CN106316184A - Cement self-stress expansion clinker and preparation method thereof - Google Patents
Cement self-stress expansion clinker and preparation method thereof Download PDFInfo
- Publication number
- CN106316184A CN106316184A CN201510405039.6A CN201510405039A CN106316184A CN 106316184 A CN106316184 A CN 106316184A CN 201510405039 A CN201510405039 A CN 201510405039A CN 106316184 A CN106316184 A CN 106316184A
- Authority
- CN
- China
- Prior art keywords
- cao
- caso
- expansive clinker
- cement
- clinker
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004568 cement Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910052925 anhydrite Inorganic materials 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 239000004606 Fillers/Extenders Substances 0.000 claims description 33
- 238000001354 calcination Methods 0.000 claims description 26
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 13
- 239000008187 granular material Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims 1
- 239000004567 concrete Substances 0.000 abstract description 30
- 239000004566 building material Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 9
- 238000003837 high-temperature calcination Methods 0.000 abstract description 4
- 239000004570 mortar (masonry) Substances 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 98
- 239000000292 calcium oxide Substances 0.000 description 51
- 239000011575 calcium Substances 0.000 description 27
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 22
- 229910052791 calcium Inorganic materials 0.000 description 22
- 239000000463 material Substances 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 15
- 238000005253 cladding Methods 0.000 description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 229910001653 ettringite Inorganic materials 0.000 description 11
- 239000011707 mineral Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000011162 core material Substances 0.000 description 5
- 230000003111 delayed effect Effects 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 235000011132 calcium sulphate Nutrition 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910002703 Al K Inorganic materials 0.000 description 2
- 229910002552 Fe K Inorganic materials 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 229910003110 Mg K Inorganic materials 0.000 description 2
- 229910002794 Si K Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 ettringite) Chemical compound 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000001149 cognitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001595 contractor effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical group [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- UFLSLGGVXPPUDQ-UHFFFAOYSA-N dicalcium oxygen(2-) Chemical compound [O--].[O--].[Ca++].[Ca++] UFLSLGGVXPPUDQ-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a cement self-stress expansion clinker and a preparation method thereof. The cement is expandedThe swelling clinker comprises: CaO and CaSO4The expansion clinker has a core-shell structure, wherein CaO is mainly used as a core and CaSO is mainly used as a core4Is a shell. The expansion clinker is prepared by mixing raw materials for providing CaO and raw materials for providing CaSO4The raw material is formed by high-temperature calcination at 1250-1500 ℃, and CaO and CaSO are contained in the raw material4The weight ratio of (A) to (B) is about 1 (0.15 to 0.67). The expansion clinker obtained by the invention has high expansion energy, has a shrinkage compensation effect on cement building materials, and has the effect of reducing cracks of mortar and concrete buildings.
Description
Technical field
The present invention relates to compensating shrinkage of concrete additive agent field, relate particularly to a kind of cement seif-citing rate
Expansive clinker.Especially, the present invention relates to one and be mainly composed of CaO and CaSO4Cement from should
Power expansive clinker and the manufacture method of this expansive clinker.
Background technology
Extender refers to a kind of additive for cement, when cement setting hardens, and extender volume
Expand, play and compensate contraction, tension reinforcing steel bar generation prestressing force and be sufficient filling with the effect in cement gap.Swollen
The primary categories of swollen dose includes: alumite plumping agent, sulphoaluminate expander, calcium oxide extender, ferrum
Bits extender, MgO expansion agent, calcium oxide-calcium sulphoaluminate composite expanding agent etc..
The reason producing crack during armored concrete hardening is complex.Generally, it is considered that concrete shrinkage and
Shrinkage is the main cause producing crack.Therefore, it may be desirable to, mix in concrete and can reach
Compensate its extender shunk.Extender joins in normal concrete, generates and expand knot in a large number after adding water
Brilliant hydras-hydrated calcium aluminate sulfate (i.e. ettringite), makes concrete produce appropriateness and expands, adjacent at reinforcing bar
Under the constraint of position, setting up 0.2～0.7MPa compressive pre-stress in the structure, this compressive pre-stress can substantially support
The shrinkage tensile stress that the concrete that disappears produces in hardening process, meanwhile, has postponed the generation process shunk.
When concrete starts to shrink at, its stretching resistance be enough to resist shrinkage stress, thus prevent or reduce coagulation
Soil shrinkage cracking.And the entringite produced makes concrete finer and close, thus substantially increase concrete
The anti-crack and anti-seepage performance of structure.At present, the most consistent expansive concrete using extender preparation
Replace normal concrete to solve building and split the problem oozed.
Cement expansive material is widely used in underground waterproof seepage control project, super-long structural and all kinds of large-scale
Concrete construction engineering, is one of effective technology preventing Shrinkage Cracking of Concrete.Domestic existing expansion
The ettringite that it is main expansion source with calcium sulphoaluminate or calcium oxide composite sulfur calcium aluminate that agent is the most all belonging to
Type extender.
Calcium oxide as a kind of expansive clinker at first Japanese invention popularization and application, calcium sulphoaluminate master
If being studied total institute by Chinese building material to develop and promote the most at home and apply.Later along with compound swollen
The appearance of swollen dose, the expansion sources such as selective oxidation calcium, calcium sulphoaluminate, MgO, it is combined into single source, multi-source
Extender.Applying through market for many years and find, the mineral of identical chemical constituent are without calcining as swollen
When swollen dose, activity is the lowest, only forms expansive clinker by calcining, could be by big for the expansion character of extender
Width improves.Expansive clinker has become the core material of extender the most.But this type of grog and clinker
Mineral composition be sufficiently close to, although can by adjust grog mineral composition change the demand to water
Amount, but the water generation hydration reaction that need to be necessary, could meet the expansion compensation to cement building material and receive
Contracting effect.Therefore, expansive clinker shows with the matching of cement as the core material of cement building material additive
Obtain particularly important.
Cement building material shrinks and is generally divided into four-stage: plastic shrinkage, chemistry self-constriction, temperature shrinkage and
Dry shrinkage.As the expansive clinker formed with inorganic mineral, its expansion energy plays and too early can be lost in water
The plastic stage of mud building materials, cement building material then cannot be able to be formed swollen because of hydropenia at the dry shrinkage of middle and late stage
Swollen.
So, chemistry self-constriction and two stages of temperature shrinkage are to cause cement building material cracking and durable pass
Key period, is also the Main Stage that can play a role of expanding material.The expansion master of MgO type extender
There is the middle and late stage shunk at cement building material, it is impossible to meet compensation demand.In the market some are swollen
The hydration rate of swollen dose is very fast, the phase of expansion is short, heat release is concentrated, and its effective expansion can be lost largely
In the plastic shrinkage stage, and increase substantially temperature in the plastic stage, temperature can be accelerated and promote and early stage
Chemistry of cement reaction, be formed for highly expanded when cement building material intensity is the most enough formed, therefore can shadow
Ring the stability of building materials.The most wide variety of sulfur aluminium profiles extender is then the lowest not due to expansion rate
Can be formed concrete shrinkage-compensating effectively.Traditional calcium sulphoaluminate or calcium oxide composite sulfur calcium aluminate are swollen
Swollen dose exists a bigger hidden danger is that secondary ettringite forms (secondanz substguent ettringite
Formation, SEF) harm that brings.
So-called secondary ettringite is formed, and refers to after extender produces expansion, the calcium again occurred
Alumen is formed.Before secondary ettringite is formed, had occurred and that an entringite forming process, this time
It is the master that calcium sulphoaluminate class extender works that entringite forms (being properly termed as entringite for the first time to be formed)
Want reason.Formed for first time entringite, anhydrous calcium sulphoaluminate the chemical reaction forming entringite is:
C4A3S+8CaSO4+6CaO+96H2O→3C3A·3CaSO4·32H2O,
Wherein C4A3S represents: anhydrous calcium sulphoaluminate (3Ca.3Al2O3.CaSO4)；C3A represents tricalcium aluminate
(3CaO.Al2O3)。
In first time entringite forming process, as long as ensureing sufficient outside water supply, dead plaster is originally
Long-pending more than original 9 times that will be expanded to of health, thus reach the effect that compensating concrete shrinks.This is first years old
The contraction expanding meeting compensating concrete of secondary entringite forming process, it is clear that be favourable.And secondary calcium vitriol
Stone is formed and refers to the later stage in mortar and concrete hole, crack, interface owing to there is the material example containing aluminum
Such as aluminium oxide, so can secondary precipitation entringite.The formation of this secondary ettringite can bring entringite to postpone
Expanding (DEF), this DEF phenomenon occurs in the entringite in concrete and meets high temperature or long-term dry point
After solving dehydration, run into again water, such as precipitation, pipe leakage etc., and form second time and expand, at this moment
It is extremely harmful for expanding concrete, and now concrete is substantially at brittle state, can be unable to bear
The bulbs of pressure that DEF is formed, thus cause cement to ftracture, and this is also the most fatal cracking, it will cause
Concrete deteriorates comprehensively, it is therefore desirable to avoid the formation of secondary ettringite.To this end, reduce herein or do not introduce
Forming the raw material of secondary ettringite, such as aluminum, aluminium oxide, calcining simultaneously forms specific nucleocapsid structure,
Thus reduce the formation of entringite, it is to avoid water generation reexpansion met by concrete.
