CN1181002C - High-efficiency cement - Google Patents

High-efficiency cement Download PDF

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Publication number
CN1181002C
CN1181002C CNB981024041A CN98102404A CN1181002C CN 1181002 C CN1181002 C CN 1181002C CN B981024041 A CNB981024041 A CN B981024041A CN 98102404 A CN98102404 A CN 98102404A CN 1181002 C CN1181002 C CN 1181002C
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cement
gypsum
total amount
content
blended material
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CN1238312A (en
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龙 曹
曹龙
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302Water reducers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The present invention relates to high efficiency cement. The cement is composed of portland cement clinkers, composite materials, gypsum, water-reducing type additives according to the weight ratio of 10 to 95: 0 to 80: 3 to 10: 0 to 20 of clinkers, composite materials, gypsum, and water-reducing type additives, additives are acked on the surfaces of particles and are embedded in cracks, the grain compositions of each raw material is clinkers and gypsum, the particle diameters are mainly centralized between 3 to 30 mu, and the particle diameters or partial particle diameters of composite materials are mainly centralized below 5 mu. The shape of particles approaches to a sphere shape or an equilateral long block shape, the average spheroidal degrees is larger than 0.60, free calcium oxide in clinkers used by cement is allowed to be broadened to 3.0%, magnesium oxide is allowed to be broadened to 10.0%, and the alkali content is allowed to be broadened to 1.5%.

Description

Cement
The present invention relates to a kind of material of construction, particularly relate to a kind of cement.
As everyone knows, silicate cement is widely used in the every field of national economy as a kind of material of construction, and the important foundation effect is played in progress to human civilization.Along with further investigation and the practice of people to cement, the concrete of finding the silicate cement preparation also has following shortcoming: common intensity only can reach about 1/3 of aggregate intensity, wear resistance, impermeability, erosion resistance, alkali resistant aggregate reaction ability, segregation, layering, bad performances such as interfacial transition zone not exclusively adapt to the modern architecture engineering.Chinese patent application 94104016.X proposes a kind of high-effect concrete cement special, it is characterized in that label is material modified greater than adding in 525# (the containing 525#) silicate cement, superplasticizer, expandable material, by label greater than the mixed grinding of 525# (containing 525#) silicate cement 60~80%, material modified 10~15% to 80 μ tail over below 5% high-effect concrete cement special.This patent has mainly solved the high-effect concrete department that constructs and has purchased multiple starting material and admixture simultaneously, at the construction field (site) or concrete mixing station repeatedly measure, calculate, operate, complex process is had relatively high expectations to construction management simultaneously, has carelessness just may cause the problem of accident resulting from poor quality of projects slightly.
Purpose of the present invention: overcome the defective of prior art, provide a kind of and producing and using each stage that good effect and high performance cement are all arranged.
Technical solution of the present invention: a kind of cement, is 10~95% by raw material weight than cement clinker, blended material is 0<~80%, gypsum is 3~10%, and the water reducing type admixture is 0<~2.0%, and the water reducing type admixture is wrapped in cement particle surface and inlays in the particle crack, cement clinker, gypsum does not comprise that the grain composition of the blended material that 5 μ are following is that grain diameter mainly concentrates on 3 μ~30 μ, and the grain diameter of blended material mainly concentrates on below 5 μ.
The following cement granules content of this cement 3 μ accounts for 10.0~50.0% of cement total amount less than the above cement granules content of 15%, 30 μ of cement total amount less than the following blended material granule content of 15%, 5 μ of cement total amount.
A kind of cement, when blended material was zero, the grain composition of cement clinker, gypsum was that grain diameter mainly concentrates on 3 μ~30 μ, and water reducing type admixture content is 0<~2.0%, and the water reducing type admixture is wrapped in cement particle surface and inlays in the particle crack.
The following cement granules content of this cement 3 μ less than the above cement granules content of 15%, 30 μ of cement total amount less than 15% of cement total amount.
A kind of cement, when the water reducing type admixture is zero, is 10~95% by raw material weight than cement clinker, blended material is 0<~80%, gypsum is 3~10%, cement clinker, gypsum, the grain composition that does not comprise the blended material that 5 μ are following is that grain diameter mainly concentrates on 3 μ~30 μ, and the particle of blended material mainly concentrates on below 5 μ.
The following cement granules content of this cement 3 μ accounts for 10.0~50.0% of cement total amount less than the above cement granules content of 15%, 30 μ of cement total amount less than the following blended material granule content of 15%, 5 μ of cement total amount.
A kind of cement, when blended material and water reducing type admixture were zero, the grain composition of cement clinker, gypsum was that particle mainly concentrates on 3 μ~30 μ.
The following cement granules content of this cement 3 μ less than the above cement granules content of 15%, 30 μ of cement total amount less than 15% of cement total amount.
Blain specific surface=the 7500cm of the following grain diameter of 5 μ 2/ g~30000cm 2/ g.
The cement granules shape is subglobular, or near etc. length of side block, the average spherical degree of cement granules is greater than 0.6.
Free calcium oxide content in the cement clinker allows to be loosened to 3.0%, but should satisfy the calcium oxide content that dissociates in the cement simultaneously less than 1.8%.
Content of magnesia in the cement clinker allows to be loosened to 10.0%, but should satisfy in the cement content of magnesia simultaneously less than 6.0%.
Alkali content in the cement (is converted into equivalent Na 2O) allow to be loosened to 1.5%.
The present invention satisfies manufacture of cement stage high grade, less energy-consumption, low noxious gas emission, low cost simultaneously, the waste reside comprehensive utilization amount is big, raw material sources are extensive; But cement construction stage height application property (high workability, high cohesion), the modernization of adaptation construction industry, lower noise pollute, low cost; Cement stone (concrete) stage high-durability (high-wearing feature, high permeability resistant, high corrosion resistance, high frost resistance, high alkali resistance aggregate reaction).
The grog that uses in the cement of the present invention is conventional Portland clinker, and except that free calcium oxide, magnesium oxide, three indexs of alkali content can exceed standard, all the other performances must meet the requirement of the country one belongs to's national standard to Portland clinker.Blended material is meant all blended materials that meet the country one belongs to's national standard to permission use blended material in the cement, but with no endoporus blended material better performances.Gypsum is meant that all the country one belongs to's national standards that meets are to allowing to use all gypsum of gypsum in the cement.The water reducing type admixture is meant that all water reducing type admixtures that allow in the country one belongs to's national standard cement or the concrete to use that meet all can use, but with naphthalenesulfonate formaldehyde condensation compound, water-soluble melamine sulfonate formaldehyde condensation products effect is better, as better with the compound result of use of graft copolymer.Water reducer generally at the construction field (site) or concrete mixing station add, it removes complicated operation, construction management is had relatively high expectations outside the shortcoming, the more important thing is that it can not give full play to the usefulness of water reducer, after water reducer adds in the concrete, at first be dissolved in water, again from solution to the cement particle surface adsorption and enrichment, in this process, water contacts with cement particle surface, and carry out aquation at once, and having produced hydrated product, this part hydrated product had both increased the cement slurry internal resistance, adsorbed a part of water reducer hydrophobic group again, also consumed a part of water, therefore caused the water reducer consumption to increase, effect reduces.When water reducer adds during at cement grinding, in grinding process, extruding in the steel ball forging, hit, under the mechanical force such as friction, evenly be wrapped in cement particle surface and embedding cement granules recessed part or the crack, when