CN1330601C - High sulfide resistant cement demixture and preparation thereof - Google Patents

High sulfide resistant cement demixture and preparation thereof Download PDF

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Publication number
CN1330601C
CN1330601C CNB2005101205071A CN200510120507A CN1330601C CN 1330601 C CN1330601 C CN 1330601C CN B2005101205071 A CNB2005101205071 A CN B2005101205071A CN 200510120507 A CN200510120507 A CN 200510120507A CN 1330601 C CN1330601 C CN 1330601C
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blast furnace
furnace slag
properties
correcting agent
mass ratio
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CN1792972A (en
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马保国
罗忠涛
高小建
张美香
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

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Abstract

The present invention relates to a cement admixture with high resistance to sulfur and a preparation method thereof. The present invention is characterized in that the present invention is mainly prepared by water quenched slag of a blast furnace, modifiers and shrinkage reducing functional components; the mass ratio of the water quenched slag of a blast furnace and the modifier is 100: 0.01 to 0.02; the mass percentages of the water quenched slag of a blast furnace, the modifier and the shrinkage reducing functional components are from 95 to 99 % of the water quenched slag of a blast furnace and the modifier, and from 1 to 5 % of the shrinkage reducing functional components; the modifier is polycarboxylic acid type super dispersers and triethanolamine grinding aids; the mass ratio of the polycarboxylic acid type super dispersers and the triethanolamine grinding aids is 1: 0.7 to 1; the shrinkage reducing functional components are alkylenediol or polyoxyalkylene glycol and silica fume; the mass ratio of the alkylenediol or polyoxyalkylene glycol and the silica fume is 1: 15 to 20. The present invention has high sulfur resistant performance under the corrosion environments by various sulphate, and has the characteristics of low alkali content and low production cost.

