced composites and process for producing thereof
WO2016032896A1 (en) * 2014-08-27 2016-03-03 Louisiana Tech University Foundation; A Division Of Louisiana Tech University Foundation, Inc. Geopolymer with nanoparticle retardant and method
US9308511B2 (en) 2009-10-14 2016-04-12 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Fabricating porous materials using thixotropic gels
US9365691B2 (en) 2010-08-06 2016-06-14 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Fabricating porous materials using intrepenetrating inorganic-organic composite gels
CN107074651A (en) * 2014-08-13 2017-08-18 保利阿格有限公司 The aggregate of geo-polymer and geo-polymer
EP3378847A1 (en) 2017-03-21 2018-09-26 Sociedad Anónima Minera Catalano-Aragonesa Procedure for decorating ceramic materials produced with inorganic polymers
CN109081640A (en) * 2018-09-13 2018-12-25 福建瑞森水泥制品发展有限公司 A kind of geo-polymer composite pole and preparation method thereof
US10170759B2 (en) 2013-06-21 2019-01-01 Arizona Board Of Regents On Behalf Of Arizona State University Metal oxides from acidic solutions
CN109678406A (en) * 2019-03-05 2019-04-26 西南科技大学 A kind of preparation method of porous pollucite profile
US20190202739A1 (en) * 2017-12-19 2019-07-04 Nexans Device Comprising a Cable or a Cable Accessory Containing a Fire-Resistant Composite Layer
CN110204261A (en) * 2019-05-28 2019-09-06 广西大学 A kind of low viscosity lower shrinkage geology polymer material and preparation method thereof
US10544060B2 (en) 2015-03-27 2020-01-28 Hoffmann Green Cement Technologies Composition for metakaolin construction material, related method for manufacturing said composition, and use for producing construction elements
US10829382B2 (en) 2017-01-20 2020-11-10 Skysong Innovations Aluminosilicate nanorods
US10926241B2 (en) 2014-06-12 2021-02-23 Arizona Board Of Regents On Behalf Of Arizona State University Carbon dioxide adsorbents
CN116003009A (en) * 2022-12-28 2023-04-25 长安大学 Fly ash base polymer for roadbed improvement layer and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5116217A (en) * 1974-07-31 1976-02-09 Aikoh Co Yokono aruminakaizaibutsukyushu narabini hoonyofunmatsusoseibutsu
JPS53147722A (en) * 1977-05-30 1978-12-22 Nisshin Eng Inorganic coating composition
JPS5614463A (en) * 1979-07-18 1981-02-12 Giichi Sawara Method of producing aciddproof cement of high resistance to water
US4640715A (en) * 1985-03-06 1987-02-03 Lone Star Industries, Inc. Mineral binder and compositions employing the same
US4906408A (en) * 1987-12-02 1990-03-06 Commissariat A L'energie Atomique Means for the conditioning of radioactive or toxic waste in cement and its production process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5116217A (en) * 1974-07-31 1976-02-09 Aikoh Co Yokono aruminakaizaibutsukyushu narabini hoonyofunmatsusoseibutsu
JPS53147722A (en) * 1977-05-30 1978-12-22 Nisshin Eng Inorganic coating composition
JPS5614463A (en) * 1979-07-18 1981-02-12 Giichi Sawara Method of producing aciddproof cement of high resistance to water
US4640715A (en) * 1985-03-06 1987-02-03 Lone Star Industries, Inc. Mineral binder and compositions employing the same
US4906408A (en) * 1987-12-02 1990-03-06 Commissariat A L'energie Atomique Means for the conditioning of radioactive or toxic waste in cement and its production process

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 1976, Derwent World Patents Index; Class L02, AN 1976-23059X *
DATABASE WPI Week 1978, Derwent World Patents Index; Class G02, AN 1978-10724B *
DATABASE WPI Week 1981, Derwent World Patents Index; Class L02, AN 1981-24337D *

