CN101244908A - Sweat gland type corrosion resistant concrete and method of manufacturing the same - Google Patents

Sweat gland type corrosion resistant concrete and method of manufacturing the same Download PDF

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Publication number
CN101244908A
CN101244908A CNA2008100136769A CN200810013676A CN101244908A CN 101244908 A CN101244908 A CN 101244908A CN A2008100136769 A CNA2008100136769 A CN A2008100136769A CN 200810013676 A CN200810013676 A CN 200810013676A CN 101244908 A CN101244908 A CN 101244908A
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cement
sweat gland
corrosion resistant
resistant concrete
gland type
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Inventor
王�琦
金志杰
李晓枫
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Jinan University
University of Jinan
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/457—Non-superficial impregnation or infiltration of the substrate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/34—Natural resins, e.g. rosin
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/36—Bituminous materials, e.g. tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0066—Film forming polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • C04B2103/0082—Segregation-preventing agents; Sedimentation-preventing agents
    • C04B2103/0083—Bleeding-preventing agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/26—Corrosion of reinforcement resistance

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

Abstract

The invention belongs to the technical field on polymer cement material method study, and relates to the design of sweat gland-type anti-eclipse cement taking polymer as main admixture and a preparation method of anti-eclipse cement. The sweat gland-type anti-eclipse cement is formed by cement and polymer which accounts for 2 to 20 percent of the cement; the polymer is any one element, two or three elements among asphalt, rosin and paraffin; under the stimulation of external temperature, the polymer flows inside the cement in the manner of sweat gland type and secretes, and corrosion resistant cement with a layer of protective film is formed on the surface of the cement. The sweat gland-type anti-eclipse cement has the advantages of using cheap polymer-paraffin, asphalt powder, rosin, etc. as fillers and having the characteristics of low cost, strong practicability, high strength, good corrosion resistant performance, little percolation ratio and lower cost, etc. The preparation method of the sweat gland-type anti-eclipse cement has simple operation, no pollution and wider application scope.

Description

Sweat gland type corrosion resistant concrete and preparation method thereof
Technical field
The invention belongs to the technical field of polymer water mud material method research, relating to by superpolymer is the design of the sweat gland type corrosion resistant concrete of main adulterant, and the preparation method of corrosion resistant concrete.
Background technology
In recent years, development along with Materials Science and Engineering, cement material has also obtained very fast development, the development of polymer-modified cement is also than comparatively fast, the polymkeric substance that adds 5%-20% in cement can make cement slurry form a kind of inorganic and organic interpenetrating(polymer)networks, can improve the ultimate compression strength and the corrosion resistance nature of cement stone greatly.
By microanalysis as can be known cement in hydration process, will in matrix, form gel pore, transitional pore, pore and macropore four class holes.The size in total porosity in these holes, the distribution in aperture, aperture and shape all will impact the resistance to compression and the bending strength of matrix.General cement-base composite material mainly is made up of aquation crystalline mineral and gelinite, water and a spot of air of unhydrated cement clinker particle, cement.Therefore it is a heterogeneous porous insert of solid-liquid-gas.The intensity of its material also just is being subjected to the restriction of these factors and is influencing.The adding of polymkeric substance has changed the variation relation of these factors, thereby has influenced the raising of intensity.Though but the pore structure of polymer cement based composites makes moderate progress, still also exist a large amount of holes to cause the intensity of cement stone and corrosion resistance good inadequately.At present, macro-defect-free cement is primarily aimed at and changes the hole that cement forms strengthen its intensity and corrosion resistance nature in hydration process.
Summary of the invention
The present invention is directed to present cement products a lot of defectives are arranged on macroscopic view, for example porosity is bigger, major defects such as poor corrosion resistance prepare a kind of void content that can reduce cement stone, can improve the resistance to corrosion of cement stone again and improve the sweat gland type corrosion resistant concrete of the intensity of cement stone.
Another object of the present invention is to provide the preparation method of above-mentioned cement.
The present invention is achieved by the following scheme:
Sweat gland type corrosion resistant concrete of the present invention; superpolymer by cement and by mass of cement 2-20% is formed; described superpolymer be pitch, rosin and paraffin any, two or three; under extraneous thermal stimulus; superpolymer at cement internal flow justacrine, forms the corrosion resistant concrete of layer protecting film in the mode of sweat gland type at cement surface.
The sweat gland type corrosion resistant concrete of the invention described above, described superpolymer can add by a kind of of following proportioning: the pitch of 3-10%; 3-10% rosin; 3-10% paraffin; 2-10% pitch and the rosin of 2%-10%; The paraffin of the pitch of 1-8%, the rosin of 1%-8% and 1%-8%.
The preparation method of the sweat gland type corrosion resistant concrete of the invention described above is characterized in that adopting following steps:
(1) takes by weighing superpolymer and be ground into 100-300 purpose fine powder;
(2) superpolymer is joined in the cement, stir, make sweat gland type corrosion resistant concrete.
Sweat gland type corrosion resistant concrete of the present invention can be prepared into various cement products by the following method.For example: sweat gland type corrosion resistant concrete mixes with other auxiliary material, adds water, stirs the maintenance moulding; Goods after the moulding are heated to 100-150 ℃, carry out maintenance 2-24 hour, get product.
The invention discloses paraffin, asphalt powder, low softening points such as rosin, water insoluble, not with the superpolymer of alkali reaction sweat gland type sweat gland type corrosion resistant concrete as addition material, and the principle against corrosion of sweat gland type corrosion resistant concrete.Sweat gland type corrosion resistant concrete is based on silicate cement; polymkeric substance with low softening point is an addition material; under certain environment and temperature condition; polymkeric substance produces mobile in cement; it can flow along the space in the cement as plant-growth; add the space in the water blockoff mud, and can form layer protecting film at cement surface, thereby played erosion-resisting effect as perspiring.
Sweat gland type corrosion resistant concrete of the present invention is an example with No. 425 ordinary Portland cements, specifically tests its time of coagulation, standard water consumption, ultimate compression strength before the corrosion, the ultimate compression strength after the antiacid brine corrosion.
Sweat gland type corrosion resistant concrete of the present invention records the complex cement that adds behind the pitch according to GB/T1346-2001, and its consumptive use of water normal consistence is 132ml ± 2, and the presetting period is about 9h, and final setting time is about 12h.According to same detection method, record adding rosin complex cement, its consumptive use of water normal consistence 131ml ± 2, the presetting period is about 3h, and final setting time is about 5h.
The sweat gland type polymer cement is that the softening temperature of superpolymer such as rosin is lower according to paraffin, pitch, can soften into the bigger semi-fluid of viscosity at a certain temperature.
Beneficial effect is among the present invention, utilizes cheap superpolymer-paraffin, asphalt powder, rosin etc. as weighting material, and it is low, practical to have a cost, intensity height, characteristics such as corrosion resistance is good, and percolation ratio is little, and cost is lower.
Preparation method of the present invention, only need adulterant proportionally be added to make in the Portland cement its sclerosis just can, simple to operate, this product is a refuse reclamation, and is pollution-free, the scope of application also relatively extensively.
Description of drawings
Fig. 1 is the variation diagram of sweat gland type corrosion resistant concrete of the present invention in hydration process.As shown in the figure: begin from add additive in cement, material all is very equally distributed globe in the cement, finishes etc. aquation, produces C in the cement slurry 3S, C 2S and Ca (OH) 2Deng hydrated product; begin to be filled into the gap of hydrated product among the present invention from additive; then under 100-150 ℃ temperature in the maintenance processes; the high temperature rheology of superpolymer makes their softening holes of having filled in the cement stone; and similar perspiration seals cement surface; play the effect of protective layer, thereby reach erosion-resisting effect.
Fig. 2 is the XRD figure of embodiments of the invention 3.
Fig. 3 is the XRD figure of embodiments of the invention 4.
Fig. 4 is the SEM figure of embodiments of the invention 3.
Fig. 5 is the SEM figure of embodiments of the invention 4
Fig. 6 is the SEM figure of blank cement-like.
Embodiment:
Embodiment 1
1. concrete operations are as follows:
Step 1, measure 5 grams, 300 order asphalt powders, 8 grams, 200 order rosin, join in No. 425 ordinary Portland cements of 87 grams, stir, add gauge water, in clean slurry stirrer, stirring.Make superpolymer well to be scattered in the cement, make sweat gland type corrosion resistant concrete.
Step 2, the sweat gland type corrosion resistant concrete of step 1 is put into the grinding tool of 2*2*2, maintenance in the fixed temperature and humidity maintaining box is until its final set.This step has just made the cement of forming, is beneficial to and tests.
Step 3, the sample of forming is put into thermostat container remain on 100-150 ℃ of left and right sides high temperature maintenance, the actual working environment of simulation cement keeps 2-24 hour because in thermostat container the time of maintenance relevant with the intensity of maintenance fate in the environment.
Can obtain reasonable sweat gland type corrosion resistant concrete of the present invention by above-mentioned steps, in finished product, superpolymer has all filled up the space of ordinary Portland cement.By measuring, the intensity of cement products does not reduce and improves, the intensity height of yet preceding than corrosion ordinary Portland cement after its corrosion.
