CN105819719B - A kind of enhanced geo-polymer and preparation method thereof - Google Patents
A kind of enhanced geo-polymer and preparation method thereof Download PDFInfo
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- CN105819719B CN105819719B CN201610141817.XA CN201610141817A CN105819719B CN 105819719 B CN105819719 B CN 105819719B CN 201610141817 A CN201610141817 A CN 201610141817A CN 105819719 B CN105819719 B CN 105819719B
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Classifications
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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
-
- 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
-
- 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
Abstract
The present invention provides a kind of enhanced geo-polymer and preparation method thereof, using the raw material such as phosphate and/or polyphosphate, higher territory, flyash, waterglass, alkali compounds, silica, water, it is blended by its parts by weight, by the raw material ground and mixed into uniform sizing material, slurry is injected into mould, is conserved under room temperature or low temperature (20 80 DEG C) and obtains product.The geo-polymer product that formula of the present invention and preparation method obtain, high temperature resistant, chemicals-resistant, and there is excellent mechanical property, its compression strength reaches more than 150MPa, meets the requirement of construction material, high temperature coating.High intensity in the present invention polymers preparation method compared with traditional building material production technology, have the advantages that technique is simple, it is low, easily operated to save the energy, environmental protection, cost.
Description
Technical field
The present invention relates to a kind of enhanced geo-polymer and preparation method thereof, belongs to inorganic nonmetal gelled materials neck
Domain.
Background technology
Geo-polymer is to study one of very active inorganic non-metallic material in the world in recent years.It is with clay,
Industrial residue or slag etc. are primary raw material, and alkali or acid are exciting agent, through appropriate process, are led under lower temperature conditions
Cross a kind of Novel Inorganic Polymers material that chemical reaction obtains.Geo-polymer has intensity height, hardens fast, acid-alkali-corrosive-resisting
Deng the special performance better than Portland cement, while have the advantages that material enriches, is cheap, saving the energy, therefore
Cause the great interest of domestic and international materials specialist.
The forming principle of geo-polymer is mainly alkali-activator excitation sial source material, causes silicon oxygen bond and alumina key
Fracture-restructuring, form inorganic chain structure, similar to macromolecular polymerization reaction formed chain structure.Geo-polymer gathers
It is as follows to close reaction：Under alkali-activator effect, the SiO in sial source material2And Al2O3Covalent bond destroys fracture, and formation is similar to be had
The oligomeric oxygen-octahedron and aluminum-oxygen tetrahedron of machine high polymer monomer；Then the process of a polycondensation is carried out again, these oligomeric oxygen
Tetrahedron and aluminum-oxygen tetrahedron are reconfigured using water as medium, discharge unnecessary water, the network structure body of the Si-O-Al of Cheng Xin
System.The three-dimensional net structure of geo-polymer shares bridging oxygen key connection by oxygen-octahedron and aluminum-oxygen tetrahedron and forms, and this three
Dimensional-oxide network structure determines its excellent performance, so as to determine its multipurpose.
And it is current, the compression strength of geology polymer material is in below 100MPa, it is necessary to come over the ground by other reinforcing agents
Matter polymer carries out humidification.And the addition of other reinforcing agents, cost was not only added, but also complicate processing technology.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of enhanced in view of the deficiency of the prior art
Geo-polymer and preparation method thereof, the geo-polymer are formed under conditions of no more than 100 DEG C, and with very high strong
Degree.
The present invention is to solve the problems, such as that used technical solution set forth above is：
A kind of enhanced geo-polymer, its raw materials by weight portion meter include：, 10-80 parts of metakaolin, flyash 0-
40 parts, 10-80 parts of waterglass, 5-30 parts of alkali compounds, 0-50 parts of silica, 5-30 parts of water, phosphate and/or poly phosphorus
0.1-2 parts of hydrochlorate.