concrete is constructed, water contacts with the water reducer integument earlier, rather than contact with cement particle surface, so just effectively reduced the hydration of cement, water-reduction is brought into play preferably, water reducer directly adds when changing at cement grinding in concrete construction and adds, and can bring up to 30~40% to the water-reducing rate of high efficiency water reducing agent from 15~25%, and water-reducing effect increases more than 60%.Conventional silicate cement calcium oxide, silica weight approximate 3 than (writing a Chinese character in simplified form c/s), hear rate about 110% during clinker burning, decomposing and decompose because of lime carbonate all of Carbon emission needs heat to cause, from energy-conservation and minimizing temperature effective angle, should reduce c/s ratio in the cement, higher c/s is than also the direct or indirect calcium hydroxide crystal that causes in the cement stone is more, bigger; PH value is higher; Hydration heat is more; Reduced F-CaO, MgO, alkali (Na 2O, K 2O) aquation generates CSH (B), MSH, R 2The chance of OASH; Form the enrichment of calcium hydroxide crystal in the interfacial transition zone of gathering materials, above phenomenon all can cause cement stone homogeneity variation, produces tiny crack, causes cement strength to reduce, and the weather resistance variation also should reduce c/s ratio the cement from improving cement stone quality angle.Cement stone final product be CSH (B) (c/s=0.78) when advocating peace the less water garnet, the over-all properties of cement stone is better, is converted into the chemical component weight ratio that participates in the hydration reaction component in the cement raw material to be: 0.78SiO 2+ 0.55Al 2O 3+ 0.35Fe 2O 3+ 0.7SO 3=CaO+1.4MgO+0.9 (Na 20+0.66K 20).Each feed particles grating of cement, particle shape should satisfy hydrated reaction of cement speed, the requirement of flowability and cohesiveness, these three parameters are contradiction sometimes.Cement is thin more, and spherical degree is more little, and voidage is big more, and the hydration rate of cement is fast more; Cement is thin more, and spherical degree is more little, and voidage is more little, and hour hydrability activity is big more, and cohesiveness is big more; And the spherical degree of cement is big more, and voidage is more little, and hour hydrability activity is more little, and the flowability of cement is good more.Conventional cement generally adopts the one-level grinding, granulometric range is at 0.5 μ~100 μ, the above particle of 30 μ is more than 30%, has cement about 30% not participate in the hydration process of cement, and the cohesiveness of cement is lower, voidage is higher, cause water requirement to increase, concrete layering, segregation, bad interfacial transition zone cause the concrete workability to reduce, intensity reduces, the weather resistance variation.Facts have proved that making pumping not produce the following particle of cement 3 μ of obvious layering, segregation, use from the levelling concrete should be greater than 30%, but the one-level grinding cement grinding to 30% being irrational below particle diameter 3 μ.This is that the following content of grog particle 3 μ increases substantially because when grinding arrived this particle diameter, the unit grinding pow consumption increased substantially, concrete is just a large amount of aquations in construction process, and flocculation causes effective gelling amount to reduce on the contrary, the mobile reduction causes the cement strength retraction, the weather resistance variation.Adopt process for producing high strength multifunctional cement or high speed self collision mill (grinding machine that material mainly relies on self speed to pulverize greater than 100 meter per seconds run foul of each other) can both reduce grog, the above granule content of gypsum 30 μ effectively, reduce the following granule content of 3 μ again, thereby cause the effective gelling amount of cement to increase, the mobile raising, intensity improves, and can also reduce the unit grinding pow consumption significantly.