Cited By (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7745363B2 (en) 2005-05-09 2010-06-29 Corning Incorporated Geopolymer composites and structures formed therefrom
WO2006121823A3 (en) * 2005-05-09 2008-08-21 Corning Inc Geopolymer composites and structures formed therefrom
EP1971562B1 (en) 2005-12-06 2015-03-18 James Hardie Technology Limited Method of manufacture of shaped geopolymeric particles
EP1801084A1 (en) * 2005-12-20 2007-06-27 Pavel Svoboda Fly-ash concrete compositon, method of preparation by geo-polymeric reaction of activated fly-ash and its use.
WO2008012438A3 (en) * 2006-07-28 2008-03-13 Cordi Geopolymere Sarl Geopolymeric cement based on fly ash and harmless to use
WO2008012438A2 (en) * 2006-07-28 2008-01-31 Red Lion Cement Technology Limited Geopolymeric cement based on fly ash and harmless to use
FR2904307A1 (en) * 2006-07-28 2008-02-01 Joseph Davidovits GEOPOLYMERIC CEMENT BASED ON FLY ASH AND A HIGH SAFETY OF USE.
CN101541707B (en) * 2006-07-28 2012-11-07 红狮子水泥技术有限公司 Geopolymeric cement based on fly ash and harmless to use
WO2008017413A1 (en) * 2006-08-07 2008-02-14 Services Petroliers Schlumberger Pumpable geopolymer formulation and application for carbon dioxide storage
EP1887064A1 (en) * 2006-08-07 2008-02-13 Services Pétroliers Schlumberger Geopolymer composition and application for carbon dioxide storage
AU2007283145B2 (en) * 2006-08-07 2013-03-28 Schlumberger Technology B.V. Pumpable geopolymer formulation and application for carbon dioxide storage
WO2008017109A1 (en) * 2006-08-07 2008-02-14 Alcoa Of Australia Limited Method for management of contaminants in alkaline process liquors
US7794537B2 (en) 2006-08-07 2010-09-14 Schlumberger Technology Corporation Geopolymer composition and application in oilfield industry
US7846250B2 (en) * 2006-08-07 2010-12-07 Schlumberger Technology Corporation Geopolymer composition and application for carbon dioxide storage
AU2007283146B2 (en) * 2006-08-07 2013-03-28 Schlumberger Technology B.V. Pumpable geopolymer formulation for oilfield application
AU2007283446B2 (en) * 2006-08-07 2013-11-14 Alcoa Of Australia Limited Method for management of contaminants in alkaline process liquors
WO2008017414A1 (en) * 2006-08-07 2008-02-14 Services Petroliers Schlumberger Pumpable geopolymer formulation for oilfield application
NO347297B1 (en) * 2006-08-07 2023-09-04 Schlumberger Technology Bv Pumpable geopolymer mixture for use in oil fields
EP1887065A1 (en) * 2006-08-07 2008-02-13 Services Pétroliers Schlumberger Geopolymer composition and application in oilfield industry
EP2093200A1 (en) 2008-02-19 2009-08-26 Services Petroliers Schlumberger Pumpable geopolymer formulation for oilfield application
EP2389345A2 (en) * 2009-01-22 2011-11-30 The Catholic University Of America Tailored geopolymer composite binders for cement and concrete applications
US9834479B2 (en) 2009-01-22 2017-12-05 The Catholic University Of America Tailored geopolymer composite binders for cement and concrete applications
EP2389345A4 (en) * 2009-01-22 2013-08-14 Univ America Catholic Tailored geopolymer composite binders for cement and concrete applications
WO2011020975A2 (en) 2009-08-21 2011-02-24 Laboratoire Central Des Ponts Et Chaussees Geopolymer cement and use thereof
US8444763B2 (en) 2009-08-21 2013-05-21 Institut Francais Des Sciences Et Technologies Des Transports, De L'amenagement Et Des Reseaux Geopolymer cement and use therof
US9308511B2 (en) 2009-10-14 2016-04-12 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Fabricating porous materials using thixotropic gels
CZ305657B6 (en) * 2009-11-05 2016-01-27 Unipetrol Výzkumně Vzdělávací Centrum, A. S. Liquid geopolymeric resin for producing volume-stable reinforced composites and process for producing thereof
US9242900B2 (en) 2009-12-01 2016-01-26 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Porous geopolymer materials
US8535437B2 (en) 2009-12-17 2013-09-17 Schlumberger Technology Corporation Pumpable geopolymers comprising a fluid-loss agent
WO2011072785A1 (en) 2009-12-17 2011-06-23 Services Petroliers Schlumberger (Sps) Pumpable geopolymers comprising a fluid-loss agent
WO2011072786A1 (en) 2009-12-17 2011-06-23 Services Petroliers Schlumberger (Sps) Pumpable geopolymers comprising a setting accelerator
US9206343B2 (en) 2009-12-17 2015-12-08 Schlumberger Technology Corporation Pumpable geopolymers comprising a setting accelerator
US9222010B2 (en) 2009-12-17 2015-12-29 Schlumberger Technology Corporation Pumpable geopolymers comprising a mixing aid and dispersing agent