By such scheme, the phosphate is pressed for the one or more in sodium dihydrogen phosphate, potassium dihydrogen phosphate, aluminum phosphate etc.
The mixture of arbitrary proportion.
By such scheme, the polyphosphate is pressed for the one or more in sodium tripolyphosphate and aluminium triphosphate etc. appoints
The mixture of meaning ratio.
By such scheme, the metakaolin, flyash, the particle diameter of silica are no more than 250 mesh.Preferably, institute
The particle diameter of metakaolin, flyash, silica is stated in the range of 250~8000 mesh.
By such scheme, the waterglass covers GB/T 4209-1996《Industrial waterglass》Middle Multiple Type, usual mould
Number is 1~4, may be selected from the waterglass of liquid -1 (modulus 3.5-3.7), the waterglass of liquid -2 (modulus 3.1-3.4), the waterglass (mould of liquid -3
Number 2.6-2.9), one kind in waterglass of liquid -4 (modulus 2.2-2.5) etc..
By such scheme, the alkali compounds is one kind in sodium hydroxide, potassium hydroxide and sodium carbonate etc..
The preparation method of above-mentioned enhanced geo-polymer, above-mentioned raw materials is stirred evenly as shaping is conserved after slurry,
It can obtain enhanced geo-polymer.
The preparation method of above-mentioned enhanced geo-polymer, specifically comprises the following steps：
(1) count in parts by weight, prepare 0.1-2 parts of raw material phosphate and/or polyphosphate, 10-80 parts of metakaolin,
0-40 parts of flyash, 10-80 parts of waterglass, 5-30 parts of alkali compounds, 0-50 parts of silica, 5-30 parts of water；
(2) the ready waterglass of step (1) and alkali compounds are uniformly mixed, then stand and obtain alkali-activator；
(3) by the ready phosphate of step (1) and/or polyphosphate, and metakaolin, flyash and titanium dioxide
Silicon is uniformly mixed (when the dosage of flyash and/or silica is 0 in step (1), i.e., need not add flyash in this step
And/or silica), the alkali-activator ground and mixed that step (2) obtains is added thereto, while it is ready to add step (1)
Water mixes, and obtains uniform sizing material；
(4) uniform sizing material obtained by step (3) is injected into mould, sealing reaction 2-15 days at 20-80 DEG C, you can increased
Strong type geo-polymer.
By such scheme, using stirring and/or ultrasound during mixing in step (2), to being uniformly mixed
By such scheme, step (2) the middle 1-2 days time stood.
The present invention produces H using phosphate or polyphosphoric acids salt hydrolysis+, promote waterglass fast hydrolyzing to generate more hydrogen
Oxygen radical ion, and then promote the structure disintegration of the aluminium oxide and silica in metakaolin, make Si-O and Al-O covalent bond quilts
Fracture is destroyed, dissociates [SiO4]4-[AlO4]5-Plasma, then regroups under water and alkali effect, forms Si-O-
Al-O spacial frameworks.Importantly, discharge H+Phosphate or polyphosphate generate a kind of water-insoluble double salt,
So as to which free alkali metal ion be wrapped, this double salt becomes the second phase, is evenly distributed in the geo-polymer
In, the mechanical property of geo-polymer is enhanced, and make geo-polymer that there is more preferable chemicals-resistant property.
Compared with prior art, the beneficial effects of the invention are as follows：
1) in enhanced geo-polymer of the present invention, due to phosphate or polyphosphoric acids salt hydrolysis produce second
Phase, is dispersed in geo-polymer with micro-, nanoscale, enhances the mechanical property of geo-polymer, its compression strength
More than 150MPa is reached.
2) preparation method of enhanced geo-polymer of the present invention, since the hydrolysis of phosphate or polyphosphate is urged
Change acts on, and accelerates the silica in higher territory and flyash and alumina structural damage, and the chain type for forming silicon-oxygen-aluminium is inorganic
Polymer architecture, therefore, shaping speed are fast, conserved at room temperature or 20~80 DEG C 2-15 days it is i.e. plastic.
