CN103396017A - Wrought material of ultralow temperature cementing material and preparation method of wrought material - Google Patents

Abstract

The invention discloses a wrought material of an ultralow temperature cementing material. C3S-C2S-CaO is a main component of the wrought material; and the wrought material is prepared by adding excess CaO into a cement raw material with a CaO-SiO2-Al2O3-Fe2O3-SO3 quinary system, and calcining under a reasonable firing temperature. The wrought material has characteristics of fast solidification, fast hardening, early strength, high strength, and the like. Especially, early stage heat release amount is large, so that the wrought material is capable of preventing the generation of concrete freezing damages, and promoting normal growth of the strength of thin-layer concrete. Under conditions without special anti-freezing measures, freshly mixed concrete is capable of withstanding early stage freezing damages under ultralow temperature, and promoting normal growth of the strength. The wrought material is especially suitable for pouring, grouting, spray anchoring, and reinforcing of ever frozen soil foundations in high and cold ever frozen soil areas, broken ice crevasses and landslides, ancient (contemporary) glaciers, riverbeds, and soft laminated palisades.

Description

A kind of ultra-low temperature glue gel material grog and method for making thereof

Technical field

The present invention relates to a kind of building cementing material, specifically a kind of ultra-low temperature glue gel material grog, also comprise its method for making in addition.

Background technology

In the eighties, because of Research Institute of Building Materials Industry, invented C ₂S-

The aluminosulfate cement of system, be called for short CAS cement, and this cement is a large amount of owing to containing

Therefore mineral, have fast solidifying, the fast characteristics such as hard, early strong, high-strength.These characteristics have solved the various quality problems that occur in OPC cement winter construction journey effectively, are the ideal materials of the winter construction journeys such as current slip casting, injection, soil consolidation.But the cost of material own is high, is unfavorable for spread, while under condition of ultralow temperature, constructing in addition, also must add special-purpose admixture and the winter that adapts to execute Insulation, could meet the construction quality requirement.This technology obtains national invention second prize.

The nineties, C invented in Chinese building material institute ₃S- The Alite-sulphoaluminate of series, the patent No. 86103018, this cement is except keeping the OPC cement properties, also have the CAS cement characteristics of solidifying, early strong, high-strength and microdilatancy soon concurrently, this technology is gain the national patent, and indivedual producers produce in batches, but without the producer of long-term production.

In the soil consolidation technical field, the Roadbond of Britain (patent No. 4941924) product is liquid, sulfuric acid degreasing citric acid oil, tensio-active agent, retardant etc., consists of, and approximately 3.75 liters of stostes can make the clay hardening of 20 cubic metres.Commercially available prod, South Africa " Yi Nengda " volume can make loose clay as body of wall and roadbed under 2.0% condition.Chinese building material institute develops a kind of superpolymer liquid solidifying agent, can make sand and sandy soil effectively fixed, and the fixed expense in top layer 0.5 yuan/square meter only.But the common feature of these products is: one all needs to add cement and lime subsidiary material just can reach ideal effect; Its two, in the very low temperature situation, can not use at all.

The high-strength solidifying agent of a kind of powder of Chinese building material institute development, can fixed sand factor less than 30% clay, intensity is up to 7.OMPa, make roadbed, riverbed, levee slope, mud effectively fixed, but volume is generally greatly more than 10%, and when the very low temperature eternal frozen ground was fixed, because hydration heat is low, gain in strength is slow, consolidation effect obviously weakened.

Cement jet, anchor,, protect very low temperature winter construction journey, also be based on OPC cement both at home and abroad and add the modified version admixtures researchs such as low-dosage high efficient antifreeze, rapid hardening, bleed, toughener.On coagulation, aspect proportioning and constructional method, still adopt the increasing cement consumption to improve cement mark, adopt hot water to stir and strengthen the test of the comprehensive means such as Insulation and the research of dried (wetting) pressure spray process.The insider makes every effort to find a kind of low cost, high-performance, is particularly suitable for special gelatin gel material and the engineering utilisation technology of condition of ultralow temperature construction, but there is no at present play-by-play.

