CN103058568A - Portland cement early strength agent and application method thereof - Google Patents
Portland cement early strength agent and application method thereof Download PDFInfo
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- CN103058568A CN103058568A CN2013100224559A CN201310022455A CN103058568A CN 103058568 A CN103058568 A CN 103058568A CN 2013100224559 A CN2013100224559 A CN 2013100224559A CN 201310022455 A CN201310022455 A CN 201310022455A CN 103058568 A CN103058568 A CN 103058568A
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Abstract
The invention discloses an admixture used for improving the early strength of Portland cement and an application method of the admixture. Applicable object of the admixture comprises common Portland cement or mixed cement. The admixture can enhance the early strength of the Portland cement and a gelling composition and reduce water requirement. The method used for enhancing the early strength of the Portland cement comprises that the following substances are added in the cement, preferably are added in a process of grinding the cement: (a) at least one high efficiency water reducing agent containing polyoxyethylene group; (b) a low molecular sugar; and (c) an alkali metal or alkaline-earth metal sulfate. Polyhydroxy amine is optionally added in the grinding step of the other application methods, and preferably the admixture is added in the process of grinding the cement after the admixture is prepared into an aqueous solution.
Description
Background technology
The present invention relates to the admixture for cement, more particularly, the present invention relates to for increasing cement early strength admixture, improve the method for cement early strength.
Here said cement refer to can with the inorganic hydraulic material of gelling of steeping in water for reconstitution unboiled water reaction, for the manufacture of such as sand-cement slurry and concrete material.Cement can comprise, for example ordinary Portland cement or mixed cement, and the latter can be metallurgical Portland blastfurnaceslag cement or the silicate cement that mixes with pozzolanic materials.Therefore, mixed cement generally contains following one or more pozzolanic materials: such as slag, calcined kaolin, flyash, natural volcanic ash, this makes cement manufacturers replace the part Portland clinker with it, and the decrease cost produces economic benefit thus.
Between the manufacturers of the manufacturers of mixed cement and ordinary Portland cement, there is the competition between Financial cost and technical feature.Therefore, the human consumer often need to make a choice between the mixed cement of ordinary Portland cement and less expensive, and mixed cement often has the early strength of less and higher water requirement.Therefore the inventor thinks and need to suitably improve this class cement, improves and reduce the admixture of water requirement especially for the early strength of mixed cement.
Summary of the invention
The invention provides the early strong water reducing admixture of silicate cement, for increasing the method for silicate cement and cementitious composition early strength and reduction water requirement.Admixture of the present invention is considered to can be used for silicate cement, mixed cement, for example ordinary Portland cement and mixed cement, and this admixture has reduced cement cost, does not reduce but the user can find the technical performance index of trass cement.
The present invention is included in the following material of adding in the cement for increasing the method for cement early strength, preferably adds in the pulverizing cement process: (a) at least a high efficiency water reducing agent that contains polyoxyethylene group; (b) a kind of low molecular sugar; (c) a kind of basic metal or alkaline earth metal sulphate.A kind of polyhydroxy amine of optional adding in the grinding step of other application methodes.
The present invention contains for the admixture that improves cement early strength: the high efficiency water reducing agent that (a) contains at least a kind of polyoxyethylene group; (b) a kind of low molecular sugar; (c) a kind of basic metal or alkaline earth metal sulphate; (d) optionally contain a kind of polyhydroxy amine.Optional admixture is made the aqueous solution or is made solid powder in cement pulverizing course, add.Cement composition of the present invention comprises the mixture that cement and above-mentioned polyoxyethylene high efficiency water reducing agent, low molecular sugar and basic metal or alkaline earth metal sulphate mix mutually.
Hereinafter describe further aspect of the present invention and advantage in detail.
