CN105502981A - Modified calcium aluminophosphate mineral - Google Patents

Modified calcium aluminophosphate mineral Download PDF

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Publication number
CN105502981A
CN105502981A CN201510928967.0A CN201510928967A CN105502981A CN 105502981 A CN105502981 A CN 105502981A CN 201510928967 A CN201510928967 A CN 201510928967A CN 105502981 A CN105502981 A CN 105502981A
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Prior art keywords
mineral
modified calcium
calcium aluminate
mineralizer
raw material
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CN201510928967.0A
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CN105502981B (en
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王守德
杨帅
芦令超
赵丕琪
宫晨琛
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University of Jinan
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University of Jinan
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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
    • C04B12/02—Phosphate cements
    • C04B12/025—Phosphates of ammonium or of the alkali or alkaline earth metals

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a modified calcium aluminophosphate mineral. The modified calcium aluminophosphate mineral is obtained in the mode that raw materials, a modifying agent and a mineralizing agent are calcined at the temperature of 1,450-1,550 DEG C, the heat preservation time ranges from 1 h to 3 h, and the temperature is rapidly reduced to the indoor temperature; the modifying agent is BaO or SrO. The modified calcium aluminophosphate mineral is high in early-stage hydration activity, the 7d hydration degree is 80% or above, and the 7d hydration degree is higher than that of non-modified calcium aluminophosphate mineral by 20% or above; the compressive strength is remarkably improved, the long-term strength is continuously increased, the resultant temperature of the modified calcium aluminophosphate mineral is reduced by about 30-70 DEG C, an energy saving effect and a cost reducing effect are remarkable, and the modified calcium aluminophosphate mineral is suitable for large-scale industrial application and popularization.