WO2011072784A1 (en) 2009-12-17 2011-06-23 Services Petroliers Schlumberger Pumpable geopolymers comprising a mixing aid and dispersing agent
US9394202B2 (en) 2010-05-03 2016-07-19 Schlumberger Technology Corporation Compositions and methods for well cementing
EP2385029A1 (en) 2010-05-03 2011-11-09 Services Pétroliers Schlumberger Compositions and method for well cementing
US9365691B2 (en) 2010-08-06 2016-06-14 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Fabricating porous materials using intrepenetrating inorganic-organic composite gels
CN103946181A (en) * 2011-09-21 2014-07-23 亚利桑那州立大学董事会(代理及代表亚利桑那州立大学的法人团体) Geopolymer resin materials, geopolymer materials, and materials produced thereby
US9296654B2 (en) 2011-09-21 2016-03-29 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Geopolymer resin materials, geopolymer materials, and materials produced thereby
US20140342156A1 (en) * 2011-09-21 2014-11-20 Dong-kyun Seo Geopolymer resin materials, geopolymer materials, and materials produced thereby
US20160168032A1 (en) * 2011-09-21 2016-06-16 Dong-kyun Seo Geopolymer resin materials, geopolymer materials, and materials produced thereby
CN109776032A (en) * 2011-09-21 2019-05-21 亚利桑那州立大学董事会(代理及代表亚利桑那州立大学的法人团体) Geopolymer resin material, geopolymer and material prepared therefrom
WO2013044016A3 (en) * 2011-09-21 2013-05-30 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Geopolymer resin materials, geopolymer materials, and materials produced thereby
US9862644B2 (en) 2011-09-21 2018-01-09 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University Geopolymer resin materials, geopolymer materials, and materials produced thereby
CN102491658A (en) * 2011-12-08 2012-06-13 湖南科技大学 Method for preparing geopolymeric material from bentonite
US9346711B2 (en) 2012-08-16 2016-05-24 Halliburton Energy Services, Inc. Geopolymer cement compositions and methods of use
WO2014028792A1 (en) * 2012-08-16 2014-02-20 Halliburton Energy Services, Inc. Geopolymer cement compositions and methods of use
US9840653B2 (en) 2012-08-16 2017-12-12 Halliburton Energy Services, Inc. Geopolymer cement compositions and methods of use
EP2727894A1 (en) 2012-10-30 2014-05-07 Sociedad Anónima Minera Catalano-Aragonesa Forming of ceramic materials made with inorganic polymers
US10170759B2 (en) 2013-06-21 2019-01-01 Arizona Board Of Regents On Behalf Of Arizona State University Metal oxides from acidic solutions
US11745163B2 (en) 2014-06-12 2023-09-05 Arizona Board Of Regents On Behalf Of Arizona State University Carbon dioxide adsorbents
US10926241B2 (en) 2014-06-12 2021-02-23 Arizona Board Of Regents On Behalf Of Arizona State University Carbon dioxide adsorbents
CN107074651A (en) * 2014-08-13 2017-08-18 保利阿格有限公司 The aggregate of geo-polymer and geo-polymer
US10239786B2 (en) 2014-08-13 2019-03-26 Polyagg Pty Ltd Geopolymers and geopolymer aggregates
US10087107B2 (en) 2014-08-27 2018-10-02 Louisiana Tech Research Corporation Geopolymer with nanoparticle retardant and method
WO2016032896A1 (en) * 2014-08-27 2016-03-03 Louisiana Tech University Foundation; A Division Of Louisiana Tech University Foundation, Inc. Geopolymer with nanoparticle retardant and method
US9604880B2 (en) 2014-08-27 2017-03-28 Louisiana Tech Research Corporation Geopolymer with nanoparticle retardant and method
US10544060B2 (en) 2015-03-27 2020-01-28 Hoffmann Green Cement Technologies Composition for metakaolin construction material, related method for manufacturing said composition, and use for producing construction elements
US10829382B2 (en) 2017-01-20 2020-11-10 Skysong Innovations Aluminosilicate nanorods
EP3378847A1 (en) 2017-03-21 2018-09-26 Sociedad Anónima Minera Catalano-Aragonesa Procedure for decorating ceramic materials produced with inorganic polymers
US20190202739A1 (en) * 2017-12-19 2019-07-04 Nexans Device Comprising a Cable or a Cable Accessory Containing a Fire-Resistant Composite Layer
US10961156B2 (en) * 2017-12-19 2021-03-30 Nexans Device comprising a cable or a cable accessory containing a fire-resistant composite layer
CN109081640A (en) * 2018-09-13 2018-12-25 福建瑞森水泥制品发展有限公司 A kind of geo-polymer composite pole and preparation method thereof
CN109678406A (en) * 2019-03-05 2019-04-26 西南科技大学 A kind of preparation method of porous pollucite profile
CN110204261A (en) * 2019-05-28 2019-09-06 广西大学 A kind of low viscosity lower shrinkage geology polymer material and preparation method thereof
CN116003009A (en) * 2022-12-28 2023-04-25 长安大学 Fly ash base polymer for roadbed improvement layer and preparation method thereof
CN116003009B (en) * 2022-12-28 2023-08-11 长安大学 Fly ash base polymer for roadbed improvement layer and preparation method thereof

