CN1219719C - Barium containing sulpho- ferro- aluminate cement - Google Patents
Barium containing sulpho- ferro- aluminate cement Download PDFInfo
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- CN1219719C CN1219719C CN 200310105554 CN200310105554A CN1219719C CN 1219719 C CN1219719 C CN 1219719C CN 200310105554 CN200310105554 CN 200310105554 CN 200310105554 A CN200310105554 A CN 200310105554A CN 1219719 C CN1219719 C CN 1219719C
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- Prior art keywords
- aluminate
- cement
- ferro
- sulphur
- barium
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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
- C04B7/003—Barium or strontium cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
- C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
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- 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)
Abstract
The present invention relates to aluminate cement containing barium, sulphur and iron, which uses sulphur and iron barium aluminate calcium and dicalcium silicate as main minerals and belongs to the technical field of cement materials. The present invention discloses aluminate cement containing barium, sulphur and iron. Cement clinker of the aluminate cement contains 5 to 80% of sulphur and iron barium aluminate calcium, wherein the sulphur and iron barium aluminate calcium (C[4-x]BxA[3-y]FyS in short) has the molecular formula of (3-X)CaO. XBaO. (3-Y)Al2O3. Fe2O3. CaSO4 (X and Y are from 0.10 to 3). Compared with rapid hardening sulphate aluminium cement, the present invention has the advantages of low sintering temperature and low cost.
Description
(1) technical field under
The invention belongs to the technical field of cement material, relate to the baric sulphur ferro-aluminate cement of taking mineral by barium-bearing calcium sulfo-ferrite aluminate and Dicalcium Phosphate (Feed Grade) as the leading factor.
(2) background technology
At present, there is some shortcoming and defect in a large amount of quick hardening sulphoaluminate cements that use, mainly show as firing temperature higher (being 1350 ℃), later strength instability, material cost height.Titanate-containing sulpho-aluminate cement utilize baric industrial residue or barite mine tailing for raw material substitution a large amount of gypsum, reduced cement cost; But because the aluminium element in the cement minerals is provided by expensive bauxitic clay, make the cost of titanate-containing sulpho-aluminate cement also be much higher than ordinary Portland cement, limited titanate-containing sulpho-aluminate cement and used widely.
(3) summary of the invention
In order further to reduce this cement cost, reduce firing temperature, the present invention utilizes the aluminium element in cheap iron powder or the replacement of the ferro element in the scum barium-bearing calcium sulfo-aluminate, provide a kind of to take the novel concrete of ore deposit phase system as the leading factor by barium-bearing calcium sulfo-ferrite aluminate and Dicalcium Phosphate (Feed Grade), it is low to have firing temperature, the early strength height, setting rate is fast, the advantage that cost is low.
The present invention is achieved through the following technical solutions:
The invention discloses a kind of baric sulphur ferro-aluminate cement, its cement clinker contains the barium-bearing calcium sulfo-ferrite aluminate of 5-80% (weight), and wherein barium-bearing calcium sulfo-ferrite aluminate (is abbreviated as C
4-xBxA
3-yF
yS) molecular formula is,
(3-x)CaO·xBaO·(3-y)Al
2O
3·yFe
2O
3·CaSO
4(x，y＝0.10～3)。
Baric sulphur ferro-aluminate cement of the present invention, its optimal components ratio are the barium-bearing calcium sulfo-ferrite aluminate that contains 40-80% (weight) in the cement clinker.