2. test result
Adopt above-mentioned step, add different asphalt powder and colophonium powder and test.And carry out following test, compare with the cement that does not add superpolymer.The results are shown in Table 1.
Ultimate compression strength, Na 2SO 4Corrosion back ultimate compression strength, anti-Na 2CO 3Corrosion ultimate compression strength, all test adopts national testing standard to test.In the table temperature be complex cement after final set, complex cement is placed on the temperature of maintenance in the high temperature.
Table 1
Figure A20081001367600051
Embodiment 2
Adopt above-mentioned identical method, in cement, add pitch, rosin and paraffin, test.Test result sees Table 2.
Table 2
Figure A20081001367600061
Embodiment 3
Adopt above-mentioned identical method, add pitch in cement, all the other are cement, and test result sees Table 3.
Table 3
Embodiment 4
Adopt above-mentioned identical method, add rosin in cement, test result sees Table 4.
Table 4
After pitch, rosin, paraffin and the cementitious composite, the intensity of common 425 silicate cements of the compressive strength rate of the sweat gland type corrosion resistant concrete of making is slightly high, and its corrosion-resistant degree is better than the corrosion-resistant degree of Portland cement as can be seen from the table.Angle from microcosmic, it is because superpolymer such as pitch, rosin are filled and are scattered in the cement slurry that ultimate compression strength increases, improved pore structure, porosity is descended, make system become more closely knit, and along with the continuous aquation of cement, the part additive extend through in the hydrated cementitious product, refinement particle diameter, so ultimate compression strength can increase.And from cement products by sodium sulfate and yellow soda ash corrosive result, may be the calcium sulfate (CaSO that generates 4) and lime carbonate (CaCO 3) gel pore and part kapillary are stopped up, make cement stone degree of compactness increase, anti-permeability performance also is improved, and the ultimate compression strength of sample is further improved.
Test case 1
Get the sweat gland type corrosion resistant concrete among the embodiment 3, its test XRD figure as shown in Figure 2.
As shown in Figure 2, P70 is the XRD figure that adds the sweat gland type corrosion resistant concrete of 6% asphalt powder, and P700 adds the sweat gland type corrosion resistant concrete of asphalt powder through Na 2SO 4XRD figure after the corrosion, P710 adds the sweat gland type corrosion resistant concrete of asphalt powder through Na 2CO 3XRD figure after the corrosion.The sweat gland type corrosion resistant concrete goods are through Na 2SO 4, Na 2CO 3After the corrosion, Ca (OH) 2Diffraction peak all very sharp-pointed, peak value is all very high, shows Ca (OH) 2Content height in body of cement, advantages of good crystallization has proved Na simultaneously 2SO 4, Na 2CO 3The amount of infiltrating in the body of cement is few.By P700 and P70 diffraction peak relatively, add complex cement behind the asphalt powder through Na 2SO 4After the corrosion, Ca (OH) 2Content reduces not obvious, CaSO 4The content increasing amount also seldom proves absolutely the anti-Na of cement after compound 2SO 4Corrosive nature is better than ordinary Portland cement, compares P710 and P70 diffraction peak, Ca (OH) equally 2Content reduces also not obvious, CaCO 3The content increasing amount also seldom illustrates the anti-Na of complex cement 2CO 3Corrosive nature is also good.
To sum up, the anti-Na of sweat gland type corrosion resistant concrete that adds asphalt powder 2SO 4, Na 2CO 3The corrosive nature effect is all good.
Test case 2
Get the sweat gland type corrosion resistant concrete among the embodiment 4, its test XRD figure as shown in Figure 3.
As seen from Figure 3, S70 is the XRD figure that adds 10% rosiny sweat gland type corrosion resistant concrete, and S700 adds the complex cement of colophonium powder through Na 2SO 4XRD figure after the corrosion, S710 adds the complex cement of colophonium powder through Na 2CO 3XRD figure after the corrosion.Blank sample is through Na 2SO 4After the corrosion, Ca (OH) 2Diffraction peak in XRD figure is not obvious, and its relative content is obviously few than other compositions, is because outside most of Ca (OH) 2With Na 2SO 4Reaction, and the hole in the blank sample is more, Na 2SO 4Penetrate into inner further reaction.Simultaneously, CaSO 4Sharp-pointed with the diffraction peak of ettringite, peak value is the typical case comparatively, and Ca (OH) has been described more 2With the Na that infiltrates in the body of cement 2SO 4Reaction generates CaSO 4And ettringite, so CaSO 4Many with ettringite content in blank sample, better crystallinity degree proves that the corrosion resistance of blank sample is bad.Can find out by S700, S710 among the figure, through Na 2SO 4, Na 2CO 3After the corrosion, Ca (OH) 2Diffraction peak very sharp-pointed, peak value is very high, and Ca (OH) is described 2Content height in body of cement, advantages of good crystallization has also illustrated Na simultaneously 2SO 4, Na 2CO 3The amount of infiltrating in the body of cement is few, and the density of cement is greatly improved.By S700 and S70 diffraction peak relatively, add complex cement behind the colophonium powder through Na 2SO 4After the corrosion, Ca (OH) 2Content reduces not obvious, CaSO 4The content increasing amount also seldom proves absolutely the anti-Na of cement after compound 2SO 4Performance is good, compares S710 and S70 diffraction peak, Ca (OH) equally 2Content reduces also not obvious, CaCO 3The content increasing amount also seldom, the anti-Na of complex cement 2CO 3Performance is also fine.
To sum up, the anti-Na of complex cement that adds colophonium powder 2SO 4, Na 2CO 3Corrosive nature is all relatively good.
Test case 3
Get the sweat gland type corrosion resistant concrete among embodiment 3 and the embodiment 4, and blank cement-like, its test SEM figure is shown in Fig. 4-6.Wherein Fig. 4 is the SEM figure that adds 6% bituminous sweat gland type corrosion resistant concrete, and Fig. 5 is the SEM figure that adds 10% rosiny sweat gland type corrosion resistant concrete, and Fig. 6 is the SEM figure of blank sample cement.
Scanning electronic microscope provides the microscopic appearance figure of complex cement and blank cement sample effectively.
From Fig. 4, Fig. 5 and Fig. 6 more as can be seen, by analysis chart 6 can find be since the size of cement slurry mesoporosity between tens nanometers to tens micron, at blank sample cement sample upper layer, the C-S-H gel of very small particles shape, tabular and sheet Ca (OH) are arranged 2Deng the microscopic appearance of hydrated cementitious product, one-piece construction is loose, and the cavity is more.Obviously see pitch from Fig. 4 and Fig. 5, the rosin superpolymer is filled in the hole of sample after melting, the hole of sand-cement slurry inside and capillary channel quantity obviously reduce, some polymkeric substance have been filled in the hole, the pore structure of cement stone has also had tangible change, mean pore size is diminished, the macropore hole that diminishes, the microporosity coefficient improves, and has increased degree of compactness so to a great extent, after pore dimension reduces, just reduced fissured length, closely knit complete hydrated product is also arranged on every side, and in conjunction with tight, hole is few each other for hydrated product, increased degree of compactness, non-microcracked generation.In addition, polymkeric substance has also strengthened the bonding between cement stone inner particles, has reduced pore dimension at the interface, has improved interface structure.This also can explain and add the reason that the ultimate compression strength of cement can improve behind the polymkeric substance.
Therefore this patent is an addition material with paraffin, asphalt powder and colophonium powder, according to these superpolymer softening flowability at a certain temperature, the sweat gland type corrosion resistant concrete system is proposed, can be good at improving the anticorrosive effect of cement products, not only the weather resistance raising to common buildings plays an important role, and the raising of large scale computer ultra-large type Architectural Equipment weather resistance is had important economic value.

