CN105621907A - Calcium-base geopolymer and preparation method thereof - Google Patents
Calcium-base geopolymer and preparation method thereof Download PDFInfo
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- CN105621907A CN105621907A CN201610030400.6A CN201610030400A CN105621907A CN 105621907 A CN105621907 A CN 105621907A CN 201610030400 A CN201610030400 A CN 201610030400A CN 105621907 A CN105621907 A CN 105621907A
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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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
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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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
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- 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
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a calcium-base geopolymer and a preparation method thereof. Granulated blast-furnace cinder, metakaolin and fly ash used as main raw materials are utilized to prepare the calcium-base geopolymer by using liquid water glass as an alkaline excitant under normal temperature conditions without high-temperature calcination. The calcium-base geopolymer is prepared from 70-90% of granulated blast-furnace cinder, 0-30% of fly ash and 0-30% of metakaolin. The alkaline excitant adopts the liquid water glass which accounts for 2-10 wt% of the multielement composite powder. Compared with the prior art, by using the granulated blast-furnace cinder, fly ash and metakaolin as the main raw materials, the calcium-base geopolymer has the advantages of low production cost and energy consumption, and embodies the idea of sustainable development on greenness and cyclic utilization. The preparation process does not need high-temperature calcination, and the calcium-base geopolymer can be prepared at normal temperature, thereby greatly saving the production cost and lowering the energy consumption. In the production process, the emissions of CO2 and other greenhouse gases are very low. The calcium-base geopolymer prepared at normal temperature has excellent mechanical properties and broad market application prospects.
Description
Technical field
The invention belongs to building material field, particularly relate to a kind of calcio geopolymer and preparation method thereof.
Background technology
Portland cement since inventing for 1824, and it applies the great development having promoted human society on a large scale, but also creates some environmental problems urgently to be resolved hurrily therewith simultaneously, and the living environment of the mankind in serious threat. Traditional portland cement adopts " two mill single firing " technique, consumes the non-renewable energy resources such as substantial amounts of oil, coal and natural gas, and its energy consumption accounts for world's total energy consumption about 15%; Also give off substantial amounts of greenhouse gases CO simultaneously2, cause global average temperature to rise year by year and by initiation such as sea level rise, a series of environmental problems such as pest and disease damage increases and huge disaster on the earth. At present, the emission factor of the unit cement carbon dioxide of developing country is generally higher than developed country, produces 1t cement and to discharge the carbon dioxide close to 1t in air. World's cement production about 2,900,000,000 tons in 2009, it is contemplated that be up to the height of 6,000,000,000 tons, rough calculation to the year two thousand fifty, the carbon dioxide of 6,000,000,000 tons will be discharged in air. The demand of cement is continuously increased along with World Economics develops rapidly, and the consumption of resource the environmental problem that produces is day by day serious. If not searching out effective measures to reduce the discharge of greenhouse gases, bring serious consequence will to the conditions of existence of the mankind. Meanwhile, concrete structure uses environment to go from bad to worse, and people's activity space constantly extends, and mechanical property and endurance quality to inorganic coagulation material require increasingly harsher. The carrying capacity of environment that the mankind are depended on for existence by the continuous production of traditional portland is increasing, and the resource of consumption gets more and more, and its drawback being not suitable with modern civilization is also completely exposed. It addition, along with industrial expansion, the industrial solid castoff of the Si-Al material such as substantial amounts of flyash, metallurgical slag, industrial residue, building castoff takies a large amount of land resource and serious environment pollution. Therefore existing portland cement system how is transformed, the novel inorganic Binder Materials of research and development low-carbon environment-friendly, it is not only demand and the calling in epoch, is also a current scientific worker important topic in the urgent need to address.
Calcio geopolymer refers to the hydraulic cementing materials being primary product with inorganic mineral high polymer that the aluminosilicate material of calcic or industrial residue and appropriate alkali-activator are made at normal temperatures. Calcio geopolymer is the high-performance inorganic polymeric material that a class is novel, is a class of most future in alkaline activity Binder Materials. Due to the inorganic polycondensation three-dimensional oxide network structure that it is special so that calcio geopolymer has the high-temperature behavior higher than macromolecular material, cement, pottery and metal and mechanical performance numerous sides; On the other hand, energy consumption and three wastes discharge amount in calcio geopolymer manufacture process are all non-normally low, material is environmentally friendly and can be recycled well, the maintenance molding at ambient temperature of this material, without maintenance of equipment and hot environment, there is the advantage that energy consumption is low, be a kind of sustainable development " green material ". But the prior art indicate that, some alkali-activated carbonatite Binder Materials have the disadvantage that with alkali slag cement prepared by single slag composition, although its intensity is high and early strength is good, but its product mostly is inorganic mineral oligomer, and its Behavior of Hardened Cement Paste shrinks and fragility is relatively big, therefore its durability is under some influence; With alkali-activated carbonatite Binder Materials prepared by the material such as metakaolin or flyash, though its product is inorganic mineral high polymer, having good endurance quality, but it needs higher curing temperature, under room temperature, its cement strength is relatively low.