Baric sulphur ferro-aluminate cement of the present invention, the weight percent of described each mineral of cement clinker is:
Barium-bearing calcium sulfo-ferrite aluminate: 5-80%
Dicalcium Phosphate (Feed Grade): 10-40%
Tricalcium silicate: 0-50%
Tricalcium aluminate: 0-20%
Ferro-aluminate: 3-20%
Baric sulphur ferro-aluminate cement of the present invention, the preferable weight percent of each mineral is in its cement clinker:
Barium-bearing calcium sulfo-ferrite aluminate: 40-80%
Dicalcium Phosphate (Feed Grade): 10-40%
Tricalcium silicate: 0-20%
Tricalcium aluminate: 0-20%
Ferro-aluminate: 3-20%
In the cement clinker of the present invention, the better weight percent of the composition of above-mentioned mineral is:
Barium-bearing calcium sulfo-ferrite aluminate: 50-70%
Dicalcium Phosphate (Feed Grade): 20-30%
Tricalcium silicate: 4-10%
Tricalcium aluminate: 3-10%
Ferro-aluminate: 3-10%
Cement of the present invention, the raw material component of its cement is by weight percentage:
CaO： 20-35％
SiO
2： 3-8％
Al
2O
3：10-20％
Fe
2O
3：3-10％
SO
3： 3-6％
BaO： 3-15％
The barium-bearing calcium sulfo-ferrite aluminate mineral are a kind of hydraulicity mineral with outstanding high-early-strength performance, and its firing temperature is low, and can utilize industrial residue production.Making the employed main raw material of these mineral is Wingdale, low-grade bauxite, iron powder or scum and baric mine tailing or waste residue, just can easy fired below 1300 ℃.The ultimate compression strength of the barium-bearing calcium sulfo-ferrite aluminate mineral of manufacturing was at 1 day, 3 days and reach 33.2MPa, 54.3MPa and 65.6MPa the 7 day length of time respectively, and its hydration and hardening speed is very fast, was a kind of high gelling mineral with outstanding high-early-strength performance.
Present technique is that high-early-strength type barium-bearing calcium sulfo-ferrite aluminate mineral and Dicalcium Phosphate (Feed Grade) mineral are compound, forms the novel concrete clinker mineral system of taking mineral with barium-bearing calcium sulfo-ferrite aluminate as the leading factor.This cement had both had the advantage that high-early-strength cement is had, and production cost is low, the common construction project that can be widely used in having the high quality requirement, construct at a high speed.Silicate cement is with tricalcium silicate (C
3S claims A Lite again), Dicalcium Phosphate (Feed Grade) (C
2S), tricalcium aluminate (C
3A) and ferro-aluminate (C
4AF) be essential mineral, C
3The content of S need expend a large amount of high-quality limestone mineral resources generally more than 50%, and need just can burn till under 1450 ℃ of hot conditionss, causes energy consumption too high.Simultaneously, the early stage performance of making of silicate cement is on the low side at present, and it is low mainly to show as cement early strength, and hydration and hardening speed is slow, and time of coagulation is long.And the barium-bearing calcium sulfo-ferrite aluminate mineral have good high-early-strength performance, and firing temperature is low, and about about 1250 ℃ is a kind of low temp and early strength mineral of excellent property.
The present invention is with C
4-xB
xA
3Al among the S is replaced by Fe, forms with C by high temperature solid state reaction
4-xBxA
3-yF
yS-C
2S takes the new cement clinker ore deposit phase system of mineral as the leading factor.Different with silicate cement, aluminosulfate cement, Portland clinker is by C
3S-C
2S-C
3A-C
4Four kinds of essential minerals of AF are formed, and sulphoaluminate cement clinker is by C
4A
3S-C
2S-C
4Three kinds of essential minerals of AF are formed, and baric sulphur ferro-aluminate cement grog is by CBFAS-C
2S-C
3S-C
3A-C
4The new system of five kinds of mineral compositions of AF.The barium-bearing calcium sulfo-ferrite aluminate mineral just can form below 1250 ℃ in a large number, and C in the grog
3S, C
2S content is low, makes baric sulphur iron aluminic acid cement clinker just can burn till about 1200 ℃-1300 ℃, reduces 150-250 ℃ than the firing temperature of silicate cement, reduces 50-150 ℃ than the firing temperature of aluminosulfate cement, has saved the energy.Particularly baric sulphur ferro-aluminate cement utilizes cheap baric industrial residue and iron powder to be main raw material, makes baric sulphur ferro-aluminate cement cost decline to a great extent than quick hardening sulphoaluminate cement.This cement early strength reaches more than 30% than the silicate cement raising approximately, and later strength also has increase to a certain degree, and the cement setting setting rate is fast.The use of baric sulphur ferro-aluminate cement has unusual effect to comprehensive raising construction quality, quickening speed of application, is particularly suitable for the large-scale construction project of Highrise buildings, high-grade highway, airport, the contour specification of quality of bridge and tunnel.In addition, because the effect that also has compensate for shrinkage of barium-bearing calcium sulfo-ferrite aluminate mineral, thereby can reduce the shrinking percentage of cement, reduce shrinkage crack, improve the weather resistance of concrete works.Present technique technology is simple, adopts the producing apparatus of existing silicate cement fully.