Summary of the invention
The present invention is to be provided is a kind of extender grog, and this extender grog expansion energy is high, is to expand
Core material, it is possible to compensate the contraction of cement building material, the most significantly control entringite delayed expansion simultaneously
(DEF) hidden danger.
After the present inventor's further investigation, find by providing CaO and containing CaSO4Weight ratio
For 1:(0.15～0.67) containing CaO with containing CaSO4Raw material, form main composition or base after calcining
Originally CaO and CaSO it is configured to4The extender grog of ad hoc structure, using the teaching of the invention it is possible to provide the expansion effect of improvement
Really, reduce entringite delayed expansion (DEF) hidden danger simultaneously.
The present invention provides the preparation method of a kind of cement seif-citing rate expansive clinker, including:
A) according to CaO, CaSO4Weight ratio be 1:(0.15～0.67), it is provided that the raw material containing CaO
With containing CaSO4Raw material, mainly comprised, preferably be basic composition is containing CaO and CaSO4Former
The raw mixture of material；
B) by this raw mixture about 1250 DEG C～1500 DEG C calcine such as 20～60 minutes, formed with
CaO is core, CaSO4Nucleocapsid structure expansive clinker for shell.Specifically, material is the highest
Temperature-heat-source interacts calcining, and (wherein, described mutual calcining is: Flow of Goods and Materials direction is sprayed with flame
In opposite direction, namely top fire calcining), form CaSO4As liquid phase with CaO as solid phase binding
Nucleocapsid structure.
In one preferred embodiment of the invention, CaO and CaSO in step a)4Weight ratio be
1:(0.45～0.55)；In presently preferred embodiment, CaO and CaSO in step a)4
Weight ratio be 1:(0.45～0.50), wherein most preferably weight ratio is 1:0.46-1:0.48.
As providing the raw material containing CaO to be, but it is not limited to: containing CaCO3Natural minerals,
Containing CaCO3Trade waste or recycle thing, such as limestone, aragonite, calcite, Chalk,
Limestone, marble, Tufa etc.；Or containing Ca (OH)2Natural minerals, industrial cycle utilize
Thing, such as Calx, slaked lime, carbide slag etc..Should be containing CaCO3Natural minerals, industrial cycle
CaO content in thing is utilized to be more than 40% weight, preferably greater than 55% weight；Containing Ca (OH)2Sky
So mineral, industrial cycle utilize thing, and its CaO content is more than 55% weight, preferably greater than 70% weight.
As providing containing CaSO4Raw material can be but to be not limited to: containing the CaSO of nodeless mesh water4Mineral,
Containing CaSO4Industrial cycle utilize thing, such as natural anhydrite, dihydrate gypsum, semi-hydrated gypsum, de-
Sulfur Gypsum Fibrosum, ardealite etc.；Or the CaSO containing water of crystallization4Mineral, industrial cycle utilize thing.Described
Containing nodeless mesh water CaSO4Mineral, industrial cycle utilize thing, its CaSO4Content is more than 60% weight,
Preferably greater than 80% weight；CaSO containing water of crystallization4Mineral, industrial cycle utilize the CaSO in thing4
Content is preferably greater than 50% weight, the material of more preferably greater than 70% weight.
Calcining heat can select in the range of about 1250 DEG C～1500 DEG C.The selection of temperature should
Making at the calcination temperature, CaO is solid-state, and CaSO4It is at least partially in molten condition, thus
CaSO can be obtained after firing4The nucleocapsid structure product being combined with CaO.Preferably, in step b)
High-temperature calcination temperature be 1400～1450 DEG C.More preferably, the high-temperature calcination temperature in step b) is
About 1450 DEG C.
In above-mentioned calcination temperature range, in step b) in nucleocapsid structure forming process, CaSO4For extremely
Small part is melted liquid, and CaO remains essentially as solid-state, so that be at least partially in molten
The CaSO of state4It is coated on CaO surface, forms CaO kernel-CaSO4The nucleocapsid structure of shell expands
Clinker particles.
Preferably, also including the step c) of cooling after step b), described cooling step such as can use
Grate-cooler cools down, and the extender grog after will calcining, after kiln discharge 30～60 minutes, is cooled to
50～100 DEG C.
The time of calcining can not particularly be limited, as long as ensureing CaSO4It is wrapped in CaO surface,
Form nucleocapsid structure extender granule.Preferably, in step b), calcination time is 30～60 minutes.