Summary of the invention
For the deficiencies in the prior art, a kind of calcio geopolymer provided by the invention and preparation method thereof, the calcio geopolymer prepared by the method can make granulated blast-furnace slag, metakaolin and flyash have complementary advantages in calcio geopolymer cement stone structure forming process, water-cement ratio is greatly lowered, makes calcio geopolymer have good mechanical property and durability; Prepared calcio geopolymer is maintenance molding at ambient temperature, it is not necessary to maintenance of equipment and hot environment, has the advantage that energy consumption is low.
Realize the technical scheme of the object of the invention:
A kind of calcio geopolymer, the multiple elements design powder body being made up of granulated blast-furnace slag and metakaolin, flyash under room temperature excites at alkali-activator and obtains, and its composition of raw materials includes: 70%��90% granulated blast-furnace slag, 0��30% flyash, 10��30% metakaolins; Alkali-activator adopts the liquid glass accounting for multiple elements design powder body weight 2%��10%.
Described granulated blast-furnace slag specific surface area is 4200cm2/ g, the incorporation of granulated blast-furnace slag is preferably 80%;
Described metakaolin specific surface area is 8500cm2/ g, volume is preferably 10%;
Described flyash specific surface area is 6400cm2/ g, volume is preferably 10%;
Described liquid glass modulus n is 0.8��1.6.
The preparation method of a kind of calcio geopolymer, comprises the following steps:
1) by granulated blast-furnace slag, flyash, metakaolin according to proportioning mix homogeneously, obtaining ground granulated blast furnace slag coal ash metakaolin multiple elements design powder body, each constituent mass percentage composition of described multiple elements design powder body is: granulated blast-furnace slag 70%��90%, flyash 0��30%, metakaolin 0��30%;
2) liquid glass of different modulus n is to regulate in the undisturbed industry waterglass by chemical pure sodium hydroxide addition modulus n=3.26 to obtain, liquid glass and sodium hydroxide 1: 0.26,1: 0.24,1: 0.22,1: 0.20,1: 0.18 mix in proportion, preparation obtain modulus respectively 0.8,1.0,1.2,1.4,16 alkali activating agent solution;
3) multiple elements design powder body and alkali-activator are poured in cement mixer together stir, obtain calcio geopolymer slurry; Pouring the clean slurry being stirred in die trial vibration moulding, test specimen gang mould is put into curing temperature together and is maintained at 20 DEG C �� 1 DEG C, relative humidity, more than maintenance in the standard curing room of 90% 24 hours, continues maintenance extremely corresponding age in dampness after the demoulding. Through above-mentioned steps, calcio geopolymer can be prepared.
Beneficial effect
The invention provides a kind of calcio geopolymer and preparation method thereof, the calcio geopolymer preparation process that the method provides, without high-temperature calcination, can be prepared by normal temperatures, is greatly saved production cost, reduce energy consumption and CO in production process2Isothermal chamber gas discharging is non-normally low; This material is with the granulated blast-furnace slag of wide material sources and low cost for primary raw material; the problem solving the wasting of resources that granulated blast-furnace slag stores up for a long time and environmental pollution; calcio geopolymer has excellent mechanical property and durability; it is a kind of green and environmentally friendly Binder Materials, there is wide market application foreground.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further elaborated, but is not limitation of the invention
Embodiment
A kind of calcio geopolymer, the multiple elements design powder body being made up of granulated blast-furnace slag and metakaolin, flyash under room temperature excites at alkali-activator and obtains, and its composition of raw materials includes: 70%��90% granulated blast-furnace slag, 0��30% flyash, 10��30% metakaolins; Alkali-activator adopts the liquid glass accounting for multiple elements design powder body weight 2%��10%.
Described granulated blast-furnace slag specific surface area is 4200cm2/ g, the incorporation of granulated blast-furnace slag is preferably 80%;
Described metakaolin specific surface area is 8500cm2/ g, volume is preferably 10%;
Described flyash specific surface area is 6400cm2/ g, volume is preferably 10%;
Described liquid glass modulus n is 0.8��1.6.
By above primary raw material, it is possible to prepare the calcio geopolymer of function admirable, with low cost, environmental protection.