Summary of the invention

The special gelatin gel material grog and the method for making thereof that the purpose of this invention is to provide the special use under a kind of ultra-low temperature surroundings.This material fast solidifying except having, fast hard, early strong, high-strength, particularly early stage thermal discharge is high, this self heat energy both can stop freeze injury of concrete under ultra-low temperature surroundings to occur effectively, also can promote thin-lift concrete intensity normal growth.

Technical scheme of the present invention is achieved in that a kind of ultra-low temperature glue gel material grog, and is a kind of with C ₃S-C ₂S-

-CaO mineral coupling is the grog of main component.

The chemical constitution of described grog is in following scope: CaO=45～55%; SiO ₂=15～20%; C ₄A ₃S=12～18%; Al ₂O ₃=7～10%; Fe ₂O ₃=5～8% and a small amount of SO ₃.

The mineral composition of described grog is in following scope: C ₃S=45～55%; C ₂S=15～20%; C ₄A ₃S=12～18%; C ₄AF=7～10%; The b-CaO=5 of parcel～8% and a small amount of CaSO ₄With CaF ₂.

The method for making of ultra-low temperature glue gel material grog, CaO-SiO _2-Al ₂O ₃-Fe ₂O ₃-SO ₃In the cement slurry of quinary system, excess has been introduced CaO, and the content of excessive oxidation calcium, between b-CaO=5～8%, is controlled in basicity factor Km=1.0～1.3 scopes, and grog is made in calcining under the firing temperature of 1200 ℃～1300 ℃.

Described proportioning raw materials without cement slurry in system, count with massfraction: Wingdale 70-80%; Coal gangue 12-18%; Gypsum 5-10%; Alumina 1-5%.Can mix in addition the industrial tailings of 0.8-1.0%.

The chemical constitution of described raw material is counted with massfraction:

SiO 2	Al 2O 3	Fe 2O 3	CaO	CaF 2	SO 3
						9.0～10.0	7.0～7.2	1.5～1.9	43.0～43.6	0.2～0.3	4.0～4.2

The present invention is at CaO-SiO _2-Al ₂O ₃-Fe ₂O ₃-SO ₃In the cement slurry of quinary system, excess has been introduced CaO.Changed in cement ingredient, lime saturation factor KH can only≤1 traditional concept, Km represents with basicity factor, calculation formula is as follows:

According to basicity factor formula and petrofacies Mineral Quantitative, determine that the mineral composition calculation formula is as follows:

During batching, can set the content of excessive oxidation calcium between b-CaO=5～8%, control in basicity factor Km=1.0～1.3 scopes, from the Portland cement chemical equilibrium, the K value is generally less than 1.0, otherwise, there will be excessive CaO.The present invention C ₄A ₃The S mineral have replaced C ₃The A mineral have improved early strength, with the calcium oxide b-CaO mineral of excessive parcel, improve heat and expansion energy, have realized that new chemical equilibrium is also key problem in technology of the present invention.Facts have proved: the gelling material of introducing this mineral preparation not only has enough early expansion energy, overcomes the destruction that concrete produces because of contraction, and the early water heat-transmission of concentrating can be provided, and resists the freeze injury impact, keeps concrete strength normally to bring into play.

The excess calcium oxide mineral that the present invention introduces, the form that exists in grog, must be phase in the middle of black, C ₄A ₃S mineral or other b-CaO that wraps up mutually, rather than form free f-CaO or the dead roasting f-CaO of secondary precipitation after other mineral.The former, early strong hydration heat is high, swell increment is large, stationary phase is short, and latter's late expansion, be attributed to toxic mineral.

Fe in grog ₂O ₃Reasonable content be also key problem in technology of the present invention, Fe ₂O ₃Can only form the middle phase C of black ₄AF, Fe ₂O ₃Content is too low, the C of formation ₄The AF liquid phase is just low, and the CaO mineral in grog just can not wrap up fully, and too high grog easily forms bulk or ring formation, and impact is produced.

Al in grog ₂O ₃Mainly with C ₄A ₃The form of S mineral exists, Al ₂O ₃Content is too low, the C of formation ₄A ₃S is just low, and early strength can not meet, and the late expansion amount is large.

By the research of different material, chemical composition, mineral coupling, firing condition, determined optimum mix, calcining system and the manufacturing condition of this grog.

The present invention is a kind of with C ₃S-C ₂S- -CaO is composition and the manufacture method of the very low temperature special gelatin gel material of main ingredient, due to this system, introduced the middle phase of high calcium of superfluous surface parcel, both kept the silicate cement good characteristic, have again early strong, high-strength characteristics of aluminosulfate cement, also have high hydration heat and expansion energy.The series product of preparation solidifying, fast hard, speed of response soon are exceedingly fast, and during aquation, are subjected to hardly the impact of low temperature environment, be particularly suitable under condition of ultralow temperature spray, anchor,, protect and repairing, rush construction engineering.

Embodiment

Below in conjunction with specific embodiment, the present invention is explained.

(1) charge calculation:

According to former, chemistry of fuel composition analysis, charge calculation is in Table 1.

Table 1

。

(2) raw material preparation:

Control out mill raw material T-CaCO ₃=76% ± 0.5; SO ₃=4.0% ± 0.2; Fineness 0.08mm tails over≤8%, and class's qualification rate is more than 80%.The raw meal powder that goes out mill must, through mechanical storehouse or pneumatic blending homogenizing storehouse homogenizing, guarantee that the every control index of kiln raw material reaches more than 98%.The grog chemical analysis composition of preparation is in Table 2.

Table 2

。

(3) grog burns till:

While by common raw material, being made into newly to join raw material, while namely adding excessive GaO, adopt hot joining method long flame calcining process.Namely in the situation that section stops kiln, stop feeding, strengthen air draft, reduce kiln temperature to new batching optimal temperature, after 1 hour, can feed virgin material, after 3 hours, can normally burn till special gelatin gel material grog.Grog chemical composition and mineral composition in Table 3, table 4.

Table 3

Table 4

The above; it is only preferably embodiment of the present invention; but protection scope of the present invention is not limited to this; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; according to technical scheme of the present invention and inventive concept thereof, be equal to replacement or changed, within all should being encompassed in protection scope of the present invention.

Claims (7)

1. a ultra-low temperature glue gel material grog, is characterized in that, and is a kind of with C ₃S-C ₂S-

-CaO mineral coupling is the grog of main component.

2. ultra-low temperature glue gel material grog according to claim 1, is characterized in that, the chemical constitution of described grog is in following scope: CaO=45～55%; SiO ₂=15～20%; C ₄A ₃S=12～18%; Al ₂O ₃=7～10%; Fe ₂O ₃=5～8% and a small amount of SO ₃.

3. ultra-low temperature glue gel material grog according to claim 1, is characterized in that, the mineral composition of described grog is in following scope: C ₃S=45～55%; C ₂S=15～20%; C ₄A ₃S=12～18%; C ₄AF=7～10%; The b-CaO=5 of parcel～8% and a small amount of CaSO ₄With CaF ₂.

4. as the method for making of the described ultra-low temperature glue gel material of claim 1-3 any one grog, it is characterized in that CaO-SiO _2-Al ₂O ₃-Fe ₂O ₃-SO ₃In the cement slurry of quinary system, excess has been introduced CaO, and the content of excessive oxidation calcium, between b-CaO=5～8%, is controlled in basicity factor Km=1.0～1.3 scopes, and grog is made in calcining under the firing temperature of 1200 ℃～1300 ℃.

5. the method for making of ultra-low temperature glue gel material grog according to claim 4, is characterized in that, described proportioning raw materials without cement slurry in system is counted with massfraction: Wingdale 70-80%; Coal gangue 12-18%; Gypsum 5-10%; Alumina 1-5%.

6. the method for making of ultra-low temperature glue gel material grog according to claim 5, is characterized in that, mixes the industrial tailings of 0.8-1.0% outward.

7. the method for making of ultra-low temperature glue gel material grog according to claim 6, is characterized in that, the chemical constitution of described raw material is counted with massfraction:

SiO ₂ Al ₂O ₃ Fe ₂O ₃ CaO CaF ₂ SO ₃ 9.0～10.0 7.0～7.2 1.5～1.9 43.0～43.6 0.2～0.3 4.0～4.2

。