3) the geo-polymer product that formula of the present invention and preparation method obtain, high temperature resistant, chemicals-resistant, and have
There is excellent mechanical property, its compression strength reaches more than 150MPa, meets the requirement of construction material, high temperature coating.This
High intensity in invention polymers preparation method compared with traditional building material production technology, have technique is simple, save the energy,
The advantages that environmental protection, cost are low, easily operated.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of enhanced geo-polymer prepared by embodiment 1.
Embodiment
For a better understanding of the present invention, with reference to the example content that the present invention is furture elucidated, but the present invention is not only
It is limited only to the following examples.
Embodiment 1
A kind of enhanced geo-polymer, its raw materials by weight portion meter include：0.1 part of sodium tripolyphosphate, 2000 mesh are inclined
10 parts of kaolin, 10 parts of the waterglass of liquid -2 (modulus 3.1-3.4), 5 parts of sodium hydroxide, 5 parts of water.
The preparation method of above-mentioned enhanced geo-polymer, specifically comprises the following steps：
(1) count in parts by weight, prepare 0.1 part of raw material sodium tripolyphosphate, 10 parts of 2000 mesh metakaolin, the waterglass of liquid -2
10 parts of (modulus 3.1-3.4), 5 parts of sodium hydroxide, 5 parts of water；
(2) the ready waterglass of step (1) and sodium hydroxide are mixed, it is ultrasonic after stirring, 24h is then stood, is obtained
Alkali-activator；
(3) the ready sodium tripolyphosphate of step (1) and metakaolin are uniformly mixed, add step (2) thereto and obtain
The alkali-activator ground and mixed arrived, while add the ready water of step (1) and mix, obtain uniform sizing material；
(4) uniform sizing material obtained by step (3) is injected into mould, sealing reaction 15 days at 20 DEG C, you can obtain enhanced
Geo-polymer.
Intensity test：
The geo-polymer surface of mechanical property manufactured in the present embodiment enhancing is smooth, flawless, according to GB/T-4740-
1999 ceramic material compression strength experimental methods carry out intensity test, its compression strength is 151MPa.
From figure 1 it appears that during geo-polymer is prepared by metakaolin, shape after polyphosphoric acids salt hydrolysis
Into the second phase phosphate, this is mutually in flower-shaped Particle distribution in geo-polymer matrix, to the mechanical strength of geo-polymer
With improvement result.
Embodiment 2
A kind of enhanced geo-polymer, its raw materials by weight portion meter include：2 parts of sodium dihydrogen phosphate, 8000 mesh are higher
80 parts of ridge soil, 80 parts of 8000 mesh flyash, 80 parts of the waterglass of liquid -4 (modulus 2.2-2.5), 30 parts of potassium hydroxide, 8000 mesh dioxies
50 parts of SiClx, 30 parts of water.
The preparation method of above-mentioned enhanced geo-polymer, specifically comprises the following steps：
(1) count in parts by weight, prepare 2 parts of raw material sodium dihydrogen phosphate, 80 parts of 8000 mesh metakaolin, 8000 mesh flyash
80 parts, 80 parts of the waterglass of liquid -4 (modulus 2.2-2.5), 30 parts of potassium hydroxide, 50 parts of 8000 mesh silica, 30 parts of water；
(2) the ready waterglass of step (1) and potassium hydroxide are mixed, it is ultrasonic after stirring, 24h is then stood, is obtained
Alkali-activator；
(3) the ready sodium dihydrogen phosphate and metakaolin of step (1), flyash and silica are uniformly mixed, to
The alkali-activator ground and mixed that step (2) obtains wherein is added, while adds the ready water of step (1) and mixes, is obtained uniformly
Slurry；
(4) uniform sizing material obtained by step (3) is injected into mould, sealing reaction 2 days at 80 DEG C, you can obtain enhancedly
Matter polymer.
