CN103130437A - Gypsum and calcium oxide melt inclusion expansion clinker, concrete expansion agent, and preparation method and application thereof - Google Patents
Gypsum and calcium oxide melt inclusion expansion clinker, concrete expansion agent, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a gypsum and calcium oxide melt inclusion expansion clinker, a concrete expansion agent, and a preparation method and application thereof, belonging to the field of construction materials. The expansion clinker provided by the invention is prepared by mixed grinding and high-temperature burning of limestone, gypsum and aluminum oxide and/or aluminum sulfate. The concrete expansion agent is prepared by grinding the expansion clinker together with a calcium sulphoaluminate cement clinker, calcium stearate or/and triethanolamine until the specific surface area is 140-400 m<2>/kg. According to the invention, the expansion clinker has high restrained expansion rate and high clinker weathering resistance; the concrete expansion agent has the functions of cracking resistance, seepage resistance, shrinkage compensation and the like, and has the advantage of long product shelf life (up to 6 months). The concrete expansion agent can be used for cracking resistance and seepage resistance of a common concrete structure, and can greatly enhance the durability of the concrete.
Description
Technical field
The invention belongs to the material of construction technical field of concrete additives, particularly relate to a kind of gypsum and calcium oxide melt inclusions cement expansive material and preparation method thereof and its application in the raising concrete is resisted shrinkage.
Background technology
Cement concrete is present the most large construction material in the world, and is cheap, is widely used.But the easy shrinkage cracking of cement concrete, wherein, dry shrinkage (comprising self-desiccation shrinkage) and temperature shrinkage are two kinds of topmost contractions, have had a strong impact on concrete weather resistance.In order to solve the problem of the easy shrinkage cracking of cement concrete, the researchist has invented expansive cement or cement expansive material.Especially cement expansive material, easy to use with it, more favored flexibly.Up to now, the patent documentation of relevant cement expansive material and preparation method thereof is a lot, as:
The Japanese documentation of the clear 53-13650 of publication number (applicant: the preparation method who discloses a kind of cement expansive material Onoda Cement Co., Ltd).To adopt Wingdale, clay, silica and copper ashes batching, silicon rate 1-4, iron rate 0.5-4 is through 1300 ℃ of-1600 ℃ of expanding materials that calcining obtains.Essential mineral is tricalcium silicate, crystal calcium oxide and calcium aluminoferrite.This cement expansive material has grog weathering resistance ability, and the swelling agent shelf-time is short, the shortcoming of the easy dead roasting of calcium oxide.
The Japanese documentation of the clear 53-31170 of publication number (applicant: the preparation method who discloses a kind of cement expansive material Onoda Cement Co., Ltd).To adopt Wingdale and clay ingredient, silicon rate 1-4, iron rate 0.5-4 obtains expansive clinker through 1300 ℃ of-1600 ℃ of calcinings, then obtains swelling agent with the gypsum combined grinding of 10%-20%.This cement expansive material has grog weathering resistance ability equally, and the swelling agent shelf-time is short, the shortcoming of the easy dead roasting of calcium oxide.
The Japanese documentation of the clear 54-25050 of publication number (applicant: the preparation method who discloses a kind of cement expansive material Sumitomo Cement Co., Ltd.).To adopt Wingdale and iron ore batching, silicon rate 1-4, iron rate 0.5-4 is through 1200 ℃ of-1450 ℃ of expanding materials that calcining obtains.The essential mineral of this swelling agent is crystal calcium oxide and calcium iron sosoloid.This cement expansive material has grog weathering resistance ability, the shortcoming that the swelling agent shelf-time is short.
The Japanese documentation of publication number JP 2010-228971 (applicant: the preparation method who discloses a kind of cement expansive material Pacific Ocean material Co., Ltd.).Be mainly that employing tricalcium silicate parcel free calcium oxide is grog, then obtain swelling agent with the gypsum combined grinding.In grog, silica content is no less than 2%, the crystal size 20 μ m-60 μ m of free calcium oxide.This cement expansive material has grog weathering resistance ability, the shortcoming that the swelling agent shelf-time is short.
The Japanese documentation of publication number JP 2010-150113 (applicant: the preparation method who discloses a kind of cement expansive material Pacific Ocean material Co., Ltd.).The employing Wingdale is main raw material, siliceous raw material 0.1-9.0 %, and ferriferous raw material content 0.5-2.0%, main is the fluorochemical of admixture 0.1-1.0%, free calcium oxide content is no less than 45%.This cement expansive material has grog weathering resistance ability, the shortcoming that the swelling agent shelf-time is short.
The Chinese patent literature of publication number CN85100902B (applicant: the preparation method who National Building Materials Industry Bureau Building Materials Institute of Science and Technology) discloses a kind of cement expansive material.Be to adopt Wingdale, clay and ferriferous raw material to prepare burden in proportion, be sintered into expansive clinker through 1400 ℃-1600 ℃.Expansive clinker contains 50-70%C
3S, the clean CaO of 25-60%, 1-5%C
4AF, 2-8%C
3A。This expansive clinker and natural alumstone below 15% are become swelling agent with dihydrate gypsum intergrinding below 10%.This cement expansive material has grog weathering resistance ability, and the swelling agent shelf-time is short, the shortcoming of the easy dead roasting of calcium oxide.