Claims (7)

1. sweat gland type corrosion resistant concrete, it is characterized in that: the superpolymer by cement and by mass of cement 2-20% is formed, described superpolymer be pitch, rosin and paraffin any, two or three.
2. sweat gland type corrosion resistant concrete according to claim 1 is characterized in that: described superpolymer is the pitch of 3-10%.
3. sweat gland type corrosion resistant concrete according to claim 1 is characterized in that: described superpolymer be 3-10% rosin.
4. sweat gland type corrosion resistant concrete according to claim 1 is characterized in that: described superpolymer be 3-10% paraffin.
5. sweat gland type corrosion resistant concrete according to claim 1 is characterized in that: described superpolymer be 2-10% pitch and the rosin of 2%-10%.
6. sweat gland type corrosion resistant concrete according to claim 1 is characterized in that: described superpolymer is the pitch of 1-8%, the rosin of 1%-8% and the paraffin of 1%-8%.
7. the preparation method of the described sweat gland type corrosion resistant concrete of claim 1 is characterized in that adopting following steps:
(1) takes by weighing superpolymer and be ground into 100-300 purpose fine powder;
(2) superpolymer is joined in the cement, stir, make sweat gland type corrosion resistant concrete.
CNA2008100136769A 2008-01-24 2008-01-24 Sweat gland type corrosion resistant concrete and method of manufacturing the same Pending CN101244908A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102459121A (en) * 2009-05-20 2012-05-16 国际壳牌研究有限公司 Sulphur cement product

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102459121A (en) * 2009-05-20 2012-05-16 国际壳牌研究有限公司 Sulphur cement product
CN102459121B (en) * 2009-05-20 2014-12-17 国际壳牌研究有限公司 Sulphur cement product

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