Also Published As

Publication number Publication date
NZ527772A (en) 2005-10-28

Similar Documents

Publication Publication Date Title
WO2005019130A1 (en) Geopolymers and methods for their production
US9834479B2 (en) Tailored geopolymer composite binders for cement and concrete applications
Fernández-Jiménez et al. The role played by the reactive alumina content in the alkaline activation of fly ashes
Guo et al. Compressive strength and microstructural characteristics of class C fly ash geopolymer
KR101621029B1 (en) Single-phase hydraulic binder, methods for the production thereof and building material produced therewith
Li et al. Properties and mechanism of high-magnesium nickel slag-fly ash based geopolymer activated by phosphoric acid
Zhang et al. Structure characterization of hydration products generated by alkaline activation of granulated blast furnace slag
KR101621024B1 (en) Single-phase hydraulic binder, methods for the production thereof and structural material produced therewith
Zulkifly et al. Effect of phosphate addition on room-temperature-cured fly ash-metakaolin blend geopolymers
JP2016534964A (en) Self-foaming geopolymer composition containing aluminum dross
Kumar et al. Microstructural properties of alkali-activated metakaolin and bottom ash geopolymer
Shekhovtsova et al. Effect of activator dosage, water-to-binder-solids ratio, temperature and duration of elevated temperature curing on the compressive strength of alkali-activated fly ash cement pastes
Snellings et al. In situ synchrotron X-ray powder diffraction study of the early age hydration of cements blended with zeolitite and quartzite fines and water-reducing agent
Kim et al. Immobilization mechanism of radioactive borate waste in phosphate-based geopolymer waste forms
Li et al. Effects of mineral admixtures and lime on disintegration of alkali-activated slag exposed to 50 C
Chithiraputhiran Kinetics of alkaline activation of slag and fly ash-slag systems
Zha et al. Experimental study on the effects of calcium-rich materials on the early compressive strength of completely decomposed granite (CDG) base-geopolymer
Sagoe-Crentsil et al. Alkali-activated binders: early age nucleation reactions, chemical phase evolution and their implications on system properties
EP0895971A1 (en) Alkaline sulfoaluminosilicate hydraulic cement and process for its manufacture
JP6831976B2 (en) Shrinkage reducing agent for geopolymer and cured geopolymer
CN118344044A (en) Additive for inhibiting alkali aggregate reaction of concrete and preparation method and application thereof
Gao et al. Chemistry, design and application of hybrid alkali activated binders
Chindaprasirt et al. Improved acid rain resistance of high calcium fly ash-sodium hydroxide geopolymer mortar cured at ambient temperature by incorporating rice husk ash
Muduli et al. Wetting and drying cycle effect on strength of geopolymer fly ash building brick
MacKenzie et al. New trends in the chemistry of inorganic polymers for advanced applications

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase