CN1300034C - High-activity shrinkage-compensating mineral admixture and preparation method thereof - Google Patents
High-activity shrinkage-compensating mineral admixture and preparation method thereof Download PDFInfo
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- CN1300034C CN1300034C CNB2005100188204A CN200510018820A CN1300034C CN 1300034 C CN1300034 C CN 1300034C CN B2005100188204 A CNB2005100188204 A CN B2005100188204A CN 200510018820 A CN200510018820 A CN 200510018820A CN 1300034 C CN1300034 C CN 1300034C
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Abstract
The present invention relates to a high activity mineral admixture with a compensation and shrinkage effect on cement concrete and a making method of the high activity mineral admixture. The high activity mineral compensation and shrinkage admixture is formed by mixing steel slag, scoria, sulphate aluminate cement clinkers and gypsum, wherein the components of the high activity mineral admixture comprise the following mass ratio: the steel slag: the scoria: the sulphate aluminate cement clinkers: the gypsum equals to 40 to 60%: 20 to 40%: 10 to 20%: 5 to 10%, and a component sum is 100%; the Przibram dry powdery high activity mineral compensation and shrinkage admixture with a specific surface area of 400 to 500m<2>/kg, high activity and a compensation and shrinkage function is obtained by mixing and milling the steel slag, the scoria, the sulphate aluminate cement clinkers and the gypsum. The present invention has the high activity and the compensation and shrinkage function; the activity index and the expansion rate parameter of the high activity mineral compensation and shrinkage admixture can be larger than or equal to 80% (an intensity rate), from 0.03% to 0.05% of 28d and from 0.01% to 0.03% of 180d respectively.
Description
Technical field
The invention belongs to the ceramic class, be specifically related to a kind of high-activity mineral blending material that cement concrete is had the compensate for shrinkage effect and preparation method thereof.
Background technology
The application of mineral admixture in cement concrete not only improved the additional utilization value of industrial residue, and the protection environment reduces the concrete cost, but also has improved traditional performance of cement concrete greatly, prolongs its work-ing life.But, existing mineral admixture such as slag, silicon ash, zeolite powder, phosphorus slag, metakaolin, flyash, coal gangue, although active high, it is bigger, easy to crack to utilize its concrete batching to shrink; Though and utilize the slag breeze concrete batching to have the compensate for shrinkage effect because its activity is low, so utilization ratio is relatively low.Simultaneously, for mineral admixture, it has only played effects such as filler, pozzolanic activity, reduction water consumption in cement concrete, also can not reach the effect of concrete being played the compensate for shrinkage function far away.
Summary of the invention
The object of the present invention is to provide and a kind ofly promptly have high reactivity and have high-activity shrinkage-compensating mineral admixture of compensate for shrinkage function and preparation method thereof again.
To achieve these goals, technical scheme of the present invention is: high-activity shrinkage-compensating mineral admixture, it is mixed by slag, slag, sulphoaluminate cement clinker and gypsum, its each component mass percent is: slag: slag: sulphoaluminate cement clinker: gypsum=(40～60%): (20～40%): (10～20%): (5～10%), each component sum are 100%; Slag, slag, sulphoaluminate cement clinker and gypsum are through mixing, grinding, and obtaining Blain specific surface is 400～500m
2The dry powder of/kg has the high-activity shrinkage-compensating mineral admixture of high reactivity and compensate for shrinkage function.
This high-activity shrinkage-compensating mineral admixture adopts the preparation of one of following three kinds of methods:
1, the preparation method of high-activity shrinkage-compensating mineral admixture, comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=(40～60%): (20～40%): (10～20%): (5～10%), choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with independent respectively grinding to the specific surface area of various raw materials is 400～500m
2/ kg mixes then, adorns bag at last, seals, seals up for safekeeping.
2, the preparation method of high-activity shrinkage-compensating mineral admixture, comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=(40～60%): (20～40%): (10～20%): (5～10%), choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with independent respectively grinding to the specific surface area of various raw materials is 200～400m
2/ kg mixes then, is 400～500m with mixture grinding to specific surface area
2/ kg adorns bag at last, seals, seals up for safekeeping.
3, the preparation method of high-activity shrinkage-compensating mineral admixture, comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=(40～60%): (20～40%): (10～20%): (5～10%), choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with various raw material separated pulverizing to diameter less than 50mm, mix then, it is 400～500m that the mixture grinding is reached specific surface area
2/ kg adorns bag at last, seals, seals up for safekeeping.
The high reactivity of high-activity shrinkage-compensating mineral admixture and microdilatancy principle can think as follows:
Sulphoaluminate cement clinker and gypsum can carry out following reaction immediately under the effect of water:
In fact, as long as calcium ion, aluminate and the sulfate ion of proper concn are arranged in the solution, just can form ettringite.In the ordinary course of things, aluminate ion is by C
3A, CA, C
12A
7, CA
2Provide Deng calcium aluminate, dihydrate gypsum or dehydrated gyp-provide sulfate ion, Calucium Silicate powder (C
3S, C
2S) aquation provides calcium ion; And anhydrous calcium sulphoaluminate (3CaO3Al
2O
3CaSO
4) then can provide above-mentioned various ion simultaneously.When CaO concentration in the liquid phase is low, Al
2O
3Equilibrium concentration is higher, and the degree of supersaturation during ettringite (AFt) crystallization is little, and crystallization is slow, and crystalline form is bigger, and away from original solid phase surface, separates out with dispersed; Then opposite when CaO concentration reaches capacity in the liquid phase, the very fast reunion of ettringite is separated out with fine crystals radially at original solid phase surface.These two kinds of ettringite all have the slurry of making expansible ability, but the former disperses to be filled in the space of original water-filling, and the latter is a support with original solid phase, and overlap joint intersected with each other just has more significant swelling capacity.Simultaneously, 2CaOSiO in the CaO in the slag, MgO and the sulphoaluminate cement clinker
2Aquation can keep Ca in the liquid phase (OH)
2High density, aluminium glue is at gypsum and Ca (OH)
2Effect under, generate AFt, reach the compensate for shrinkage effect, its chemical reaction process can be represented by the formula:
Slag and scoriaceous compound action mechanism are: slag is mainly made the micro-aggregate of gelling system in early days in aquation, and the hydrated product of aquation later stage generating portion increases liquid phase alkalescence, and aquation takes place in liquid phase slag simultaneously, with Ca (OH)
2, CaSO
4Reaction generates crystal such as C-S-H gel and AFt, is the main source of this system network skeleton; Slag is that to scoriaceous promoter action the slag aquation discharges Ca on the one hand
2+And OH
-, Ca wherein
2+With the silica reaction of low polymerization degree, OH
-Promote scoriaceous depolymerization; Crystalline inducing action in the slag on the other hand.Slag and slag compound hydrated product mainly contain Calucium Silicate powder and variant thereof, and its general formula is: CaOAl
2O
3XSiO
2YH
2The O mineral abbreviate C-S-Al-H as.The aluminium glue of sulphoaluminate cement clinker and gypsum reaction generation also can be accelerated the Ca of slag betwixt
2+Melt, promote the aquation of slag, the reactive behavior of system is improved.
Contain f-CaO, f-MgO in the slag, and CaO, MgO and water is when carrying out chemical reaction, after the reaction of the absolute volume of its solid phase respectively than having increased by 77%, 97.92% before the reaction, but with regard to CaO, MgO-H
2The O system, reacted cumulative volume can reduce because chemistry reduces.In fact, all gelling material (comprising cement, gypsum etc.) when Dang Heshui carries out chemical reaction, have all produced chemistry inevitably and have reduced.Yet CaO, MgO-H in practice,
2The O system is mixed and stirred the back volume and has been increased really, and the reason that produces so significant volumetric expansion can be analyzed from two aspects: whether two class substance transfer mate (1) hydration process.The one, water molecules (or OH
-) enter CaO, MgO particle inside, and hydration reaction takes place with it, generate hydrated product; The 2nd, hydrated reaction product is to original water-filling space transfer.(2) volume of voids increment.The increase of solid volume causes that the available simple geometric model of the increase of volume of voids comes proximate explanation such as Fig. 1 in addition.Among Fig. 1: bead-solid phase initial volume; Big ball-solid phase final volume; The initial volume of the interval-hole between the bead; Draw part-volume of voids increment that oblique line is arranged; The final volume that comprises the interval-hole between the oblique line ball partly.
Its chemical equation is as follows:
But since slag through 1650 ℃ high-temperature calcination after, f-CaO wherein, f-MgO are in the dead roasting state, so hydration activity is lower, but after its specific surface area reaches certain numerical value, its hydration activity can be improved, thus special stipulation of the present invention the specific surface area of steel-making slag powder.For f-CaO, f-MgO in AFt and this system as expansion sources, difference of time has guaranteed that this mineral admixture can prolonged expansion thereby it expands, because it is early stage that the generation of AFt mainly occurs in aquation, and the calcium oxide expansion time is in advance in magnesium oxide, so the expansion time of f-CaO can be thought in mid-term, f-MgO then can think in the later stage, thereby arrive sustainable expansible function.
The present invention utilizes slag, slag, sulphoaluminate cement clinker and gypsum to prepare a kind of high-activity concrete mineral admixture with compensate for shrinkage function.Four kinds of interaction between component in this system, coordinated development, it utilizes sulphoaluminate cement clinker and gypsum early response to generate the volumetric expansion performance behind f-CaO, the f-MgO further hydration in the compensate for shrinkage function of ettringite and the slag, produce with cement in the corresponding expansion rule of the shrinkage character of different aquation courses, effectively improvement is concrete in early days, shrink late period and cracking, improves the weather resistance of anti-permeability performance and construction work; Scoriaceous high reactivity in the performance system simultaneously, thus make it promptly have the function that high reactivity also has the prolonged expansion compensate for shrinkage.The activity index of this high-activity shrinkage-compensating mineral admixture and rate of expansion index can reach respectively: activity index 〉=80% (intensity rate); 28d rate of expansion: 0.03～0.05%; 180d rate of expansion 0.01～0.03%.
Description of drawings
Fig. 1 is volume of voids increment effect figure of the present invention
Embodiment
Example 1: high-activity shrinkage-compensating mineral admixture, it is mixed by slag, slag, sulphoaluminate cement clinker and gypsum, and its each component mass percent is: slag: slag: sulphoaluminate cement clinker: gypsum=40%: 40%: 15%: 5%.
The preparation method of above-mentioned high-activity shrinkage-compensating mineral admixture, comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=40%: 40%: 15%: 5%, choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with independent respectively grinding to the specific surface area of various raw materials is 400～500m
2/ kg mixes then, adorns bag at last, seals, seals up for safekeeping.
The activity index of this high-activity shrinkage-compensating mineral admixture and rate of expansion index can reach respectively: activity index 〉=80% (intensity rate); 28d rate of expansion: 0.03～0.05%; 180d rate of expansion 0.01～0.03%.
High-activity shrinkage-compensating mineral admixture must be under the dry moistureproof condition, otherwise the inefficacy of can luming.
Example 2: high-activity shrinkage-compensating mineral admixture, it is mixed by slag, slag, sulphoaluminate cement clinker and gypsum, and its each component mass percent is: slag: slag: sulphoaluminate cement clinker: gypsum=45%: 35%: 14%: 6%.
The preparation method of above-mentioned high-activity shrinkage-compensating mineral admixture, comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=45%: 35%: 14%: 6%, choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with independent respectively grinding to the specific surface area of various raw materials is 200m
2/ kg mixes then, with the mixture grinding to specific surface area 400～500m
2/ kg adorns bag at last, seals, seals up for safekeeping.
The activity index of this high-activity shrinkage-compensating mineral admixture and rate of expansion index can reach respectively: activity index 〉=80% (intensity rate); 28d rate of expansion: 0.03～0.05%; 180d rate of expansion 0.01～0.03%.
Example 3: high-activity shrinkage-compensating mineral admixture, it is mixed by slag, slag, sulphoaluminate cement clinker and gypsum, and its each component mass percent is: slag: slag: sulphoaluminate cement clinker: gypsum=46%: 30%: 18%: 6%.
The preparation method of above-mentioned high-activity shrinkage-compensating mineral admixture, comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=46%: 30%: 18%: 6%, choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with various raw material separated pulverizing to diameter less than 50mm, mix then, it is 400～500m that the mixture grinding is reached specific surface area
2/ kg adorns bag at last, seals, seals up for safekeeping.
The activity index of this high-activity shrinkage-compensating mineral admixture and rate of expansion index can reach respectively: activity index 〉=80% (intensity rate); 28d rate of expansion: 0.03～0.05%; 180d rate of expansion 0.01～0.03%.
Example 4: high-activity shrinkage-compensating mineral admixture, it is mixed by slag, slag, sulphoaluminate cement clinker and gypsum, and its each component mass percent is: slag: slag: sulphoaluminate cement clinker: gypsum=50%: 20%: 20%: 10%.
The preparation method of above-mentioned high-activity shrinkage-compensating mineral admixture, comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=50%: 20%: 20%: 10%, choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with independent respectively grinding to the specific surface area of various raw materials is 400～500m
2/ kg mixes then, adorns bag at last, seals, seals up for safekeeping.
The activity index of this high-activity shrinkage-compensating mineral admixture and rate of expansion index can reach respectively: activity index 〉=80% (intensity rate); 28d rate of expansion: 0.03～0.05%; 180d rate of expansion 0.01～0.03%.
Example 5: high-activity shrinkage-compensating mineral admixture, it is mixed by slag, slag, sulphoaluminate cement clinker and gypsum, and its each component mass percent is: slag: slag: sulphoaluminate cement clinker: gypsum=55%: 24%: 13%: 8%.
The preparation method of above-mentioned high-activity shrinkage-compensating mineral admixture, comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=55%: 24%: 13%: 8%, choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with independent respectively grinding to the specific surface area of various raw materials is 300m
2/ kg mixes then, with the mixture grinding to specific surface area 400～500m
2/ kg adorns bag at last, seals, seals up for safekeeping.
The activity index of this high-activity shrinkage-compensating mineral admixture and rate of expansion index can reach respectively: activity index 〉=80% (intensity rate); 28d rate of expansion: 0.03～0.05%; 180d rate of expansion 0.01～0.03%.
Example 6: high-activity shrinkage-compensating mineral admixture, it is mixed by slag, slag, sulphoaluminate cement clinker and gypsum, and its each component mass percent is: slag: slag: sulphoaluminate cement clinker: gypsum=60%: 20%: 10%: 10%.
The preparation method of above-mentioned high-activity shrinkage-compensating mineral admixture, comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=60%: 20%: 10%: 10%, choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with various raw material separated pulverizing to diameter less than 50mm, mix then, it is 400～500m that the mixture grinding is reached specific surface area
2/ kg adorns bag at last, seals, seals up for safekeeping.
The activity index of this high-activity shrinkage-compensating mineral admixture and rate of expansion index can reach respectively: activity index 〉=80% (intensity rate); 28d rate of expansion: 0.03～0.05%; 180d rate of expansion 0.01～0.03%.
Application example of the present invention:
Mineral admixture as cement concrete: in concrete, mix 5%～30% high-activity shrinkage-compensating mineral admixture, can obtain having the cement concrete material of fine mechanical property and microdilatancy performance.The steps include: to weigh up cement, high-activity shrinkage-compensating mineral Additive, stone, sand, water, solid water reducing admixture FDN by metering earlier, pour into cement, high-activity shrinkage-compensating mineral Additive, stone, sand, solid water reducing admixture in the stirred vessel respectively then, dry mixing 30s mixes it, then water is poured into slowly and stirred 30s in the stirred vessel, pour out moulding after guaranteeing to stir, on shaking table, vibrate 30s, mark to support and after the length of time, test its intensity, degree of free swelling according to GB.Part of test results such as table 1.
Table 1 is mixed the high-activity shrinkage-compensating mineral admixture concrete mix
| Cement (Kg/m 3) | High-activity shrinkage-compensating mineral Additive proportioning and volume (Kg/m 3) | W/C | Sand coarse aggregate ratio | FDN | Intensity (MPa) | Degree of free swelling (%) | |||
| Slag: slag: sulphoaluminate cement clinker: gypsum | Volume | (％) | (gelling material %) | 28d | 90d | 28d | 180d | ||
| 390 | 40％∶40％∶15 ％∶5％ | 0 | 0.41 | 40 | 0.85 | 43.5 | 50.1 | -2.1 | -4.2 |
| 351 | 39 | 0.41 | 40 | 0.85 | 44 | 52.3 | 3.1 | 1.1 | |
| 312 | 78 | 0.41 | 40 | 0.85 | 44.6 | 52.5 | 3.4 | 1.2 | |
| 273 | 117 | 0.41 | 40 | 0.85 | 42.3 | 50.2 | 4 | 1.3 | |
| 520 | 45％∶35％∶14 ％∶6％ | 0 | 0.33 | 39 | 1.3 | 58 | 65.2 | -3.4 | -4.5 |
| 468 | 52 | 0.33 | 39 | 1.3 | 58.9 | 67 | 4.5 | 2.1 | |
| 416 | 104 | 0.33 | 39 | 1.3 | 56.7 | 66.2 | 4.6 | 2.5 | |
| 364 | 156 | 0.33 | 39 | 1.3 | 54.2 | 64.2 | 4.9 | 2.5 | |
| 460 | 46％∶30％∶18 ％∶6％ | 0 | 0.39 | 40 | 1 | 52.4 | 55.8 | -2.9 | -4.3 |
| 414 | 46 | 0.39 | 40 | 1 | 51.5 | 58.8 | 3.6 | 1.6 | |
| 368 | 92 | 0.39 | 40 | 1 | 50.7 | 59.1 | 4 | 2 | |
| 322 | 138 | 0.39 | 40 | 1 | 49.2 | 57.5 | 4.1 | 2.2 | |
| 460 | 50％∶20％∶20 ％∶10％ | 0 | 0.39 | 40 | 1 | 52.4 | 55.8 | -2.9 | -4.3 |
| 414 | 46 | 0.39 | 40 | 1 | 50.5 | 55.5 | 3.2 | 1.3 | |
| 368 | 92 | 0.39 | 40 | 1 | 50.7 | 56.1 | 3.6 | 1.5 | |
| 322 | 138 | 0.39 | 40 | 1 | 48.9 | 54.3 | 3.8 | 1.6 | |
| 390 | 55％∶24％∶13 ％∶8％ | 0 | 0.41 | 40 | 0.85 | 43.5 | 50.1 | -2.1 | -4.2 |
| 351 | 39 | 0.41 | 40 | 0.85 | 42 | 48.9 | 3.5 | 1.9 | |
| 312 | 78 | 0.41 | 40 | 0.85 | 42.6 | 49.1 | 4.2 | 2 | |
| 273 | 117 | 0.41 | 40 | 0.85 | 40.3 | 46.8 | 4.4 | 2.4 | |
| 560 | 60％∶20％∶10 ％∶10％ | 0 | 0.31 | 39 | 1.5 | 71.1 | 75.6 | -4 | -5.4 |
| 504 | 56 | 0.31 | 39 | 1.5 | 70.3 | 80.1 | 3 | 2 | |
| 448 | 112 | 0.31 | 39 | 1.5 | 69.5 | 79.8 | 3.2 | 2.1 | |
| 392 | 168 | 0.31 | 39 | 1.5 | 68.8 | 78.6 | 3.5 | 2.2 |
Claims (4)
1. high-activity shrinkage-compensating mineral admixture, it is characterized in that: it is mixed by slag, slag, sulphoaluminate cement clinker and gypsum, its each component mass percent is: slag: slag: sulphoaluminate cement clinker: gypsum=40～60%: 20～40%: 10～20%: 5～10%, and the each component sum is 100%; Slag, slag, sulphoaluminate cement clinker and gypsum are through mixing, grinding, and obtaining Blain specific surface is 400～500m
2The dry powder of/kg has the high-activity shrinkage-compensating mineral admixture of high reactivity and compensate for shrinkage function.
2. the preparation method of high-activity shrinkage-compensating mineral admixture as claimed in claim 1, it is characterized in that: comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=40～60%: 20～40%: 10～20%: 5～10%, choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with independent respectively grinding to the specific surface area of various raw materials is 400～500m
2/ kg mixes then, adorns bag at last, seals, seals up for safekeeping.
3. the preparation method of high-activity shrinkage-compensating mineral admixture as claimed in claim 1, it is characterized in that: comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=40～60%: 20～40%: 10～20%: 5～10%, choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with independent respectively grinding to the specific surface area of various raw materials is 200～400m
2/ kg mixes then, is 400～500m with mixture grinding to specific surface area
2/ kg adorns bag at last, seals, seals up for safekeeping.
4. the preparation method of high-activity shrinkage-compensating mineral admixture as claimed in claim 1, it is characterized in that: comprise the steps: 1). by the each component mass percent be: slag: slag: sulphoaluminate cement clinker: gypsum=40～60%: 20～40%: 10～20%: 5～10%, choose slag, slag, sulphoaluminate cement clinker and gypsum; 2). with various raw material separated pulverizing to diameter less than 50mm, mix then, it is 400～500m that the mixture grinding is reached specific surface area
2/ kg adorns bag at last, seals, seals up for safekeeping.
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| US5580508A (en) * | 1986-04-04 | 1996-12-03 | Ube Industries, Ltd. | Process for preparing calcium silicate articles |
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