The Chinese patent literature of publication number CN101774777A (applicant: Jiangsu Botexin Materials Co., Ltd and Jiangsu architecture science research institute company limited) discloses a kind of preparation method of cement expansive material.To adopt after Wingdale and 5-10% composite mineralizer intergrinding to be sintered into the calcium oxide expansive clinker through 1100 ℃-1300 ℃, then with porous zeolite and flyash isodispersity carrier proportionally grinding become swelling agent.Composite mineralizer is comprised of the gypsum of 50-70% and the copper ashes of 30-50%.This cement expansive material has grog weathering resistance ability, the shortcoming that the swelling agent shelf-time is short.
The Chinese patent literature of publication number CN102329093A (applicant: the preparation method who discloses a kind of cement expansive material Shenzhen continental rise Investment Co., Ltd).Be to adopt Wingdale 70-85%, white clay 8-15%, gypsum 2-5%, iron powder 2-5% intergrinding, be sintered into expansive clinker through 1350 ℃-1450 ℃.Expansive clinker contains 12-23%C
3S, 50-70% free CaO, 5-15%C
4AF, 5-10%C
3A。With this grog again with anhydrite and metakaolin, high alumina or calcined diatomite in proportion intergrinding become swelling agent.This cement expansive material has grog weathering resistance ability, the shortcoming that the swelling agent shelf-time is short.
The Chinese patent literature of publication number CN102162244A (applicant: the preparation method who China Building Material Scientific Research General Institute) discloses a kind of cement expansive material.To adopt 40%-80wt% Wingdale and 20%-60wt% gypsum intergrinding, in rotary kiln through 1300 ℃ of-1500 ℃ of high-temperature calcinations, again with the ratio of this calcined material according to 20%-80wt%, with the calcium sulphoaluminate cement clinker of 20%-80wt% or alunite (calcining or non-calcining) or aluminous cement grog or its mixture intergrinding to specific surface area 150-400m
2/ kg makes cement expansive material.This cement expansive material has grog weathering resistance ability, the shortcoming that the swelling agent shelf-time is short.
All contain free calcium oxide in above-mentioned swelling agent, the mineral of parcel free calcium oxide are mainly C
3S or calcium iron sosoloid or gypsum-cao solid soln, ubiquity expansive clinker easy-weathering, therefore the problem such as the grog staging life is short, and the swelling agent finished product quality guaranteed period after grinding is short need to make improvements raising.
Summary of the invention
The gypsum and the calcium oxide melt inclusions expansive clinker that the purpose of this invention is to provide a kind of high-expansion energy and weathering resistance ability, and gypsum and the calcium oxide melt inclusions cement expansive material that can extend the finished product quality guaranteed period.
For achieving the above object, the present invention is by the following technical solutions:
A kind of gypsum and calcium oxide melt inclusions expansive clinker are prepared in 1300 ℃-1500 ℃ (preferred 1300～1400 ℃) lower high-temperature calcination by the raw material that comprises following weight percentage: 40wt%-80wt% Wingdale (calcium carbonate); 20wt%-60wt% gypsum (can be dihydrate gypsum, semi-hydrated gypsum or anhydrite); The aluminum oxide of Wingdale and gypsum summation 0.1wt%-1.0wt% and/or Tai-Ace S 150 (preferably sulfuric acid aluminium).
Described raw material preferably includes: 40wt%-80wt% Wingdale (calcium carbonate); 20wt%-60wt% gypsum (anhydrite); And aluminum oxide and/or the Tai-Ace S 150 of Wingdale and gypsum summation 1.0wt%.
More preferably, described gypsum and calcium oxide melt inclusions expansive clinker are that the raw material of following weight percentage obtains 1300 ℃ of calcinings: 70wt% Wingdale (calcium carbonate), the Tai-Ace S 150 of 30wt% gypsum (anhydrite) and Wingdale and gypsum summation 0.5wt%-1.0wt%.
The present invention further provides the preparation method of described gypsum and calcium oxide melt inclusions expansive clinker, is to specific surface area 140-400m with described Wingdale, gypsum, aluminum oxide and/or Tai-Ace S 150 intergrinding
2/ kg makes raw material, through 1300 ℃-1500 ℃ (preferred 1300～1400 ℃ or 1300 ℃) high-temperature calcinations, obtains gypsum and calcium oxide melt inclusions expansive clinker in rotary kiln.
Second aspect present invention is to provide a kind of gypsum and calcium oxide melt inclusions cement expansive material, it is obtained by the raw material intergrinding, and described raw material comprises the component of following weight percentage: the above-mentioned gypsum of component one: 20wt%-80wt% and calcium oxide melt inclusions expansive clinker; Component two: 20wt%-80wt% calcium sulphoaluminate cement clinker, alunite or aluminous cement grog; Component three: the calcium stearate of component one and component two summation 0.01wt%-0.5wt% is or/and trolamine.
Wherein, described component three is preferably calcium stearate, or calcium stearate and trolamine compound use.Component three is preferably component one and the calcium stearate of component two summation 0.05wt% and the trolamine of 0.05wt%.
The preferred calcium sulphoaluminate cement clinker of described component two.
The present invention prepares the method for described gypsum and calcium oxide melt inclusions cement expansive material, be with gypsum and calcium oxide melt inclusions expansive clinker, calcium stearate or/and trolamine, calcium sulphoaluminate cement clinker or alunite and/or aluminous cement grog intergrinding to specific surface area 140-400m
2/ kg obtains gypsum and calcium oxide melt inclusions cement expansive material.
Described gypsum and calcium oxide melt inclusions cement expansive material improve the application of concrete in resisting the concrete of shrinkage in preparation and also belong to the present invention.During application, cement expansive material of the present invention is added in concrete material, can improve concrete and resist shrinkage.
Adopt above scheme, cement expansive material of the present invention has the functions such as cracking resistance, impervious, compensate for shrinkage in application, have advantages of that expansion character is high, the waterproof rate of expansion is large, itself have batching wide material sources, production technique simply, easily burn till, grog weathering resistance ability is strong, the long advantages such as (reaching half a year) of shelf life of products.Compare with swelling agent of the prior art, have that early expansion is large, the later stage shrink little, do not produce the later stage detrimental expansion, can reduce or remit concrete structure and produce harmful cracks because of early-age shrinkage, dry shrinkage and cold shrinkage, overcome the structural leakage problem, the anti-crack and anti-seepage that can be used for the general concrete structure, and can increase substantially concrete weather resistance.The present invention has the following advantages:
1. due to gypsum and calcium oxide melt inclusions expansive clinker weathering resistance ability strong (generally over 14 days), under the conventional terms of packing of the cement expansive material of its preparation, shelf life of products is grown (reaching half a year).And the existing calcium oxide expansion agents grog shelf-time used is no more than 7 days, and under the conventional terms of packing of the swelling agent product that makes, shelf life of products is no more than 3 months.Therefore the present invention is convenient produces and application management, reduces the grog waste, also reduces simultaneously rotten grog contaminate environment, is conducive to ecological environmental protection.
2. gypsum and calcium oxide melt inclusions expansive clinker limited expansion rate are high, press the concrete expansion standard test, its salient features---limited expansion rate is all higher than standard code, and also higher than existing product performance, therefore prepared swelling agent in use just can reduce volume.
3. starting material are easy to get, and preparation technology is simple, and cost reduces greatly, and economic results in society are remarkable.
Below in conjunction with specific embodiment, the present invention is described in further details.
Description of drawings
Fig. 1 is gypsum of the present invention and calcium oxide melt inclusions expansive clinker stereoscan photograph.
Embodiment
First aspect of the present invention provides the strong gypsum of a kind of weathering resistance ability and calcium oxide melt inclusions expansive clinker.It is to form by following raw material high-temperature calcination.In calcination process, gypsum melting parcel CaO has avoided most of free calcium oxide to be directly exposed in air.Its composition of raw materials comprises the component of following weight percentage: 40wt%-80wt% Wingdale (calcium carbonate), 20wt%-60wt% gypsum (anhydrite), and aluminum oxide and/or the Tai-Ace S 150 of Wingdale and anhydrite summation 0.1wt%-1.0wt%.
Preferred assembly is: 40wt%-80wt% Wingdale (calcium carbonate), 20wt%-60wt% gypsum (anhydrite), 1.0wt% aluminum oxide and/or the Tai-Ace S 150 of Wingdale and anhydrite summation.
Most preferred gypsum and calcium oxide melt inclusions expansive clinker, be by 70wt% Wingdale (calcium carbonate), 30wt% gypsum (anhydrite) and 0.5wt%-1.0wt%(account for Wingdale and gypsum summation percentage composition) Tai-Ace S 150 blend grinding after obtain 1300 ℃ of calcinings.
Correspondence of the present invention also provides a kind of method for preparing above-mentioned gypsum and calcium oxide melt inclusions expansive clinker: (can be dihydrate gypsum, semi-hydrated gypsum or anhydrite with 40wt%-80wt% Wingdale (calcium carbonate), 20wt%-60wt% gypsum, but for fuel economy, the purpose that reduces costs, the present invention preferably adopts anhydrite), the aluminum oxide of Wingdale and gypsum summation 0.1wt%-1.0wt% and/or Tai-Ace S 150 intergrinding are to specific surface area 140-400m
2/ kg makes raw material, is preferably 50min through 1300 ℃ of-1500 ℃ of high-temperature calcination 30～90min(in rotary kiln), obtain gypsum and calcium oxide melt inclusions expansive clinker.