Description

High sulfide resistant cement demixture
Technical field
The invention belongs to the material of construction class, be specifically related to a kind of high sulfide resistant cement demixture.
Background technology
As everyone knows, the sulphate attack problem is a key issue of concrete durability aspect, China is concrete sulphate erosive prone areas, all exists the engineering that causes because of sulphate attack to destroy example as the concrete structure of coastland, the Northwest, southwest.And under the gentle time in different regions, exist dissimilar sulphate attacks.Developing high sulphate-resistant cement kind can become the technique means that engineering circle generally adopts in order to solve concrete sulphate-corrosion resistance, existing both at home and abroad a large amount of research, and lot of documents is arranged.The major technique content is:
Sulfate resisting Portland cement mainly is (promptly to control C by the control that cement clinker mineral is formed 3S, C 3A, C 4The proportion of composing of AF etc.), normally improve C 3The S ratio, high C 3S content can make concrete reach early strong purpose, improving the degree of compactness after its moulding, and makes concrete reach the effect of resisting erosion of sulfate with this.
Extraordinary sulphate-resistant cement and the production method thereof announced of CN96118342.X for example: its main chemism be the concrete plastic stage in the sclerosis elastic limit, finish CaO, CaSO 4, C 4A 3S changes into the reaction of ettringite.This technology can refinforced cement stone degree of compactness, improve the intensity and the anti-permeability performance of cement stone, thereby reach the purpose of resisting erosion of sulfate.But this type of the invention at the sulphate attack type more single, there is very big difference in action effect under different sulfate corrosion environment.On the other hand, this invention production cost is higher, remains further to be reduced production costs.
Summary of the invention
The object of the present invention is to provide a kind ofly can under multiple sulfate corrosion environment, (ettringite type, gypsum model, Thaumasite type) have high antisulphuric ability, and have the high sulfide resistant cement demixture of low alkali content, lower production cost.
Technical scheme of the present invention is: high sulfide resistant cement demixture, it is characterized in that it mainly is prepared from by blast furnace slag, properties-correcting agent, reducing function component raw material, preparation process is as follows: 1). the pre-treatment of blast furnace slag: select the commercially available blast furnace slag that meets national standard for use, with its oven dry, water ratio after the oven dry is less than 2%, and is standby; 2). the preparation of properties-correcting agent: adopting the solid solution ratio is 1: the polyocarboxy acid type hyper-dispersant of 2-3 and trolamine grinding aid are by mass ratio 1: 0.7-1 mixes, and is standby; 3). the preparation of reducing function component: aklylene glycol or polyoxyalkylene diols and silicon are grey by mass ratio 1: 15-20 mixes, and is standby; 4). the mass ratio by blast furnace slag and properties-correcting agent is 100: 0.01-0.02 chooses pretreated blast furnace slag, properties-correcting agent, adds properties-correcting agent and carry out mix grinding in pretreated blast furnace slag, makes its Blain specific surface reach 400-450m 2/ Kg gets the mix grinding material; Again with mix grinding material and function ingredients by mass percentage for the mixed of 95-99: 1-5 evenly forms, product.
Wherein silicon ash main chemical compositions is as shown in the table, and fluctuation is no more than 10% of former content.
The main composition CaO SiO 2 Al 2O 3 Fe 2O 3 MgO SO 3 Loss on ignition
Quality percentage composition (%) 0.33 90.54 0.77 1.77 1.68 0.40 2.78
All types of sulphate attack mechanism are as follows:
Ettringite (CaOAl 2O 33CaSO 431H 2O) type is with Na 2SO 4Be example.
Na 2SO 4·10H 2O+Ca(OH) 2→CaSO 4·2H 2O+2NaOH+8H 2O
3CaSO 4·2H 2O+4CaO·Al 2O 3·12H 2O+14H 2O→3CaO·Al 2O 3·3CaSO 4·31H 2O+Ca(OH
In this process, ettringite combines a large amount of crystal water on chemical structure, and its volume is about 2.5 times of former drated calcium aluminate, solid volume is enlarged markedly, it makes needle-like crystal on the mineral form in addition, mutual extrusion and produce great internal stress, thus cause destroying.
Gypsum CaSO 42H 2The O type is with Na 2SO 4Be example.
Na 2SO 4·10H 2O+Ca(OH) 2→CaSO 4·2H 2O+2NaOH+8H 2O
Be converted into gypsum from calcium hydroxide, volume increases to original 2 times, makes concrete cause expansion damage because of internal stress is excessive.
Thaumasite Ca 6[Si (OH) 6] 224H 2O[(SO 4) 2(CO 3) 2] type, (Ca (OH) wherein 2Be recycled consumption as reactant).
CaCO 3+SO 4 2-+2H 2O→CaSO 4·2H 2O+CO 3 2-
C 3S 2H 3+2(CaSO 4·2H 2O)+2CaCO 3+24H 2O→
Ca 6[Si(OH) 6] 2·24H 2O·[(SO 4) 2·(CO 3) 2]+Ca(OH) 2
So under the long term, the water mudrock structure body in the concrete is decomposed gradually, has finally formed thaumasite, ettringite, gypsum and 4 kinds of corrosion products of calcite, make concrete finally become a kind of do not have intensity, pulp shape silt particle mixture.
All exist Ca (OH) in the above all types of erosion mechanism 2Participation, and a main aspect of this product is exactly low Ca (OH) 2Content has reduced the reaction source; Therefore, the present invention can (ettringite type, gypsum model, Thaumasite type) have high antisulphuric ability under multiple sulfate corrosion environment.Have early strength and later strength bonded advantage on the other hand, increased concrete permeability resistance, stoped erosion ionic invasive channel.
The effect of blast furnace slag after the modification (being the mix grinding material) in high sulfide resistant cement demixture: the one, its Blain specific surface is 400-450m 2/ Kg can significantly improve concrete anti-permeability performance, helps stoping harmful ionic that corrodes to be invaded; The 2nd, it is low alkali, the Ca that generates after the aquation (OH) 2Content is very low, has reduced the material source of sulphate attack; The 3rd, reducing function component, properties-correcting agent etc. are disperseed evenly; The 4th, its big volume (more than 95%) mixes and can reduce production costs.
The effect of reducing function component in high sulfide resistant cement demixture: the one, the dry shrinkage of concrete value is obviously reduced, prevent the generation of tiny crack, and improve concrete crushing strength; The 2nd, it has good consistency with concrete admixtures such as the hardening accelerator of using always, water reducer, retardant.
The effect of properties-correcting agent in high sulfide resistant cement demixture: the polyocarboxy acid type hyper-dispersant has very strong dispersiveness on the one hand, and has may command concrete slump loss and compressive strength rate advantages of higher; The trolamine grinding aid can significantly improve the combined grinding effect on the other hand, significantly reduces power consumption.Trolamine has early strength function simultaneously, can improve concrete degree of compactness.
Said components and proportioning are prepared the high sulfide resistant cement demixture that just obtains a kind of excellent performance by processing requirement, after its quality such as ratio with 50-70% replaces ordinary portland cement, can obtain good technical and economical effectiveness.For example: 1, blast furnace slag powder activity wherein is higher, even adopt big volume can guarantee that still mortar has higher-strength; 2, obviously improve the serviceability of fresh concrete, can effectively control the fresh concrete slump through time loss; 3, under various types of sulphate attacks (especially TSA corrodes) environment, the loss of strength of test specimen is very little, and the resisting erosion of sulfate effect is obvious; 4, when reaching above-mentioned technical indicator, concrete physical and mechanical property is unaffected; 5, can utilize industrial waste in a large number, production technique is simple, low production cost.In a word, the development of this high sulfide resistant cement demixture can solve the problem of the high resisting erosion of sulfate of present concrete broad variety well with application, and can reduce the pollution of industrial waste to environment, and the significant social economic benefit is arranged.
Can be widely used in engineering fields such as the geographic underground pipeline of the high resisting erosion of sulfate of requirement, water conservancy, dykes and dams, harbour.
Description of drawings
Fig. 1 is technological process of production figure of the present invention
Fig. 2 (A1) is that test specimen A1 of the present invention soaks each mortar outside drawing of 360d under the TSA erosion environment
Fig. 2 (A2) is that test specimen A2 of the present invention soaks each mortar outside drawing of 360d under the TSA erosion environment
Fig. 2 (A3) is that test specimen A3 of the present invention soaks each mortar outside drawing of 360d under the TSA erosion environment
Fig. 3 be under the TSA erosion environment of the present invention each in length of time mortar folding strength variation diagram
Fig. 4 respectively corrodes mortar ultimate compression strength variation diagram in the length of time under the TSA erosion environment of the present invention
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples, embodiment should not regard limitation of the invention as.
Embodiment 1:
As shown in Figure 1, the preparation method of high sulfide resistant cement demixture, it comprises the steps: 1). the pre-treatment of blast furnace slag: select the commercially available blast furnace slag that meets national standard for use, with its oven dry, the water ratio after the oven dry is less than 2%, and is standby; 2). the preparation of properties-correcting agent: adopting the solid solution ratio is 1: polyocarboxy acid type hyper-dispersant and the trolamine grinding aid of 2-3 mix by mass ratio at 1: 1, and be standby; 3). the preparation of reducing function component: aklylene glycol or polyoxyalkylene diols and silicon are grey by mass ratio 1: 15-20 mixes, and is standby; 4). by the mass ratio of blast furnace slag and properties-correcting agent is to choose pretreated blast furnace slag, properties-correcting agent at 100: 0.01, adds properties-correcting agent and carry out mix grinding in pretreated blast furnace slag, makes its Blain specific surface reach 400-450m 2/ Kg gets the mix grinding material; The mixed that with mix grinding material and function ingredients is 97: 3 more by mass percentage evenly forms, product.
Prepare glue sand test specimen according to table 1 proportioning.
Table 1 glue sand test proportioning (mass ratio)
Sample Each component concentration
Ordinary portland cement Sulphate resisting portland cement Product of the present invention Sand Water
A1 1 - - 2.5 0.6
A2 - 1 - 2.5 0.6
A3 0.4 - 0.6 2.5 0.6
(annotate: cement is 42.5 strength grades)
His-and-hers watches 1 prepared glue sand test specimen carries out the Mechanics Performance Testing in the different length of times, result such as table 2.
Table 2 glue sand test specimen mechanical property
Sample Folding strength (Mpa) Ultimate compression strength (Mpa)
3d 7d 28d 3d 7d 28d
A1 5.40 6.49 8.25 36.20 41.10 48.20
A2 5.28 6.56 8.63 35.60 40.45 45.30
A3 5.15 6.02 8.20 33.50 38.00 46.90
The performance index such as the table 3 of high sulfide resistant cement demixture:
The performance index of table 3 high sulfide resistant cement demixture
Project Desired value Measured value
Chemical ingredients Magnesium oxide % 5.00 3.10
Water ratio % 3.00 2.30
Total alkali content % 0.75 0.18
Chlorion % 0.05 0.01
Physicals Fineness Blain specific surface m 2/kg 250 400
0.08mm tail over % 10 8.80
1.25mm tail over % 0.50 0
Time of coagulation Initial set min 〉= 45 168
Final set h≤ 10 5.50
Ultimate compression strength Mpa 7d ≥ 25.00 38.00
28d ≥ 45.00 46.90
Folding strength Mpa 7d ≥ 4.50 6.02
28d ≥ 6.50 8.20
Adopt TSA to corrode simulated environment: glue sand test specimen is at low temperature (below 15 ℃), 5%MgSO 4Solution, competent CO 2With long period of soaking under the environment at water source, the appearance change of each mortar specimen after TSA corrodes 360d such as Fig. 2 (A1), Fig. 2 (A2), Fig. 2 (A3), by Fig. 2 (A1), Fig. 2 (A2), Fig. 2 (A3) as seen: the surface of test specimen A1 is decortication fully, depth of erosion is bigger, and obvious mud shape thing appears, through this mud shape thing of microcosmic testing authentication is Thaumasite salt, illustrates that TSA takes place to be corroded; The phenomenon of test specimen A2 is identical with test specimen A1, TSA has also taken place corroded, and just erosion degree is slightly light; Test specimen A3 is that slight damage appears in edge, there is no mud shape thing and occurs.From the appearance change of test specimen relatively as can be seen its anti-TSA erosion effect be from high to low: A3>A2>A1.
Strength Changes such as the Fig. 3 of each mortar specimen after TSA corrodes 360d.As seen from Figure 4: the early strength of three kinds of test specimens (being normal curing 28d) is more or less the same, and illustrates that the big volume of high sulfide resistant cement demixture adds the early strength that does not reduce test specimen.After the TSA in each length of time corroded, each test specimen intensity all decreased, and its loss of strength rate is descending to be: A1>A2>A3.So the anti-TSA erosion effect of each test specimen is from high to low: A3>A2>A1.
Embodiment 2:
The preparation method of high sulfide resistant cement demixture, it comprises the steps: 1). the pre-treatment of blast furnace slag: select the commercially available blast furnace slag that meets national standard for use, with its oven dry, the water ratio after the oven dry is 0.5-1.9%, and is standby; 2). the preparation of properties-correcting agent: employing solid solution ratio is that 1: 2 polyocarboxy acid type hyper-dispersant and trolamine grinding aid mixes by mass ratio at 1: 0.7, and is standby; 3). the preparation of reducing function component: aklylene glycol and silicon ash mix by mass ratio at 1: 15, and be standby; 4). by the mass ratio of blast furnace slag and properties-correcting agent is to choose pretreated blast furnace slag, properties-correcting agent at 100: 0.01, adds properties-correcting agent and carry out mix grinding in pretreated blast furnace slag, makes its Blain specific surface reach 400-450m 2/ Kg gets the mix grinding material; The mixed that with mix grinding material and function ingredients is 95: 5 more by mass percentage evenly forms, product.
Embodiment 3:
The preparation method of high sulfide resistant cement demixture, it comprises the steps: 1). the pre-treatment of blast furnace slag: select the commercially available blast furnace slag that meets national standard for use, with its oven dry, the water ratio after the oven dry is 0.5-1.9%, and is standby; 2). the preparation of properties-correcting agent: employing solid solution ratio is that 1: 3 polyocarboxy acid type hyper-dispersant and trolamine grinding aid mixes by mass ratio at 1: 1, and is standby; 3). the preparation of reducing function component: polyoxyalkylene diols and silicon ash mix by mass ratio at 1: 20, and be standby; 4). by the mass ratio of blast furnace slag and properties-correcting agent is to choose pretreated blast furnace slag, properties-correcting agent at 100: 0.02, adds properties-correcting agent and carry out mix grinding in pretreated blast furnace slag, makes its Blain specific surface reach 400-450m 2/ Kg gets the mix grinding material; The mixed that with mix grinding material and function ingredients is 99: 1 more by mass percentage evenly forms, product.
Embodiment 4:
The preparation method of high sulfide resistant cement demixture, it comprises the steps: 1). the pre-treatment of blast furnace slag: select the commercially available blast furnace slag that meets national standard for use, with its oven dry, the water ratio after the oven dry is 1%, and is standby; 2). the preparation of properties-correcting agent: employing solid solution ratio is that 1: 2.5 polyocarboxy acid type hyper-dispersant and trolamine grinding aid mixes by mass ratio at 1: 0.9, and is standby; 3). the preparation of reducing function component: aklylene glycol and silicon ash mix by mass ratio at 1: 18, and be standby; 4). by the mass ratio of blast furnace slag and properties-correcting agent is to choose pretreated blast furnace slag, properties-correcting agent at 100: 0.015, adds properties-correcting agent and carry out mix grinding in pretreated blast furnace slag, makes its Blain specific surface reach 400-450m 2/ Kg gets the mix grinding material; The mixed that with mix grinding material and function ingredients is 98: 2 more by mass percentage evenly forms, product.