The preparation method of a kind of calcio geopolymer, specifically includes following steps:
1) by granulated blast-furnace slag, flyash, metakaolin according to proportioning mix homogeneously, obtaining ground granulated blast furnace slag coal ash metakaolin multiple elements design powder body, each constituent mass percentage composition of described multiple elements design powder body is: granulated blast-furnace slag 70%��90%, flyash 0��30%, metakaolin 0��30%;
2) liquid glass of different modulus n is to regulate in the undisturbed industry waterglass by chemical pure sodium hydroxide addition modulus n=3.26 to obtain, liquid glass and sodium hydroxide 1: 0.26,1: 0.24,1: 0.22,1: 0.20,1: 0.18 mix in proportion, preparation obtain modulus respectively 0.8,1.0,1.2,1.4,16 alkali activating agent solution;
3) multiple elements design powder body and alkali-activator are poured in cement mixer together stir, obtain calcio geopolymer slurry;
4) the clean slurry being stirred is poured in die trial vibration moulding, test specimen gang mould is put into together curing temperature and is maintained at 20 DEG C �� 1 DEG C, relative humidity, more than maintenance in the standard curing room of 90% 24 hours, continues maintenance in dampness and, to corresponding age, obtains calcio geopolymer after the demoulding.
Embodiment 1
The impact on the calcio geopolymer performance being primary raw material with granulated blast-furnace slag, metakaolin of the liquid glass of different moduluses
Using liquid glass as exciting agent, modulus is 0.8��1.6, the impact on calcio geopolymer performance of the liquid soluble glass of the different modulus of detection, and the preparation method of calcio geopolymer of the present invention comprises the following steps:
Market liquid waterglass adds NaOH in table 1 ratio and is configured to the liquid glass that modulus is 0.8,1.0,1.2,1.4,1.6 respectively;
By 80% (weight/mass percentage composition) graining blast-furnace cinder micro-powder and 20% (weight/mass percentage composition) metakaolin mix homogeneously, obtain granulated blast-furnace slag-metakaolin composite powder;
It is 0.45 at water-cement ratio, liquid glass volume accounts for composite granule mass ratio when being 8%, the liquid glass (the sample number into spectrum respectively A 1 of correspondence, A 2, A 3, A 4, A 5) that modulus is 0.8,1.0,1.2,1.4,1.6 is incorporated in composite granule, after agitator for cement mortar stirs 1min, inject the vibration closely knit molding of 1min in the die trial of 40mm �� 40mm �� 40mm, maintenance is to the demoulding at the standard conditions, prepares calcio geopolymer and only starches test specimen. In corresponding age, clean slurry test specimen is carried out strength test.
Test result is as shown in table 1.
The intensity of 3d, 7d, the 28d of the calcio geopolymer sample of the different modulus of water glass of table 1
As can be seen from Table 1, modulus of water glass is one of principal element affecting calcio geopolymer mechanical property. Modulus of water glass is increased to 1.6 by 0.8, and the comprcssive strength that slag is starched only reduces with the increase of liquid glass. Calcio geopolymer intensity difference prepared by modulus waterglass between 0.8��1.0 is little, shows the intensity of the calcio geopolymer prepared apparently higher than the modulus waterglass more than 1.0.
Embodiment 2
The impact on the calcio geopolymer performance being primary raw material with granulated blast-furnace slag, metakaolin of the liquid glass of different addition quantity
In market liquid waterglass, 1:0.24 adds NaOH and is configured to the liquid glass that modulus is 1.0 in proportion;
By 80% (weight/mass percentage composition) graining blast-furnace cinder micro-powder and 20% (weight/mass percentage composition) metakaolin mix homogeneously, obtain granulated blast-furnace slag-metakaolin composite powder;
It is 0.45 at water-cement ratio; liquid glass volume (by solid content) accounts for granulated blast-furnace slag mass ratio when being 2%, 4%, 6%, 8%, 10%; the waterglass of different addition quantity is incorporated in composite granule; after agitator for cement mortar stirs 1min; inject the vibration closely knit molding of 1min in the die trial of 40mm �� 40mm �� 40mm; maintenance is to the demoulding at the standard conditions, prepares calcio geopolymer and only starches test specimen. In corresponding age, clean slurry test specimen is carried out strength test.
Test result is as shown in table 2.
The intensity of 3d, 7d, the 28d of the calcio geopolymer sample of table 2 liquid glass different addition quantity
As can be seen from Table 2, along with the increase of liquid glass volume, calcio geopolymer comprcssive strength is consequently increased; Liquid glass volume increases to after to a certain degree, and the amplitude that calcio geopolymer comprcssive strength increases diminishes.
Embodiment 3
The impact on calcio geopolymer performance of the multiple elements design powder body different ratio.
The commercially available industrial waterglass (water content 65%) that modulus n is 3.26 is mixed by weight 1:0.24 with chemical pure sodium hydroxide, the preparation that stirs under room temperature makes modulus of water glass n be adjusted to 1.0, calcio geopolymer is starched the impact of test specimen mechanical property by detection multiple elements design powder body different ratio only, and the preparation method of calcio geopolymer of the present invention comprises the following steps:
Granulated blast-furnace slag, flyash, metakaolin are mixed according to table 3 ratio, obtains ground granulated blast furnace slag coal ash metakaolin multiple elements design powder body material.