In the process of preparation gypsum and calcium oxide melt inclusions expansive clinker, doping reaction has occured and has generated new mineral in Wingdale (calcium carbonate), gypsum, aluminum oxide (or Tai-Ace S 150), and reaction formula is as follows:
3CaO+3Al
2O
3+CaSO
4→3CaO·3Al
2O
3·CaSO
4
12CaO+3Al
2(SO
4)
3→3CaO·3Al
2O
3·CaSO
4+8CaSO
4
(referring to Fig. 1) can find out by the grog stereoscan photograph, and the gypsum of molten state is inclusion, newly-generated trace quantity mineral 3CaO3Al in calcination process
2O
3CaSO
4(be abbreviated as
), size is 5～10 μ m approximately, and with the calcium oxide weave in of 10～20 μ m, this mineral structure forms, and can improve on the one hand the intensity of grog, it is made moist be difficult for collapse, the more important thing is with the calcium oxide weave in
Can increase and hinder airborne moisture and the catalytic chance of calcium oxide, improve the weathering resistance performance of grog.
The present invention further studies show that: the volume of aluminum oxide and/or Tai-Ace S 150 is influential to this expansive clinker performance: when volume increases to 1.0wt% from 0.1wt%, the weathering resistance ability of gypsum and calcium oxide melt inclusions expansive clinker strengthens gradually, and the weathering disintegration time of expansive clinker can extend 1-2 doubly; The volume of aluminum oxide and/or Tai-Ace S 150 greater than 1.0wt% after, although grog weathering resistance performance continue to improve, can reduce the expansion character of grog, so its volume should not be greater than 1.0wt%.
Second aspect of the present invention provides a kind of shelf life of products long cement expansive material.Its composition of raw materials comprises the component of following weight percentage:
Component one: 20wt%-80wt% gypsum and calcium oxide melt inclusions expansive clinker;
Component two: 20wt%-80wt% calcium sulphoaluminate cement clinker, alunite or aluminous cement grog;
Component three: calcium stearate is or/and trolamine, and volume is the 0.01wt%-0.5wt% of component one and component two summations.
More excellent, component three is component one and the calcium stearate of component two summation 0.05wt% and the trolamine of 0.05wt%.
Wherein, the effect of component one is the waterproof environment to be provided when the cement expansive material product mixes concrete (the waterproof environment refers to that the external world does not keep the skin wet to concrete, moisture in concrete does not does not outwards scatter and disappear yet, as the concrete sample with the plastic film sealing) the lower significant expansion sources CaO of expansion, and the calcium sulfate that can react formation swelling property product ettringite with component two is provided.Wherein the melting gypsum plays the effect of parcel CaO, can control the speed of CaO hydration reaction, makes its (referring to CaO) produce desirable expansion effect;
Wherein, component two can be calcium sulphoaluminate cement clinker, alunite or aluminous cement grog, or alunite and the aluminous cement grog mixture of assembly in any proportion; Its effect is when the cement expansive material product mixes concrete and the gypsum in component one (calcium sulfate composition) reaction generates swelling property hydrated product ettringite;
Wherein, component three is calcium stearate or trolamine, or the mixture of both assembly in any proportion; Its effect is in gypsum and calcium oxide melt inclusions cement expansive material fine particle surface formation one deck hydrophobic membrane, plays the effect that stops the calcium oxide suction to be become damp and rotten in the cement expansive material product is preserved.
Correspondence of the present invention also provides a kind of method for preparing above-mentioned gypsum and calcium oxide melt inclusions cement expansive material, be with the calcium stearate of 20wt%-80wt% gypsum and calcium oxide melt inclusions expansive clinker, 20wt%-80wt% calcium sulphoaluminate cement clinker or alunite and/or aluminous cement grog and aforementioned both summation 0.01wt%-0.5wt% or/and the trolamine intergrinding to specific surface area 140-400m
2/ kg obtains gypsum and calcium oxide melt inclusions cement expansive material.
In grinding process, add a small amount of calcium stearate or/and trolamine can form one deck hydrophobic membrane at levigate swelling agent particle surface, this is a kind of physically encapsulation pattern.This layer hydrophobic membrane can effectively stop the reaction of airborne moisture and calcium oxide, thereby can reduce the water-intake rate of swelling agent product, extends the product staging life.Experiment shows: when grinding gypsum and calcium oxide melt inclusions expansive clinker, admixture 0.01wt%-0.5wt% calcium stearate is or/and trolamine, can reduce the water-intake rate of swelling agent product, can reduce at most 1 times, thereby improve the quality guaranteed period (when the grinding portland cement clinker, the polyvalent alcohols such as trolamine normally were used as grinding aid and use in the past) of swelling agent product.The effect of using calcium stearate to reduce the water-intake rate of swelling agent product separately is better than trolamine, and both compound use better effects if are therefore preferentially adopt both mixtures.
Embodiment implements under take technical solution of the present invention as prerequisite, has provided detailed embodiment and concrete operating process, and embodiment will help to understand the present invention, but protection scope of the present invention is not limited to following embodiment.
In following embodiment, method therefor is ordinary method if no special instructions.
Embodiment one, preparation gypsum and calcium oxide melt inclusions expansive clinker and Performance Detection thereof
Press proportioning shown in table 1, with the aluminum oxide of 40wt%-80wt% Wingdale (calcium carbonate), 20wt%-60wt% gypsum (anhydrite), the above two total amount 0.1wt%-1.4wt% and/or Tai-Ace S 150 (not add aluminum oxide and/or Tai-Ace S 150 as Comparative Examples) intergrinding to specific surface area 350m
2/ kg(140-400m
2/ kg all can), make the material cake of diameter 100mm, thickness 15mm, after 105 ℃ of oven dry, put into electric furnace and calcine, middle through 1300 ℃ of-1500 ℃ of calcining at constant temperature 120min.To expect that cake takes out the cooling grog that obtains rapidly from electric furnace.
Get a part of chamotte powder and be milled to specific surface area 350m
2/ kg is with reference to the method check limited expansion rate of existing national standard " cement expansive material " GB23439-2009 regulation.Separately get a complete grog cake and put into 18 ℃-22 ℃ of temperature, observe the grog cake weathering disintegration time in the environment of relative humidity 92%-95%.
Detected result is as shown in table 1-1, table 1-2 and table 1-3, when the volume of aluminum oxide and/or Tai-Ace S 150 increases to 1.0wt% from 0.1wt%, the weathering resistance ability of gypsum and calcium oxide melt inclusions expansive clinker strengthens gradually, and the weathering disintegration time of expansive clinker can extend 1-2 doubly; The volume of aluminum oxide and/or Tai-Ace S 150 greater than 1.0wt% after, the confined expansion rate score reduces, and can reduce the expansion character of grog, therefore, the volume of aluminum oxide and/or Tai-Ace S 150 is preferably 0.1wt%-1.0wt%.In addition, under identical volume, the effect of admixture Tai-Ace S 150 is more better.Calcining temperature on the expansion character of gypsum and calcium oxide melt inclusions expansive clinker and the impact of weathering resistance ability is: along with calcining temperature improves, limited expansion rate reduces, and the weathering resistance ability improves, and calcining temperature is preferably 1300～1400 ℃.
Proportioning raw materials and the performance test results thereof of table 1-1 gypsum and calcium oxide melt inclusions expansive clinker
Proportioning raw materials and the performance test results thereof of table 1-2 gypsum and calcium oxide melt inclusions expansive clinker
Proportioning raw materials and the performance test results thereof of table 1-3 gypsum and calcium oxide melt inclusions expansive clinker
From the listed aggregation of data examination of table 1, (the confined expansion rate score is the highest for the gypsum of example 11-14 and calcium oxide melt inclusions expansive clinker best performance, and the grog weathering disintegration time is all over 20 days simultaneously), it is by 70wt% Wingdale (calcium carbonate), obtains 1300 ℃ of calcinings after the Tai-Ace S 150 grinding of 30wt% gypsum (anhydrite) and Wingdale and gypsum summation 0.5wt%-1.0wt%.
The impact on gypsum and the calcium oxide melt inclusions expansive clinker powder water-intake rate of oxygen-freeization aluminium and Tai-Ace S 150 of test example one, detection trolamine and/or calcium stearate.
With 70wt% Wingdale (calcium carbonate), 30wt% gypsum (anhydrite) intergrinding to specific surface area 350m
2/ kg(140-400m
2/ kg all can), diameter 1600mm hole enlargement to the rotary kiln of 1900mm through 1350 ℃ of calcining at constant temperature.Chamotte powder is milled to specific surface area 350m
2/ kg, the mixture of the trolamine of admixture 0.00wt%-0.50wt%, calcium stearate or both different ratioss in grinding process (concrete volume is as shown in table 2), the gained sample is placed on 18 ℃-22 ℃ of temperature, observes the water-intake rate of chamotte powder swelling agent in the environment of relative humidity 92%-95%.
Detected result is as shown in table 2, can find out along with calcium stearate or trolamine incorporation increase to 0.5wt% from 0.01wt%, the water-intake rate of levigate chamotte powder progressively reduces, and can reduce at the most 1 times, shows that calcium stearate or trolamine have hindered the chamotte powder suction.Wherein, the effect of calcium stearate is better than trolamine, and both compound use better effects if are therefore preferentially adopt both mixtures.Consider for economy, volume should not surpass 0.5wt%.