The present invention can realize with following form: admixture (polyoxyethylene high efficiency water reducing agent, low molecular sugar and basic metal or alkaline earth metal sulphate), it can add cement (preferred mixed cement) in powder-grinding process, or add cementitious composition (comprise contain mixed cement and fines (sand)/or the composition of coarse aggregate (building stones)); Contain above-mentioned component (perhaps as mixture, perhaps more preferably in the cement manufacturing processed as cement additive) cement (or cementitious composition, such as masonry with cement, concrete); And the present invention is also as a kind of method of improving cement early strength by adding admixture component in cement pulverizing course.
Polyoxyethylene polymer is used as the high efficiency water reducing agent of portland cement, and preferred polymers is the comb shaped polymer with main chain and side group, and its polyoxyethylene group that contains or has among both in pearl-decorated curtain or side group.Comb-shaped polymer type high efficiency water reducing agent can significantly lower the water requirement of cement, can make concrete keep in a long time higher degree of mobilization.
The preferred oxyethane (EO) that has main polymer chain, for example contain carbon backbone chain/propylene oxide (PO) the type comb-shaped polymer that uses is connected with carboxyl and side group, such as the combination of ethylene oxide group, propylene oxide group and/or EO/PO group on it.Side group can be ion or non-ionic, for example many carboxylic monomers such as toxilic acid or maleic anhydride and contain multipolymer just like polyalkylene glycol mono allyl ether class monomer.
Be applicable to exemplary polyoxyethylene polymer of the present invention and contain carbon backbone chain, be connected with on it structure (I) and (II) shown in group, and optional be connected with structure such as (III) and the group (IV):
[-CRCOOZ-CH
2-]
a
(I)
[-CRCOOZ-CH
2-]
b
(II)
Wherein each R can represent hydrogen atom or methyl group independently; Z both can represent hydrogen atom, C
1-C
10Alkyl, R be alkali metal cation or its mixture also; R
/Represent hydrogen atom or be expressed as (BO) nR
//C
2-C
10Oxyalkylene group, O represention oxygen atom wherein, B represents C
2～C
10Alkylidene group, n represent integer or its mixture of 1-200; A, b, c and d are the molecular fractions of representation polymer structure, and a is about 50～70; The summation that c adds d is at least 2 to (100-a), and preferred 3～10; B is no more than (100-(a+c+d)).
Being applicable to polyoxyethylene polymer of the present invention is exactly the polyacrylic acid comb-shaped polymer specifically, and it is by polyoxyethylene amine is grafted on the poly carboxylic acid main chain, namely occur amination reaction and or imidization make.
But another polyoxyethylene polymer that is considered to be fit to can form by the polyolefin polymerization with maleic anhydride and ethylene linkage polymerization, they often use with the form of metal-salt, and they are the end reaction formation by polymkeric substance and alkali such as sodium hydroxide or calcium hydroxide.
Can consider that also polyoxyethylene polymer may not the Seeking Truth comb-type structure, namely on the main chain with side group, but may have straight chain and branched structure, or other structures also can be used as cement water reducing agent.
Recommending the polyoxyethylene polymer preferred molecular weight is 3000～100000, most preferably 15000～50000.
Based on the cement dry weight, the preferred usage quantity of the polyoxyethylene high efficiency water reducing agent that the present invention is used is 0.002～0.4%, and optimum amount is 0.005～0.25%.
Oligose can use with dry powder form in the present invention, but preferred the adding in the aqueous solution.Low molecular sugar commonly used in cement and concrete industry just can be used among the present invention, and this comprises glucose, sucrose, fructose, hexose, pentose, tetrose etc., also comprises maize treacle and molasses.In the present invention also useful gluconic acid and their salt such as Sunmorl N 60S, Trisodium Citrate, the particularly preferably mixture of Sunmorl N 60S and molasses.
Above-mentioned low molecular sugar class is used for the present invention, adds when pulverizing cement, and based on the cement dry weight, its quantity is 0.001～0.2%, and more preferably 0.002～0.1%.