(the easiest realization is flyash blended material, this is just less than 100 μ because of the particle diameter of flyash own, and more carbon residue arranged, be the high-quality grinding aid, adapt to very much little forging mill and height and carefully select powder, as blended material and flyash combined grindings such as slag, slag, Wingdales, technology is just complicated, grinding pow consumption increases, but grinding is during to equal fineness, and the cement over-all properties improves) be ground to particle diameter major part (Blain specific surface=7500cm below 5 μ separately 2/ g~30000cm 2/ g) after again and cement mixing, can reduce the cement voidage, improve cement thick liquid flowability, improve simultaneously cohesiveness again, thereby but the concrete application property is improved greatly, also improved pore structure of cement stone, interface structure, reduce cement stone voidage, thereby caused Cement Concrete intensity to significantly improve, and fundamentally improved the Cement Concrete weather resistance.(this grog refers to rotary kiln clinker to the grog that conventional cement uses, shaft kiln clinker in this way, what have because of the free calcium oxide of check is not truly free calcium oxide, therefore calcium oxide content can also improve) in free calcium oxide content can not be greater than 1.0%, otherwise, free calcium oxide is in cement stone sclerosis back aquation, volumetric expansion 97%, cause that cement stone destroys, but high-efficiency cement 85% above particle diameter is less than 30 μ, most of about 15 μ, mix the macro-mixing material in the cement, and the particle diameter major part is less than 5 μ, cement c/s is than near 1, above condition makes free calcium oxide further hydration expansion damage power transform into compensation cement convergent force and makes cement stone more closely knit, becomes the measure that improves cement quality.The free calcium oxide manipulated variable was loosened to 3.0% by 1.0% when grog burnt till, and can improve identical kiln type grog output more than 50%, burnt till specific investment decline, hear rate, power consumption reduction, and the raising of grog grindability, and grinding pow consumption also descends.The MgO in clinker content that conventional cement uses can not be greater than 5%, otherwise, magnesium oxide is in cement stone sclerosis back aquation, volumetric expansion 118%, cause that cement stone destroys, but high-efficiency cement 85% above particle diameter is less than 30 μ, most of about 15 μ, mix the macro-mixing material in the cement, and the particle diameter major part is less than 5 μ, cement c/s ratio is near 1, and above condition makes magnesium oxide further hydration expansion damage power transform into compensation cement convergent force and makes cement stone more closely knit, becomes the measure that improves cement quality.Under the resources supplIes of specific mine, the control of MgO in clinker content brings up to 10.0% by 5.0%, helps mine resources and effectively utilizes, and has great economic implications and environment protection significance.The alkali content general requirement is lower than 1.0% and (is converted into equivalent Na in the conventional cement 2O), the activity area that gathers materials is being arranged, is requiring to be lower than 0.6%, otherwise, in the cement alkali with gather materials in the activated silica reflection generate alkali-silica gel and water-swelling, concrete is destroyed.But c/s is than near 1 in the high-efficiency cement, and blended material (silicon-aluminum containing part) particle diameter major part is less than 5 μ, and the water requirement of cement is lower.Above condition makes the alkali in the high-efficiency cement just can generate the stable alkali mineral one that contain with silicon, aluminium in early days in aquation contain hydronephelite, hydrous zeolite, hydrous mica.Basically consumed the alkali in the cement, alkali can not be taken place.When high-efficiency cement was prepared high-effect concrete, general water cement ratio was lower than 0.35, and the density of concrete improves greatly, gathers materials to be in drying regime, had reduced alkali-silica gel suction and had produced the expansible possibility.Contain the higher area of alkali or contain the activity area that gathers materials at raw material, alkali content control brings up to 1.5% by 0.6% in the cement, helps mine resources and effectively utilizes, and helps reducing the concrete cost, has great economic implications and environment protection significance.
Further specify the performance of cement in conjunction with the embodiments:
Cement performance sees Table one, and the concrete performance sees Table two.