Table 2 trolamine and/or calcium stearate are on the gypsum of oxygen-freeization aluminium and Tai-Ace S 150 and the detected result of calcium oxide melt inclusions expansive clinker powder water-intake rate impact
The impact on salic gypsum and calcium oxide melt inclusions expansive clinker water-intake rate of test example two, detection trolamine and/or calcium stearate
With the aluminum oxide intergrinding of 70wt% Wingdale (calcium carbonate), 30wt% gypsum (anhydrite) and Wingdale and gypsum sum 1.0wt% to specific surface area 350m
2/ kg(140-400m
2/ kg all can), diameter 1600mm hole enlargement to the rotary kiln of 1900mm through 1350 ℃ of calcining at constant temperature.Chamotte powder is milled to specific surface area 350m
2/ kg, the mixture of the trolamine of admixture 0.00wt%-0.50wt%, calcium stearate or both different ratioss in grinding process (concrete volume is as shown in table 3), the gained sample is placed on 18 ℃-22 ℃ of temperature, observes the water-intake rate of swelling agent in the environment of relative humidity 92%-95%.
Detected result is as shown in table 3, can find out along with calcium stearate or trolamine volume increase the water absorption decreased of chamotte powder.As the water-intake rate of 3d, Comparative Examples is 12.56%, and the embodiment 3 of admixture 0.10% calcium stearate is reduced to 8.15%, has reduced 4.41%, and the minimizing amplitude reaches 35%; The embodiment 8 of admixture 0.10% trolamine is reduced to 9.98%, has reduced 2.58%, and the minimizing amplitude reaches 20%; 11 of the embodiment of admixture 0.05% calcium stearate and 0.05% trolamine are down to 6.35%, have reduced 6.21%, and the minimizing amplitude reaches 50%.
When grinding gypsum and calcium oxide melt inclusions expansive clinker, admixture 0.01wt%-0.5wt% calcium stearate can reduce the water-intake rate of swelling agent product or/and trolamine, can reduce at the most 1 times, thereby improves the quality guaranteed period of swelling agent product.When using separately, the effect of calcium stearate is better than trolamine, and both compound use better effects if are therefore preferentially adopt both mixtures.In addition, after the admixture aluminum oxide, gypsum and the calcium oxide melt inclusions expansive clinker water-intake rate of admixture aluminum oxide do not decrease yet than test example one.Embodiment 11 in comparative experimental example one and the embodiment 11 of test example two can find, under identical calcium stearate and trolamine volume condition, test example two each in length of time water-intake rate all less than the test example one of alumina doped not in the corresponding length of time.
Table 3 trolamine and/or the calcium stearate detected result on salic gypsum and the impact of calcium oxide melt inclusions expansive clinker water-intake rate
The impact on gypsum and the calcium oxide melt inclusions expansive clinker water-intake rate of sulfur acid aluminium of test example three, detection trolamine and/or calcium stearate
With the Tai-Ace S 150 intergrinding of 70wt% Wingdale (calcium carbonate), 30wt% gypsum (anhydrite) and Wingdale and gypsum sum 1.0wt% to specific surface area 350m
2/ kg(140-400m
2/ kg all can), diameter 1600mm hole enlargement to the rotary kiln of 1900mm through 1350 ℃ of calcining at constant temperature.Chamotte powder is milled to specific surface area 350m
2/ kg, the mixture of the trolamine of admixture 0.00wt%-0.50wt%, calcium stearate or both different ratioss in grinding process (concrete volume is as shown in table 3), the gained sample is placed on 18 ℃-22 ℃ of temperature, observes the water-intake rate of swelling agent in the environment of relative humidity 92%-95%.
Detected result is as shown in table 4, can find out along with calcium stearate or trolamine volume increase the water absorption decreased of chamotte powder.As the water-intake rate of 5d, Comparative Examples is 16.84%, and the embodiment 5 of admixture 0.50% calcium stearate is reduced to 4.98%, has reduced 11.86%, and the minimizing amplitude reaches 70%; The embodiment 10 of admixture 0.50% trolamine is reduced to 9.26%, has reduced 7.58%, and the minimizing amplitude reaches 45%; 11 of the embodiment of admixture 0.05% calcium stearate and 0.05% trolamine are down to 8.90%, have reduced 7.94%, and the minimizing amplitude reaches 47%.
When grinding gypsum and calcium oxide melt inclusions expansive clinker, admixture 0.01wt%-0.5wt% calcium stearate can reduce the water-intake rate of swelling agent product or/and trolamine, can reduce at the most 1 times, thereby improves the quality guaranteed period of swelling agent product.When using separately, the effect of calcium stearate is better than trolamine, both compound use better effects if, as in this test example, both mix use, when total addition content is all 0.10%, the 1d water-intake rate, be 2.67%(embodiment 3 when singly mixing calcium stearate), be 2.76%(embodiment 8 when singly mixing trolamine), and be 1.90%(embodiment 11 during both blendings).Therefore preferentially adopt both mixtures.In addition, after admixture Tai-Ace S 150, gypsum and the calcium oxide melt inclusions expansive clinker water-intake rate of admixture Tai-Ace S 150 and/or aluminum oxide do not decrease yet than test example one.The embodiment 11 of the embodiment 11 in comparative experimental example one, the embodiment 11 in test example two and test example three can find, under identical calcium stearate and trolamine volume condition, test example three each in length of time water-intake rate not only all less than the test example one of not mixing Tai-Ace S 150 and/or aluminum oxide the corresponding length of time, and less than the test example two of admixture aluminum oxide.