Intensity test：
The geo-polymer surface of mechanical property manufactured in the present embodiment enhancing is smooth, flawless, according to GB/T-4740-
1999 ceramic material compression strength experimental methods carry out intensity test, its compression strength is 153MPa.
Embodiment 3
A kind of enhanced geo-polymer, its raw materials by weight portion meter include：0.4 part of aluminium triphosphate, 250 mesh are higher
41 parts of ridge soil, 43 parts of the waterglass of liquid -1 (modulus 3.5-3.7), 6 parts of sodium carbonate, 250 mesh silica 1 parts, 9 parts of water.
The preparation method of above-mentioned enhanced geo-polymer, specifically comprises the following steps：
(1) count in parts by weight, prepare 0.4 part of raw material aluminium triphosphate, 41 parts of 250 mesh metakaolin, the waterglass of liquid -1
43 parts of (modulus 3.5-3.7), 6 parts of sodium carbonate, 250 mesh silica 1 parts, 9 parts of water；
(2) the ready waterglass of step (1) and sodium carbonate are mixed, it is ultrasonic after stirring, 24h is then stood, obtains alkali
Exciting agent；
(3) the ready aluminium triphosphate of step (1) and metakaolin, silica are uniformly mixed, added thereto
The alkali-activator ground and mixed that step (2) obtains, while add the ready water of step (1) and mix, obtain uniform sizing material；
(4) uniform sizing material obtained by step (3) is injected into mould, sealing reaction 10 days at 50 DEG C, you can obtain enhanced
Geo-polymer.
Intensity test：
The geo-polymer surface of mechanical property manufactured in the present embodiment enhancing is smooth, flawless, according to GB/T-4740-
1999 ceramic material compression strength experimental methods carry out intensity test, its compression strength is 159MPa.
Embodiment 4
A kind of enhanced geo-polymer, its raw materials by weight portion meter include：1 part of potassium dihydrogen phosphate, the higher ridge of 800 mesh
50 parts of soil, 10 parts of 800 mesh flyash, 43 parts of the waterglass of liquid -3 (modulus 2.6-2.9), 10 parts of potassium hydroxide, 10 parts of water.
The preparation method of above-mentioned enhanced geo-polymer, specifically comprises the following steps：
(1) count in parts by weight, prepare 1 part of raw material potassium dihydrogen phosphate, 50 parts of 800 mesh metakaolin, 800 mesh flyash 10
Part, 43 parts of the waterglass of liquid -3 (modulus 2.6-2.9), 10 parts of potassium hydroxide, 10 parts of water；
(2) the ready waterglass of step (1) and potassium hydroxide are mixed, it is ultrasonic after stirring, 24h is then stood, is obtained
Alkali-activator；
(3) the ready potassium dihydrogen phosphate of step (1) and metakaolin, flyash are uniformly mixed, add step thereto
Suddenly the alkali-activator ground and mixed that (2) obtain, while add the ready water of step (1) and mix, obtain uniform sizing material；
(4) uniform sizing material obtained by step (3) is injected into mould, sealing reaction 7 days at 70 DEG C, you can obtain enhancedly
Matter polymer.
Intensity test：
The geo-polymer surface of mechanical property manufactured in the present embodiment enhancing is smooth, flawless, according to GB/T-4740-
1999 ceramic material compression strength experimental methods carry out intensity test, its compression strength is 155MPa.
The above is only the preferred embodiment of the present invention, it is noted that is come for those of ordinary skill in the art
Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (9)
1. a kind of enhanced geo-polymer, it is characterised in that its raw materials by weight portion meter includes：Phosphate and/or poly
0.1-2 parts of phosphate, 10-80 parts of metakaolin, 0-40 parts of flyash, 10-80 parts of waterglass, 5-30 parts of alkali compounds, two
0-50 parts of silica, 5-30 parts of water.