Useful exemplary basic metal or alkaline earth metal sulphate class comprise calcium sulfate, sodium sulfate, vitriolate of tartar, ammonium sulfate in the present invention, and preferably sulfuric acid is received.These salts can be dissociated into their ionic species in solution.
Based on the dry weight of cement, the quantity of used vitriol is preferably 0.001～1.0%, most preferably is 0.002～0.15%.
Admixture of the present invention and method also comprise the application of polyhydroxy amine.Exemplary poly-hydroxy amine comprises alkanolamine, such as trolamine, diethanolamine, thanomin, tri-isopropanolamine etc.Based on the dry weight of cement, the preferred mass that adds (slag cement, trass cement) quality polyhydroxy amine is 0～0.15%, and most preferred range is 0.0005～0.04%.Described poly-hydroxy amine also can be used Acetates, formiate or Acrylates.For example, can use the acetic acid trolamine in method of the present invention, admixture and cement composition, this can provide improved grinding effect and/or reduce the caking of cement in packing for cement.
Can add other components in the admixture of the present invention, as adding air entrapment agent such as rosined soap or colophonium pyrolytic polymer.The quantity of this bleed compound can be 0.003%～0.02%.
In the preferred method of the present invention, use the above-mentioned optimal way that forms the high admixture component of early strength that impels to be: they to be sneaked into the aqueous solution together, then the aqueous solution is added gradually the grinding process of fiery cement.The component in the admixture preferably adds these admixtures with solution, because will evenly be diffused in the cement pulverizing course easilier.
Embodiment
Proposing above-mentioned explanation and example only is for illustrational purpose, never limits the scope of the invention.Same the following examples also only are to provide for illustrational purpose, never are the scopes of restriction institute of the present invention prescription.
Embodiment 1
According to " composite Portland cement " (GB12958-1999), the early strength of test mixing cement.With the trass cement that contains 30% slag micropowder in contrast.The intensity in one sky is 12.1MPa; 3d intensity is 20.1MPa.The water requirement of contrast is used the percentage ratio in the cement is represented, is 58.0%.
After introducing commodity polyoxyethylene high efficiency water reducing agent 0.01～0.06%, the about contrast thing of intensity of 1 day and 3 days has improved 10%.Water requirement is 43.0% of cement.
After polyoxyethylene high efficiency water reducing agent 0.03%, sodium sulfate 0.06% and trolamine 0.004% sneaked into slag cement, the strength increase of 1 day and 3 days 14% and 12%.Water requirement is 42.0%.
When water reducer, sodium sulfate and trolamine were combined with glucose or molasses, 1 day strength ratio contrast has increased by 30%, 3 day strength ratio contrast had increased by 18%.Water requirement is 40.0%.
Embodiment 2
Except replace the polyoxyethylene high efficiency water reducing agent with calcium lignin sulfonate water depressor, as described in Example 1 remaining, make the cement mixing sample that contains 30% slag micropowder, with the combination of low molecular sugar and/or salt in find water minimizing less than 4%, diminishing is not obvious.
Embodiment 3
Use naphthalenesulfonate formaldehyde condensation compound to make other slag cement sample, this water reducer uses separately or is combined with sodium sulfate, and that finds water is reduced to 10%.
Embodiment 4
Dry weight preparation admixture based on slag cement: polyoxyethylene high efficiency water reducing agent 0.01～0.1%; Sunmorl N 60S 0.02～0.1%; Sodium sulfate 0.01～0.1%; And trolamine 0.005～0.02%.
Claims (11)
1. one kind is used for improving silicate cement cementitious composition early strength and the method that reduces water requirement.Admixture of the present invention is considered to can be used for silicate cement, mixed cement, for example ordinary Portland cement and mixed cement.Be included in the following material of adding in the cement, preferably in the pulverizing cement process, add: (a) at least a high efficiency water reducing agent that contains polyoxyethylene group; (b) a kind of low molecular sugar; (c) a kind of basic metal or alkaline earth metal sulphate.A kind of polyhydroxy amine of optional adding in the grinding step of other application methodes.