Table 4 trolamine and/or calcium stearate are on the gypsum of sulfur acid aluminium and the detected result of calcium oxide melt inclusions expansive clinker water-intake rate impact
Embodiment two, preparation gypsum and calcium oxide melt inclusions cement expansive material and Performance Detection thereof
The preparation method of gypsum of the present invention and calcium oxide melt inclusions cement expansive material comprises the following steps:
1) proportioning as shown in table 5, with the aluminum oxide of 40wt%-80wt% Wingdale (calcium carbonate), 20wt%-60wt% gypsum (anhydrite) and Wingdale and gypsum sum 0.1wt%-1.0wt% and/or Tai-Ace S 150 intergrinding to specific surface area 350m
2/ kg(140-400m
2/ kg all can), diameter 1600mm hole enlargement to the rotary kiln of 1900mm through 1350 ℃ of calcining at constant temperature.Obtain gypsum and calcium oxide melt inclusions expansive clinker.
2) proportioning as shown in table 5, with 20wt%-80wt% gypsum and calcium oxide melt inclusions expansive clinker, 0.05wt% calcium stearate and 0.05wt% trolamine mixture, 20wt%-80wt% calcium sulphoaluminate cement clinker (available from Xinmi City, Henan) or alunite (available from Lujiang, Anhui) and/or aluminous cement grog (available from Jiaozhuo, Henan) intergrinding to specific surface area 140-400m
2/ kg obtains gypsum and calcium oxide melt inclusions cement expansive material.
With reference to the method check gypsum of the present invention of existing national standard " cement expansive material " GB23439-2009 regulation and the limited expansion rate of calcium oxide melt inclusions cement expansive material (take commercially available CSA, AEA, UEA, PEA swelling agent as contrast).
Detected result is as shown in table 5, can find out, the limited expansion rate of gypsum of the present invention and calcium oxide melt inclusions cement expansive material is not less than 0.15%, under the waterproof environment, limited expansion rate is not less than 0.10%, its rate of expansion has good expansion character far above currently available products, is suitable for very much resisting concrete contraction (dry shrinkage and temperature shrinkage) cracking.
The performance test results of table 5 gypsum and calcium oxide melt inclusions cement expansive material
The limited expansion rate of test example four, admixture gypsum and calcium oxide melt inclusions cement expansive material
Adopt gypsum and the calcium oxide melt inclusions cement expansive material of the embodiment of the present invention two, with the dummy of not mixing swelling agent (Comparative Examples 1) and commercially available hydration heat inhibition type swelling agent CSA(available from Tianjin, Comparative Examples 2), AEA(is available from Tianjin, Comparative Examples 3), UEA(is available from Tianjin, Comparative Examples 4), PEA(is available from Tianjin, Comparative Examples 5) test.Press the concrete mix shown in table 6, in stirrer, gypsum of the present invention and calcium oxide melt inclusions cement expansive material are stirred into required concrete mix jointly with concrete other raw material of composition, control concrete and go out machine slump 180mm-220mm.
Limited expansion rate test method according to existing national standard " cement expansive material " GB23439-2009 appendix B regulation is tested.
As shown in table 6, after the commercially available swelling agent of admixture and gypsum of the present invention and calcium oxide melt inclusions cement expansive material, under identical volume, in water of the present invention, the 14d limited expansion rate is the highest, and when in water, the 14d maintenance turns in air maintenance 28d, limited expansion rate or on the occasion of, show that concrete also is in pressured state, have and resist significantly the shrinkage cracking ability.Particularly change in air after maintenance, the concrete of admixture swelling agent of the present invention, drying shrinkage fall (in water in maintenance 14d and water maintenance 14d turn the difference between maintenance 28d limited expansion rate in air) is significantly less than Comparative Examples.The drying shrinkage fall of Comparative Examples on average is about 0.043%, and the present invention is only 0.031%.It is stronger that this shows that also the present invention resists the dry shrinkage ability.
Table 6 concrete mix
Test example five, gypsum and calcium oxide melt inclusions swelling agent quality guaranteed period are detected
Adopt gypsum and the calcium oxide melt inclusions swelling agent of the embodiment of the present invention two, the gypsum that provides with CN102162244A and calcium oxide melt inclusions swelling agent (Comparative Examples 1) and the commercially available CSA swelling agent that contains free calcium oxide (available from Tianjin, Comparative Examples 2) carry out difference staging life limited expansion rate Performance Detection.Test sample all adopts one deck to cover plastic film woven bag packing, is placed on identical finished product storehouse and deposits.7d limited expansion rate in the method check water of existing national standard " cement expansive material " GB23439-2009 regulation.