Main points of the present invention are to have invented new cement minerals-barium-bearing calcium sulfo-ferrite aluminate, burn till being lower than under 1300 ℃ of conditions, form with C by solid state reaction
4-xBxA
3-yF
yS-C
2S originally takes the new cement clinker ore deposit phase system of mineral as the leading factor, reaches the purpose that reduces firing temperature, reduction manufacture of cement cost, improves cement early strength.
The invention has the beneficial effects as follows that it is low to have a firing temperature than quick hardening sulphoaluminate cement, the advantage that cost is low.
(4) description of drawings
Fig. 1 is the XRD analysis figure of cement clinker of the present invention.
Fig. 2 is the SEM figure of cement clinker of the present invention.
(5) embodiment
Table 1 raw-meal ingredient (wt%)
| Numbering | Loss | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | BaO | SO 3 |
| 1# | 29.53 | 3.45 | 20.36 | 7.80 | 23.55 | 8.82 | 6.79 |
| 2# | 28.65 | 6.12 | 19.43 | 5.16 | 27.73 | 7.86 | 6.23 |
| 3# | 28.54 | 8.43 | 14.02 | 5.66 | 28.77 | 7.75 | 5.92 |
| 4# | 28.46 | 9.93 | 12.36 | 6.22 | 29.86 | 7.95 | 4.76 |
| 5# | 27.69 | 17.45 | 5.35 | 4.23 | 34.74 | 4.85 | 2.81 |
Table 2 clinker mineral is formed
| Numbering | C 4-xBxA 3-yF y S | C 2S | C 3S | C 3A | C 4AF |
| 1# | 78 | 15 | 0 | 0 | 7 |
| 2# | 65 | 25 | 0 | 0 | 10 |
| 3# | 53 | 30 | 8 | 4 | 5 |
| 4# | 30 | 32 | 15 | 6 | 7 |
| 5# | 10 | 35 | 45 | 5 | 5 |
Above grog is burnt till with 1800 ℃ of Si-Mo rod stoves in the laboratory, firing temperature is 1200 ℃-1280 ℃.The physicals of cement sees Table 3.
Table 3 cement physical properties
| Numbering | Fineness % | Ultimate compression strength/folding strength (MPa) | Time of coagulation h | f-CaO ％ | |||
| 1 | 3 days | 28 days | Initial set | Final set | |||
| 1# | 3-3.5 | 51.2/4.2 | 68.6/6.5 | 84.6/10.4 | 0:43 | 0:56 | 0 |
| 2# | 3-3.5 | 40.8/3.9 | 64.3/6.8 | 81.0/10.6 | 0:37 | 0:55 | 0 |
| 3# | 3-3.5 | 28.4/4.3 | 40.3/6.8 | 59.3/11.1 | 0:43 | 1:28 | 0 |
| 4# | 3-3.5 | 16.8/3.6 | 28.6/5.9 | 60.2/10.2 | 1:04 | 1:45 | 0 |
| 5# | 3-3.5 | 15.6/2.5 | 23.2/4.1 | 58.8/9.4 | 1:46 | 2:15 | 0 |
Wherein 1# grog is carried out XRD and sem analysis, seen Fig. 1 and Fig. 2.Can see in baric sulphur ferro-aluminate cement clinker mineral system, form the baric sulphur iron calcium aluminate mineral of some amount and the compound coexistence of Dicalcium Phosphate (Feed Grade) mineral.