Claims (1)

1. high sulfide resistant cement demixture, it is characterized in that it mainly is prepared from by blast furnace slag, properties-correcting agent, reducing function component raw material, preparation process is as follows: 1). the pre-treatment of blast furnace slag: choose blast furnace slag, with its oven dry, water ratio after the oven dry is less than 2%, and is standby; 2). the preparation of properties-correcting agent: adopting the solid solution ratio is 1: the polyocarboxy acid type hyper-dispersant of 2-3 and trolamine grinding aid are by mass ratio 1: 0.7-1 mixes, and is standby; 3). the preparation of reducing function component: aklylene glycol or polyoxyalkylene diols and silicon are grey by mass ratio 1: 15-20 mixes, and is standby; 4). the mass ratio by blast furnace slag and properties-correcting agent is 100: 0.01-0.02 chooses pretreated blast furnace slag, properties-correcting agent, adds properties-correcting agent and carry out mix grinding in pretreated blast furnace slag, makes its Blain specific surface reach 400-450m 2/ Kg gets the mix grinding material; Again with mix grinding material and function ingredients by mass percentage for the mixed of 95-99: 1-5 evenly forms, product.
CNB2005101205071A 2005-12-22 2005-12-22 High sulfide resistant cement demixture and preparation thereof Expired - Fee Related CN1330601C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105948553A (en) * 2016-05-17 2016-09-21 武汉理工大学 Sulfate-resistant anti-corrosion agent for cement-based material

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US5221344A (en) * 1988-05-13 1993-06-22 Eniricerche S.P.A. Concrete composition containing a superfluidifying additive
US6063183A (en) * 1996-01-03 2000-05-16 Italcementi S.P.A. Superfluidifying composition for cement compositions
CN1609032A (en) * 2004-11-09 2005-04-27 武汉理工大学 Anticracking cement with low shrinkage and low hydration heat

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Publication number Priority date Publication date Assignee Title
US5221344A (en) * 1988-05-13 1993-06-22 Eniricerche S.P.A. Concrete composition containing a superfluidifying additive
US6063183A (en) * 1996-01-03 2000-05-16 Italcementi S.P.A. Superfluidifying composition for cement compositions
CN1609032A (en) * 2004-11-09 2005-04-27 武汉理工大学 Anticracking cement with low shrinkage and low hydration heat

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复合外加剂对混凝土抗冻性能的影响 马强等,混凝土,第183期 2005 *
复合外加剂对混凝土抗冻性能的影响 马强等,混凝土,第183期 2005;混凝土中Thaumasite 硫酸盐侵蚀的形成与特征 马保国等,铁道科学与工程学报,第2卷第1期 2005;水淬矿渣微细粉配制水泥的研究 水泥,第3期 1998;水淬矿渣综合利用及发展前景 蒋伟锋,中国资源综合利用 2002 *
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