Detected result is as shown in table 7, can find out, the quality guaranteed period of gypsum of the present invention and calcium oxide melt inclusions swelling agent is relatively long.Comparative Examples 1 is after depositing 6 months, and limited expansion rate is down to 0.047% from initial 0.187%, has not reached the II type product index value of standard code.Comparative Examples 2 is after depositing 6 months, and limited expansion rate is down to 0.029% from initial 0.115%, does not also reach the II type product index value of standard code.The present invention is down to 0.068% from initial 0.191%, satisfies the II type product index value requirement of standard code fully.
7d limited expansion rate performance test results in table 8 water of different staging life
Cement expansive material of the present invention has the large characteristics of limited expansion rate, can effectively solve concrete shrinkage cracking defective, has following characteristics and beneficial effect:
1. starting material wide material sources, preparation technology is simple, and production cost is low.
2. do not use poisonous, harmful starting material in the production process of this product, be beneficial to the enforcement of suitability for industrialized production and safety and the cleaning of assurance production process, meet environmental requirement.
Product have that rate of expansion is high, the later stage shrink little, can effectively solve concrete cracking, can increase substantially concrete durability.
4. product weathering resistance ability is strong, long quality-guarantee period (reaching 6 months).
5. this product has good adaptability to the cement of different varieties, the place of production and mineral composition.
6. the product using method is simple, convenient, and operation, control are easily.
7. this product can be used for preparing expansive concrete and expansive concrete, can also be for the preparation of anticracking grout, injection material etc., applied range.
Claims (10)
1. a gypsum and calcium oxide melt inclusions expansive clinker are prepared in 1300 ℃-1500 ℃ (preferred 1300～1400 ℃) lower high-temperature calcination by the raw material that comprises following weight percentage:
40wt%-80wt% Wingdale (calcium carbonate);
20wt%-60wt% gypsum (can be dihydrate gypsum, semi-hydrated gypsum or anhydrite);
The aluminum oxide of Wingdale and gypsum summation 0.1wt%-1.0wt% and/or Tai-Ace S 150 (preferably sulfuric acid aluminium).
2. gypsum according to claim 1 and calcium oxide melt inclusions expansive clinker, it is characterized in that: described raw material preferably includes:
40wt%-80wt% Wingdale (calcium carbonate);
20wt%-60wt% gypsum (anhydrite); And
Aluminum oxide and/or the Tai-Ace S 150 of Wingdale and gypsum summation 1.0wt%.
3. gypsum according to claim 1 and calcium oxide melt inclusions expansive clinker, it is characterized in that: the raw material that is preferably following weight percentage obtains 1300 ℃ of calcinings: 70wt% Wingdale (calcium carbonate), the Tai-Ace S 150 of 30wt% gypsum (anhydrite) and Wingdale and gypsum summation 0.5wt%-1.0wt%.
4. the preparation method of the arbitrary described gypsum of claims 1 to 3 and calcium oxide melt inclusions expansive clinker, comprise Wingdale, gypsum, aluminum oxide and/or Tai-Ace S 150 intergrinding to specific surface area 140-400m
2/ kg makes raw material, through 1300 ℃-1500 ℃ (preferred 1300～1400 ℃ or 1300 ℃) high-temperature calcinations, obtains gypsum and calcium oxide melt inclusions expansive clinker in rotary kiln.
5. a gypsum and calcium oxide melt inclusions cement expansive material, obtained by the raw material intergrinding, and described raw material comprises the component of following weight percentage:
Component one: the arbitrary described gypsum of 20wt%-80wt% claims 1 to 3 and calcium oxide melt inclusions expansive clinker;
Component two: 20wt%-80wt% calcium sulphoaluminate cement clinker, alunite or aluminous cement grog;
Component three: the calcium stearate of component one and component two summation 0.01wt%-0.5wt% is or/and trolamine.
6. gypsum according to claim 5 and calcium oxide melt inclusions cement expansive material, it is characterized in that: described component three is preferably calcium stearate, or calcium stearate and trolamine compound use.
7. gypsum according to claim 6 and calcium oxide melt inclusions cement expansive material is characterized in that: component three is component one and the calcium stearate of component two summation 0.05wt% and the trolamine of 0.05wt%.
8. according to claim 5 or 6 or 7 described gypsum and calcium oxide melt inclusions cement expansive material, is characterized in that: the preferred calcium sulphoaluminate cement clinker of described component two.
9. method for preparing the arbitrary described gypsum of claim 5 to 8 and calcium oxide melt inclusions cement expansive material, with gypsum and calcium oxide melt inclusions expansive clinker, calcium stearate or/and trolamine, calcium sulphoaluminate cement clinker or alunite and/or aluminous cement grog intergrinding to specific surface area 140-400m
2/ kg obtains gypsum and calcium oxide melt inclusions cement expansive material.
10. the arbitrary described gypsum of claim 5 to 8 and calcium oxide melt inclusions cement expansive material improve the application of concrete in resisting the concrete of shrinkage in preparation.
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