Claims (6)
1. a baric sulphur ferro-aluminate cement is characterized in that: contain the barium-bearing calcium sulfo-ferrite aluminate that weight percent is 5-80% in its cement clinker, wherein barium-bearing calcium sulfo-ferrite aluminate
C
4-xBxA
3-yThe molecular formula of Fy S is,
(3-x)CaO·xBaO·(3-y)Al
2O
3·yFe
2O
3·CaSO
4，x，y＝0.10～3。
2. baric sulphur ferro-aluminate cement according to claim 1 is characterized in that: contain the barium-bearing calcium sulfo-ferrite aluminate that weight percent is 40-80% in its cement clinker.
3. baric sulphur ferro-aluminate cement according to claim 1 is characterized in that: mainly be by C in its cement clinker
4-xBxA
3-yFy S-C
3S-C
2S-C
3A-C
4The ore deposit phase system that AF forms, the weight percent of each mineral is:
Barium-bearing calcium sulfo-ferrite aluminate: 5-80%
Dicalcium Phosphate (Feed Grade): 10-40%
Tricalcium silicate: 0-50%
Tricalcium aluminate: 0-20%
Ferro-aluminate: 3-20%.
4. baric sulphur ferro-aluminate cement according to claim 3, it is characterized in that: the weight percent of described mineral is:
Barium-bearing calcium sulfo-ferrite aluminate: 40-80%
Dicalcium Phosphate (Feed Grade): 10-40%
Tricalcium silicate: 0-20%
Tricalcium aluminate: 0-20%
Ferro-aluminate: 3-20%.
5. baric sulphur ferro-aluminate cement according to claim 3, it is characterized in that: the weight percent of described mineral is:
Barium-bearing calcium sulfo-ferrite aluminate: 50-70%
Dicalcium Phosphate (Feed Grade): 20-30%
Tricalcium silicate: 4-10%
Tricalcium aluminate: 3-10%
Ferro-aluminate: 3-10%.
6. according to claim 1,2 or 3 described baric sulphur ferro-aluminate cements, it is characterized in that: the raw material component of its cement is by weight percentage:
CaO：20-35％
SiO
2：3-8％
Al
2O
3：10-20％
Fe
2O
3：3-10％
SO
3：3-6％
BaO：3-15％。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310105554 CN1219719C (en) | 2003-12-01 | 2003-12-01 | Barium containing sulpho- ferro- aluminate cement |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310105554 CN1219719C (en) | 2003-12-01 | 2003-12-01 | Barium containing sulpho- ferro- aluminate cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1546409A CN1546409A (en) | 2004-11-17 |
| CN1219719C true CN1219719C (en) | 2005-09-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310105554 Expired - Fee Related CN1219719C (en) | 2003-12-01 | 2003-12-01 | Barium containing sulpho- ferro- aluminate cement |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1670733B1 (en) | 2003-08-25 | 2017-12-13 | Westmoreland Advanced Materials, Inc. | Use of a sprayable refractory composition as refractory lining in the processing of molten aluminium |
| US8216435B2 (en) | 2004-06-07 | 2012-07-10 | Westmoreland Advanced Materials, Inc. | Calcium aluminate clinker as a refractory aggregate with and without barium addition and use thereof |
| US8563083B2 (en) | 2006-09-21 | 2013-10-22 | Westmoreland Advanced Materials, Inc. | Methods of use of calcium hexa aluminate refractory linings and/or chemical barriers in high alkali or alkaline environments |
| WO2011108065A1 (en) * | 2010-03-01 | 2011-09-09 | 電気化学工業株式会社 | Cement admixture and cement composition |
| CN101863628B (en) * | 2010-04-14 | 2012-08-29 | 武汉科技大学 | Aluminoferriate cement and preparation method thereof |
| CN112645616A (en) * | 2020-12-31 | 2021-04-13 | 山东大学 | Method for regulating and controlling mineral composition of high-iron sulphoaluminate clinker |
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2003
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Granted publication date: 20050921 Termination date: 20121201 |