2. cement early strength agent claimed in claim 1, be used as the high efficiency water reducing agent of portland cement comprising polyoxyethylene polymer, preferred polymers is the comb shaped polymer with main chain and side group, and its polyoxyethylene group that contains or has among both in pearl-decorated curtain or side group.Being applicable to polyoxyethylene polymer of the present invention is exactly the polyacrylic acid comb-shaped polymer specifically, and it is by polyoxyethylene amine is grafted on the poly carboxylic acid main chain, namely occur amination reaction and or imidization make.
3. the described polyoxyethylene polymer of claim 2 contains carbon backbone chain, be connected with on it structure (I) and (II) shown in group, and optional be connected with structure such as (III) and the group (IV):
[-CRCOOZ-CH
2-]
a
(I)
[-CRCOOZ-CH
2-]
b
(II)
Wherein each R can represent hydrogen atom or methyl group independently; Z both can represent hydrogen atom, C
1-C
10Alkyl, R be alkali metal cation or its mixture also; R
/Represent hydrogen atom or be expressed as (BO) nR
//C
2-C
10Oxyalkylene group, O represention oxygen atom wherein, B represents C
2～C
10Alkylidene group, n represent integer or its mixture of 1-200; A, b, c and d are the molecular fractions of representation polymer structure, and a is about 50～70; The summation that c adds d is at least 2 to (100-a), and preferred 3～10; B is no more than (100-(a+c+d)).
4. polyoxyethylene polymer claimed in claim 2, but can form by the polyolefin polymerization with maleic anhydride and ethylene linkage polymerization, they often use with the form of metal-salt, and they are the end reaction formation by polymkeric substance and alkali such as sodium hydroxide or calcium hydroxide.
5. the described polyoxyethylene polymer of claim 2 also can be considered, may not the Seeking Truth comb-type structure, namely on the main chain with side group, but may have straight chain and branched structure, or other structures also can be used as cement water reducing agent.
6. remove Onlly requirement 2 described polyoxyethylene polymers, recommending preferred molecular weight is 15000～50000.
7. the described cement early strength agent of claim 1 comprises low molecular sugar commonly used, such as glucose, sucrose, fructose, hexose, pentose, tetrose etc., also comprises maize treacle and molasses.Above-mentioned low molecular sugar class is used for the present invention, adds when pulverizing cement, and based on the cement dry weight, its preferred amount is 0.002～0.1%.
8. the described cement early strength agent of claim 1 comprises basic metal or alkaline earth metal sulphate.
9. the described cement early strength agent of claim 1 also comprises the application of polyhydroxy amine.
10. the described cement early strength agent preparation method's of claim 1 optimal way is: they are sneaked into the aqueous solution together, then the aqueous solution is added gradually the grinding process of fiery cement.
11. the preparation method of cement early strength agent claimed in claim 1 is, various admixtures (polyoxyethylene high efficiency water reducing agent, low molecular sugar and basic metal or alkaline earth metal sulphate), it can add cement (preferred mixed cement) in powder-grinding process, or add cementitious composition (comprise contain mixed cement and fines (sand)/or the composition of coarse aggregate (building stones)).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106348632A (en) * | 2016-08-30 | 2017-01-25 | 卓达新材料科技集团威海股份有限公司 | Composite early strength agent for 3D (three-dimensional) printing house slurry |
| CN106396460A (en) * | 2016-08-31 | 2017-02-15 | 清华大学 | Organic additive, and preparation method and applications thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106348632A (en) * | 2016-08-30 | 2017-01-25 | 卓达新材料科技集团威海股份有限公司 | Composite early strength agent for 3D (three-dimensional) printing house slurry |
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| CN106396460B (en) * | 2016-08-31 | 2018-07-13 | 清华大学 | A kind of organic admixture and its preparation method and application |
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Application publication date: 20130424 |