2. a kind of enhanced geo-polymer according to claim 1, it is characterised in that the phosphate is biphosphate
One or more of mixtures in any proportion in sodium, potassium dihydrogen phosphate, aluminum phosphate.
3. a kind of enhanced geo-polymer according to claim 1, it is characterised in that the polyphosphate is trimerization
The mixture of one or both of sodium phosphate and aluminium triphosphate in any proportion.
A kind of 4. enhanced geo-polymer according to claim 1, it is characterised in that the metakaolin, flyash,
The particle diameter of silica is no more than 250 mesh.
A kind of 5. enhanced geo-polymer according to claim 4, it is characterised in that the metakaolin, flyash,
The particle diameter of silica is in the range of 250 ~ 8000 mesh.
6. a kind of enhanced geo-polymer according to claim 1, it is characterised in that the waterglass is industry water glass
Glass, modulus are 1 ~ 4.
7. a kind of enhanced geo-polymer according to claim 1, it is characterised in that the alkali compounds is hydrogen-oxygen
Change one or more of mixtures in any proportion in sodium, potassium hydroxide and sodium carbonate.
8. the preparation method of the enhanced geo-polymer described in any one in claim 1-7, it is characterised in that
The raw material is stirred evenly as shaping is conserved after slurry, you can obtain enhanced geo-polymer.
9. the preparation method of the enhanced geo-polymer described in any one in claim 1-7, it is characterised in that
Include the following steps：
（1）Count in parts by weight, prepare raw material phosphate and/or 0.1-2 parts of polyphosphate, 10-80 parts of metakaolin, fine coal
0-40 parts grey, 10-80 parts of waterglass, 5-30 parts of alkali compounds, 0-50 parts of silica, 5-30 parts of water；
（2）By step（1）Ready waterglass and alkali compounds mixing, it is ultrasonic after stirring, then stand and obtain alkali-activated carbonatite
Agent；
（3）By step（1）Ready phosphate and/or polyphosphate, and metakaolin, flyash and silica mix
Close uniformly, add step thereto（2）Obtained alkali-activator ground and mixed, while add step（1）Ready water mixes,
Obtain uniform sizing material；
（4）By step（3）Gained uniform sizing material injects mould, sealing reaction 2-15 days at 20-80 DEG C, you can strengthened
Type geo-polymer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3841075A4 (en) * | 2018-08-22 | 2022-08-03 | The Catholic University Of America | High strength class c fly ash cementitious compositions with controllable setting |
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| CN106587682A (en) * | 2016-12-06 | 2017-04-26 | 钦州市高新技术产业服务中心 | Geopolymer and preparation method thereof |
| CN106673470A (en) * | 2016-12-09 | 2017-05-17 | 钦州市钦南区科学技术情报研究所 | Geopolymer and preparation method thereof |
| CN107746212B (en) * | 2017-10-18 | 2019-08-27 | 浙江大学 | A kind of modification enhanced ground oligomer gel material and preparation method thereof |
| CN108373277B (en) * | 2018-03-13 | 2020-12-15 | 盐城工学院 | Epoxy resin toughened metakaolin-based polymer and preparation method thereof |
| CN109231860B (en) * | 2018-09-26 | 2021-09-07 | 长安大学 | Cementing material and preparation method thereof |
| CN109704678B (en) * | 2019-01-23 | 2021-12-28 | 广东睿住住工科技有限公司 | Ultra-high performance concrete, hollow component and preparation method of hollow component |
| CN111732378B (en) * | 2020-07-06 | 2022-06-28 | 济南大学 | Geopolymer member and preparation method thereof |
| CN112028654B (en) * | 2020-09-14 | 2021-09-14 | 深圳大学 | Baking-free geopolymer composite refractory material and preparation method thereof |
| CN114230249B (en) * | 2021-12-22 | 2023-03-28 | 西安理工大学 | Inorganic polymer mortar and preparation method thereof |
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