Description

A kind of modification phosphorus calcium aluminate mineral
Technical field
The invention belongs to cement material technical field, particularly a kind of modification phosphorus calcium aluminate mineral.
Background technology
Silicate cement is, the most widely gelling material maximum at building field consumption in the world now.This cement clinker is mainly by C 3s, C 2s, C 3a and C 4aF tetra-kinds of mineral compositions.This hydrolysis product of cement is C-S-H gel, calcium hydroxide and ettringite (AFt) etc. mainly.But silicate cement is more and more difficult to the performance and the construction requirement that meet priority project or special engineering, its main drawback is that early strength is on the low side, volumetric shrinkage is excessive etc. in hydration process.Therefore, the research, the development and application that meet the special gelatin gel material of special engineering demand are of great significance with regard to tool.
Phosphor aluminate cement is the new special cement with China's independent intellectual property right, is a kind of gelling material with high-performance, low alkalinity and good biocompatibility.The main mine of this cement clinker is mutually: phosphorus calcium aluminate CaO (1-x-y) Al 2o 3xSiO 2yP 2o 5, calcium phosphate CP 1-x(A x), calcium aluminate CA 1-y(P y) and vitreum.According to patent CN1498870A, one of this cement feature is to define a kind of ternary phosphorus calcium aluminate phase in cement clinker, axle (cube) crystallographic systems such as its crystalline structure belongs to, the main diffraction pattern scope of its X-ray diffraction one is: d=0.3723-0.3754nm, 0.2629-0.2650nm and 0.2147-0.2160nm, its main chemical compositions content is: CaO (1-x-y) Al 2o 3xSiO 2yP 2o 5, x=0.146-0.206, y=0.048-0.081.As the principal character mineral of phosphor aluminate cement, the early strength of phosphorus calcium aluminate is not given prominence to, and is mainly reflected in the middle and later periods to the intensity contribution of whole system.
Due to Ba 2+(Sr 2+) radius ratio Ca 2+greatly, therefore Ba-O(Sr-O) key of key will be weaker than Ca-O key by force.Work as Ba 2+(Sr 2+) enter ore deposit phase lattice replacement Ca 2+position, lattice distortion degree can be caused to become large, and stability declines, thus is expected to improve the hydration activity being substituted crystal.It is found that and adopt Ba 2+(Sr 2+) replace Ca in silicate minerals 2+, C after replacing 3s, C 2s mineral hydration activity is all improved; Pass through Ba 2+(Sr 2+) partly replace calcium sulphoaluminate (C 4a 3s) Ca in 2+can obtain the barium-bearing calcium sulfoaluminate of series, its molecular formula is (3-x) CaOxBa (Sr) O3Al 2o 3caSO 4, i.e. C 4-xb xa 3s, it has compares C 4a 3powerful feature morning that S more gives prominence to.Inspire by above-mentioned research, method provided by the invention is by Ba 2+(Sr 2+) to introduce in phosphorus calcium aluminate mineral and the Ca replaced in mineral 2+, thus the crystalline structure of phosphorus calcium aluminate is deformed, excite the early hydration of phosphorus calcium aluminate mineral active, be aided with CaSO simultaneously 4and Fe 2o 3reduce calcining temperature.
Summary of the invention
The invention provides the active high modification phosphorus calcium aluminate mineral of a kind of early hydration.
The object of the invention is to be achieved through the following technical solutions:
A kind of modification phosphorus calcium aluminate mineral is by raw material, properties-correcting agent and mineralizer at 1450-1550 DEG C of temperature lower calcination, soaking time 1-3h, is quenched to that room temperature obtains;
The weight ratio of described raw material, properties-correcting agent and mineralizer is 100:7-14:3-5;
In described raw material, the molar percentage of each oxide compound is: SiO 28.5-11.9, P 2o 52.6-5.0, A1 2o 339.3-46.1, CaO39.4-47.2;
Described properties-correcting agent is BaO or SrO;
MgO:ZnO:Fe in described mineralizer 2o 3weight ratio be 1:1-1.5:1-2.5.
Preferably, the weight ratio of raw material, properties-correcting agent and mineralizer is 100:11:4.
Preferably, MgO:ZnO:Fe in mineralizer 2o 3weight ratio be 1:1.2:1.5.
Modification phosphorus calcium aluminate mineral of the present invention is prepared by following steps:
1) by various for cement raw material, properties-correcting agent and mineralizer separate compiling, cross 200 mesh sieves, tail over <5%;
2) molar percentage of the cement raw material after grinding according to oxide compound each in raw material is prepared burden, properties-correcting agent and the mineralizer of proportional quantity is added according to weight ratio, to add water obtained slurry by ratio of water to material 3.5:1, ball milling mixes, oven dry to water ratio is 5-8%, be pressed into pat, at 100 DEG C, dry 1h, obtain oven dry pat;
3) be placed in High Temperature Furnaces Heating Apparatus by oven dry pat and calcine under 1480-1530 DEG C of condition, soaking time is 1-3h, is quenched to room temperature;