See table one, contrast sequence number 1 and 3, the cement flows raising of process for producing high strength multifunctional cement production is more than 6% as can be seen, and intensity improves more than 20%, and this all causes with the above grog particle of 30 μ less owing to 3 μ are following.Contrast sequence number 2 and 4, the cement flows raising of process for producing high strength multifunctional cement (admixture adds when grinding) production is more than 20% as can be seen, intensity improves more than 50%, this because 3 μ are following and the above grog particle of 30 μ all less and admixture when grinding, evenly be wrapped in the grog particle surface and cause.Contrast HPC-95, HPC-50, HPC-34, HPC-10 are as can be seen, the relation with contents of grog is little in strength of cement and the cement, but it is bigger with cement each component fineness and water requirement dependency, this discovery helps reducing unit cement obnoxious flavour CO2 emissions, a large amount of comprehensive utilization industrial residues have great economy and environment protection significance.See table two, contrast sequence number 2 and 3,4 as can be seen, increasing blended material addition content (reducing the c/s ratio) is the key measure that improves the concrete weather resistance.See table one, table two, the obvious characteristic of high-efficiency cement is as can be seen: rational each feed particles grating, and reasonably there is form in admixture, reasonably the c/s ratio, thereby cement density, homogeneity are improved greatly, and the result causes high-efficiency cement intensity weather resistance to significantly improve.
The present invention is summary and has absorbed the twentieth century Cement industry, concrete industry and industrial multinomial discovery of comprehensive utilization and scientific and technological achievement, with its creationary combination and develop perfect new cement, it has been great qualitative leap for the first time since the Cement industryization, be extremely rising new cement, be particularly useful for modernization construction and modernized high-durability engineering: as Longspan Bridge, the tunnel, underground works, oceanographic engineering, hydro project, at a high speed, the high loading highway, airfield runway, Highrise buildings, nuclear reactor shell, special engineerings such as military engineering and poisonous and harmful waste treatment.The material qualitative leap must cause the innovation of constructing, derived product qualitative leap, produce new industry, have good quality, economy, environmental protection, social benefit, and make human living space and bigger being expanded of life quality, can obtain the social progress that to predict now.

Claims (8)

1. cement, it is characterized in that: is 10~95% by raw material weight than cement clinker, blended material is 0<~80%, gypsum is 3~10%, and the water reducing type admixture is 0<~2.0%, and the water reducing type admixture is wrapped in cement particle surface and inlays in the particle crack, cement clinker, gypsum does not comprise that the grain composition of the blended material that 5 μ are following is that grain diameter mainly concentrates on 3 μ~30 μ, and the grain diameter of blended material mainly concentrates on below 5 μ.
2. cement according to claim 1, it is characterized in that: the cement granules content below 3 μ is less than 15% of cement total amount, the above cement granules content of 30 μ accounts for 10.0~50.0% of cement total amount less than the following blended material granule content of 15%, 5 μ of cement total amount.
3. cement, it is characterized in that: when blended material is zero, the grain composition of cement clinker, gypsum is that grain diameter mainly concentrates on 3 μ~30 μ, and water reducing type admixture content is 0<~2.0%, and the water reducing type admixture is wrapped in cement particle surface and inlays in the particle crack.
4. cement according to claim 3 is characterized in that: the following cement granules content of 3 μ less than the above cement granules content of 15%, 30 μ of cement total amount less than 15% of cement total amount.
5. cement, it is characterized in that: when the water reducing type admixture is zero, is 10~95% by raw material weight than cement clinker, blended material is 0<~80%, gypsum is 3~10%, cement clinker, gypsum, the grain composition that does not comprise the blended material that 5 μ are following is that grain diameter mainly concentrates on 3 μ~30 μ, and the particle of blended material mainly concentrates on below 5 μ.
6. cement according to claim 5, it is characterized in that: the cement granules content below 3 μ is less than 15% of cement total amount, the above cement granules content of 30 μ accounts for 10.0~50.0% of cement total amount less than the following blended material granule content of 15%, 5 μ of cement total amount.
7. cement is characterized in that: when blended material and water reducing type admixture were zero, the grain composition of cement clinker, gypsum was that particle mainly concentrates on 3 μ~30 μ.
8. cement according to claim 7 is characterized in that: the following cement granules content of 3 μ less than the above cement granules content of 15%, 30 μ of cement total amount less than 15% of cement total amount.
CNB981024041A 1998-06-08 1998-06-08 High-efficiency cement Expired - Fee Related CN1181002C (en)

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