It is 1.0 by modulus, volume be 8% liquid glass be incorporated in multiple elements design powder body, stir after 1min in agitator for cement mortar, inject the vibration closely knit molding of 1min in the die trial of 40mm �� 40mm �� 40mm, maintenance is to the demoulding at the standard conditions, prepares calcio geopolymer and only starches test specimen. In corresponding age, clean slurry test specimen is carried out strength test.
Test result is as shown in table 3.
Table 3 different ratio multiple elements design powder body is on the clean impact starching comprcssive strength
The calcio geopolymer that as can be seen from Table 3 prepared by multiple elements design powder body has good mechanical property; in multiple elements design breeze; the volume of flyash and metakaolin respectively 20% time; the comprcssive strength of the calcio geopolymer prepared by metakaolin and granulated blast-furnace slag is higher, illustrates that the alkali-activated carbonatite activity of the flyash in multiple elements design powder body is not so good as metakaolin. Calcio geopolymer early anti pressured intension prepared by multiple elements design powder body is close to singly mixing the comprcssive strength that slag is starched only, the comprcssive strength of later stage calcio geopolymer exceedes singly mixes the comprcssive strength that slag is starched only, explanation, the hardened paste of calcio geopolymer prepared by multiple elements design powder body has excellent puts into pore structure and hydrated product so that the development of slurry later stage comprcssive strength is good.
Be can be seen that by various embodiments above; it is that calcio geopolymer prepared by primary raw material has good mechanical property by granulated blast-furnace slag, flyash, metakaolin at normal temperatures; the method preparing calcio geopolymer provided by the invention is without calcining; reduce production cost; solve industrial solid wastes and store up the problem of land occupation resource, be the concrete embodiment developed a circular economy with sustainable development.
Claims (6)
1. a calcio geopolymer, it is characterized in that, the multiple elements design powder body being made up of granulated blast-furnace slag and metakaolin, flyash under room temperature excites at alkali-activator and obtains, and its composition of raw materials includes: 70%��90% granulated blast-furnace slag, 0��30% flyash, 10��30% metakaolins; Alkali-activator adopts the liquid glass accounting for multiple elements design powder body weight 2%��10%;
Described granulated blast-furnace slag specific surface area is 4200cm2/ g, the incorporation of granulated blast-furnace slag is preferably 80%;
Described metakaolin specific surface area is 8500cm2/ g, volume is preferably 10%;
Described flyash specific surface area is 6400cm2/ g, volume is preferably 10%;
Described liquid glass modulus n is 0.8��1.6.
2. calcio geopolymer according to claim 1, it is characterised in that: described granulated blast-furnace slag specific surface area is 4200cm2/ g, the incorporation of granulated blast-furnace slag is preferably 80%.
3. calcio geopolymer according to claim 1, it is characterised in that: described metakaolin specific surface area is 8500cm2/ g, volume is preferably 10%.
4. calcio geopolymer according to claim 1, it is characterised in that: described flyash specific surface area is 6400cm2/ g, volume is preferably 10%.
5. calcio geopolymer according to claim 1, it is characterised in that: described liquid glass modulus n is 0.8��1.6.
6. the preparation method of a calcio geopolymer, it is characterised in that comprise the following steps:
1) by granulated blast-furnace slag, flyash, metakaolin according to proportioning mix homogeneously, obtaining ground granulated blast furnace slag coal ash metakaolin multiple elements design powder body, each constituent mass percentage composition of described multiple elements design powder body is: granulated blast-furnace slag 70%��90%, flyash 0��30%, metakaolin 0��30%;
2) liquid glass of different modulus n is to regulate in the undisturbed industry waterglass by chemical pure sodium hydroxide addition modulus n=3.26 to obtain, liquid glass and sodium hydroxide 1: 0.26,1: 0.24,1: 0.22,1: 0.20,1: 0.18 mix in proportion, preparation obtain modulus respectively 0.8,1.0,1.2,1.4,16 alkali activating agent solution;
3) multiple elements design powder body and alkali-activator are poured in cement mixer together stir, obtain calcio geopolymer slurry;
4) pouring the clean slurry being stirred in die trial vibration moulding, test specimen gang mould is put into curing temperature together and is maintained at 20 DEG C �� 1 DEG C, relative humidity, more than maintenance in the standard curing room of 90% 24 hours, continues maintenance extremely corresponding age in dampness after the demoulding.
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| CN106362680A (en) * | 2016-09-30 | 2017-02-01 | 东莞深圳清华大学研究院创新中心 | Burn-free coal-ash-based geological polymer high performance adsorbing material preparation method |
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