4) by broken for the oven dry pat cooled, grinding, to specifying fineness, can obtain modification phosphorus calcium aluminate mineral.
Beneficial effect of the present invention:
(1) modification phosphorus calcium aluminate mineral early hydration activity of the present invention is high, and 7d extent of hydration reaches more than 80%, exceeds more than 20% than unmodified phosphorus calcium aluminate mineral 7d extent of hydration;
(2) modification phosphorus calcium aluminate mineral 1d, 3d, 7d, 28d and 90d ultimate compression strength of the present invention is respectively 25-30MPa, 60-65MPa, 90-95MPa, 110-120MPa and 120-130MPa, 1d, 3d, 7d, 28d and 90d ultimate compression strength of not adding the phosphorus calcium aluminate mineral of properties-correcting agent is respectively 15-20MPa, 40-45MPa, 64-70MPa, 85-90MPa, 100-110MPa, meanwhile, the longterm strength of modification phosphorus calcium aluminate mineral of the present invention still constantly increases;
(3) synthesis temperature of modification phosphorus calcium aluminate mineral is the invention enables to reduce about 30-70 DEG C, significantly energy-saving and cost-reducing, be applicable to industrial large-scale promotion and use.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of modification phosphorus calcium aluminate mineral prepared by embodiment 1;
Fig. 2 is the XRD figure spectrum of modification phosphorus calcium aluminate mineral prepared by embodiment 2;
Fig. 3 is the XRD figure spectrum of P Modification calcium aluminate mineral prepared by embodiment 3;
In figure .for modification phosphorus calcium aluminate mineral diffraction peak.
Embodiment
embodiment 1
A kind of modification phosphorus calcium aluminate mineral is by raw material, properties-correcting agent and mineralizer at 1450 DEG C of temperature lower calcinations, soaking time 3h, is quenched to that room temperature obtains;
The weight ratio of described raw material, properties-correcting agent and mineralizer is 100:7:5;
In described raw material, the molar percentage of each oxide compound is: SiO 211.9, P 2o 52.6, A1 2o 346.1, CaO39.4;
Described properties-correcting agent is SrO;
MgO:ZnO:Fe in described mineralizer 2o 3weight ratio be 1:1.5:1.
A kind of modification phosphorus calcium aluminate mineral is prepared by following steps:
1) by various for cement raw material, properties-correcting agent and mineralizer separate compiling, cross 200 mesh sieves, tail over <5%;
2) molar percentage of the cement raw material after grinding according to oxide compound each in raw material is prepared burden, properties-correcting agent and the mineralizer of proportional quantity is added according to weight ratio, to add water obtained slurry by ratio of water to material 3.5:1, ball milling mixes, oven dry to water ratio is 5-8%, be pressed into pat, at 100 DEG C, dry 1h, obtain oven dry pat;
3) be placed in High Temperature Furnaces Heating Apparatus by oven dry pat and calcine under 1480-1530 DEG C of condition, soaking time is 1-3h, is quenched to room temperature;
4) by broken for the oven dry pat cooled, grinding, to specifying fineness, can obtain modification phosphorus calcium aluminate mineral.
Learn through Mechanics Performance Testing and only starch ultimate compression strength: 1d is 25MPa, 3d be 60MPa, 7d be 90MPa, 28d be 110MPa and 90d is 120MPa.
embodiment 2
A kind of modification phosphorus calcium aluminate mineral is by raw material, properties-correcting agent and mineralizer at 1500 DEG C of temperature lower calcinations, soaking time 2h, is quenched to that room temperature obtains;
The weight ratio of described raw material, properties-correcting agent and mineralizer is 100:11:4;
In described raw material, the molar percentage of each oxide compound is: SiO 210.2, P 2o 53.9, A1 2o 342.6, CaO43.3;
Described properties-correcting agent is BaO;
MgO:ZnO:Fe in described mineralizer 2o 3weight ratio be 1:1.2:1.5.
A kind of preparation method of modification phosphorus calcium aluminate mineral is with embodiment 1.
Learn through Mechanics Performance Testing and only starch ultimate compression strength: 1d is 30MPa, 3d be 65MPa, 7d be 95MPa, 28d be 120MPa and 90d is 130MPa.
embodiment 3
A kind of modification phosphorus calcium aluminate mineral is by raw material, properties-correcting agent and mineralizer at 1550 DEG C of temperature lower calcinations, soaking time 1h, is quenched to that room temperature obtains;
The weight ratio of described raw material, properties-correcting agent and mineralizer is 100:14:3;
In described raw material, the molar percentage of each oxide compound is: SiO 28.5, P 2o 55.0, A1 2o 339.3, CaO47.2;
Described properties-correcting agent is BaO;
MgO:ZnO:Fe in described mineralizer 2o 3weight ratio be 1:1:2.5.
A kind of preparation method of modification phosphorus calcium aluminate mineral is with embodiment 1.
Learn through Mechanics Performance Testing and only starch ultimate compression strength: 1d is 27MPa, 3d be 63MPa, 7d be 92MPa, 28d be 114MPa and 90d is 124MPa.

Claims (3)

1. a modification phosphorus calcium aluminate mineral, is characterized in that, is by raw material, properties-correcting agent and mineralizer at 1450-1550 DEG C of temperature lower calcination, soaking time 1-3h, is quenched to that room temperature obtains;
The weight ratio of described raw material, properties-correcting agent and mineralizer is 100:7-14:3-5;
In described raw material, the molar percentage of each oxide compound is: SiO 28.5-11.9, P 2o 52.6-5.0, A1 2o 339.3-46.1, CaO39.4-47.2;
Described properties-correcting agent is BaO or SrO;
CaSO in described mineralizer 4: B 2o 3: Fe 2o 3weight ratio be 1:1-1.5:1-2.5.
2. phosphorus calcium aluminate mineral according to claim 1, is characterized in that, the weight ratio of described raw material, properties-correcting agent and mineralizer is 100:11:4.
3. phosphorus calcium aluminate mineral according to claim 1, is characterized in that, CaSO in described mineralizer 4: B 2o 3: Fe 2o 3weight ratio be 1:1.2:1.5.
CN201510928967.0A 2015-12-15 2015-12-15 A kind of modified phosphorus calcium aluminate mineral Expired - Fee Related CN105502981B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106904850A (en) * 2017-03-21 2017-06-30 济南大学 For the composite mineralizer of phosphorus barium aluminate calcium cement
CN107117840A (en) * 2017-05-16 2017-09-01 葛洲坝石门特种水泥有限公司 The phosphor aluminate cement and its production method of a kind of utilization industrial residue production
CN109503110A (en) * 2019-01-11 2019-03-22 济南大学 A kind of middle low-activity nuclear waste incineration ash phosphorus strontium aluminate calcium cement solidification substrate
CN109592961A (en) * 2019-01-11 2019-04-09 济南大学 A kind of high temperature resistant boracic strontium phosphor aluminate cement base nuclear power concrete
CN109704714A (en) * 2019-01-11 2019-05-03 济南大学 A kind of Anti-radiation type phosphor aluminate cement base nuclear power concrete
CN109748567A (en) * 2019-01-11 2019-05-14 济南大学 A kind of middle low-activity spent resin phosphor aluminate cement base curing substrate
CN109796143A (en) * 2019-01-11 2019-05-24 济南大学 A kind of high temperature resistant Anti-radiation type boracic phosphorus strontium aluminate calcium clinker

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1498870A (en) * 2002-11-08 2004-05-26 胡佳山 Gelatinization material of phosphoaluminic salt system
CN104140216A (en) * 2014-06-24 2014-11-12 济南大学 High-iron phosphoaluminate cement clinker

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1498870A (en) * 2002-11-08 2004-05-26 胡佳山 Gelatinization material of phosphoaluminic salt system
CN104140216A (en) * 2014-06-24 2014-11-12 济南大学 High-iron phosphoaluminate cement clinker

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106904850A (en) * 2017-03-21 2017-06-30 济南大学 For the composite mineralizer of phosphorus barium aluminate calcium cement
CN106904850B (en) * 2017-03-21 2018-11-23 济南大学 composite mineralizer for phosphorus barium aluminate calcium cement
CN107117840A (en) * 2017-05-16 2017-09-01 葛洲坝石门特种水泥有限公司 The phosphor aluminate cement and its production method of a kind of utilization industrial residue production
CN107117840B (en) * 2017-05-16 2019-12-06 葛洲坝石门特种水泥有限公司 Phosphoaluminate cement produced by using industrial waste residues and production method thereof
CN109503110A (en) * 2019-01-11 2019-03-22 济南大学 A kind of middle low-activity nuclear waste incineration ash phosphorus strontium aluminate calcium cement solidification substrate
CN109592961A (en) * 2019-01-11 2019-04-09 济南大学 A kind of high temperature resistant boracic strontium phosphor aluminate cement base nuclear power concrete
CN109704714A (en) * 2019-01-11 2019-05-03 济南大学 A kind of Anti-radiation type phosphor aluminate cement base nuclear power concrete
CN109748567A (en) * 2019-01-11 2019-05-14 济南大学 A kind of middle low-activity spent resin phosphor aluminate cement base curing substrate
CN109796143A (en) * 2019-01-11 2019-05-24 济南大学 A kind of high temperature resistant Anti-radiation type boracic phosphorus strontium aluminate calcium clinker
CN109503110B (en) * 2019-01-11 2021-07-23 济南大学 Medium-low radioactive nuclear waste incineration ash calcium strontium phosphate cement curing base material
CN109748567B (en) * 2019-01-11 2021-09-07 济南大学 Medium-low radioactivity waste resin phosphoaluminate cement-based cured base material
CN109704714B (en) * 2019-01-11 2021-09-07 济南大学 Radiation-proof type phosphoaluminate cement-based nuclear power concrete

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