Preferably, after step b) or step c), also include grinding step d), grinding to described agglomerate ratio table
Area is more than 180m2/ kg, typically at 200m2/ kg to 500m2/ kg, or at 250m2/ kg is extremely
450m2/ kg, or at 300m2/ kg to 400m2/kg.Grinding is so that expansive clinker herein
Can have more preferable expansion character as required.Described grinding can use ball milling, Vertical Mill or roller mill
Etc. mode.In calcination process, owing to interacting calcining, material is constantly in mutual moving-state,
So the expansive clinker formed has multilamellar nucleocapsid structure, the granule after grinding is still for having core-shell structure copolymer knot
The expansive clinker granule of structure.
The present invention also provides for a kind of cement seif-citing rate expansive clinker, this cement seif-citing rate expansive clinker be core-
Shell structure, above-mentioned nucleocapsid structure cement seif-citing rate expansive clinker can use above-mentioned cement seif-citing rate to expand
Prepared by the preparation method of grog.
Preferably, after calcining below a diameter of 300 μm of above-mentioned clinker particles, below generally 200 μm,
It is more typically 2-100 μm, in particular 2-20 μm, during use, avoids concrete cracking.This grog
Grain is crystal grain, and described crystal grain is mainly by CaO kernel and CaSO4Shell forms, and shell is thick
Degree is 0.1-5 μm, preferably 0.1-3 μm, more preferably 0.05-2 μm.
Main by CaO kernel and CaSO4The extender grog that shell is formed is respectively with CaO, SO3For
Basic calculation, its chemical composition is CaO >=70wt%, preferably >=80wt%, more preferably >=85%, the most excellent
Choosing >=90%；SO3>=7wt%, preferably greater than >=10wt%, more preferably >=15%, remaining is brought into for raw material
Inevitably impurity, the total amount of extender grog is 100% weight.Impurity includes, but are not limited to:
Al2O3、Fe2O3And/or MgO etc., Al in this impurity2O3≤ 1% weight, preferably≤0.08% weight,
More preferably≤0.05% weight, even more preferably from≤0.02% weight；Fe2O3≤ 0.5% weight, preferably≤0.3% weight
Amount, more preferably≤0.2% weight；MgO≤5.0% weight.
Use technical scheme, have bright relative to this area existing calcium sulphoaluminate class extender
Aobvious technical advantage.The data of specific embodiment of the invention part will indicate that, the cement of the present invention is from answering
Power expansive clinker has higher expansion character, and its expansion character matches with cement building material, decreases
Effective expansion-loss of material, identical expansion rate volume is lower.Certainly should according to the cement that the present invention provides
Power expansive clinker preparation method, without adding conventional mineralizer in clinkersintering raw material, such as, contains
The mineralizer of Fe, Mg etc., further reduces other material impact on cement building material in grog, surely
Surely play expansion energy, cement building material can be made under the conditions of reinforced binding to produce the seif-citing rate of 1～3MPa, by
Step produces bulbs of pressure opposing cement building material autogenous shrinkage, thus suppresses mortar, concrete cracking, improves
The durability of cement building material.More surprisingly, the cement seif-citing rate expansive clinker of the present invention solves effectively
The thorny problem that entringite delayed expansion (DEF) of having determined brings.As it was previously stated, anhydrous calcium sulphoaluminate shape
The chemical reaction becoming entringite is the principal element that calcium sulphoaluminate class extender works, thus this area is
Some calcium sulphoaluminate class extender/expansive clinkers are required for adding the raw material containing aluminum, with in the final product
Generate anhydrous calcium sulphoaluminate.It is to say, this area is before the present invention proposes, define one
Technical common recognition, calcium sulphoaluminate class extender/expansive clinker does not has the interpolation of the aluminum of q.s impossible
Obtain good expansion effect.But, it is not limited to theory, after inventor finds that the introducing of aluminum causes
The harm of phase delayed expansion (DEF), DEF needs to meet three conditions simultaneously: 1) slurry
Or concrete needs additionally add aluminum source, there is a certain amount of sulfur and aluminum, usually more than 1% weight；
2) there is the space that entringite separates out in slurry or concrete；3) slurry or concrete can be filled
The water supply of foot.Wherein the 2nd) item and the 3rd) item condition is all unavoidable in a lot of application scenarios.
It is all component necessary to calcium sulphoaluminate class extender/expansive clinker according to traditional view, sulfur and aluminum, lacks
One can not.But, present inventors discovered unexpectedly that, the fact is not as cognitive in prior art institute
As, without extra aluminum source, only with CaO and CaSO4, the nucleocapsid structure that obtains after calcining
Cement seif-citing rate expansive clinker, it is possible to obtain good expansion effect, simultaneously because lack in final products
The aluminum of q.s, successfully avoids the DEF harm perplexing technical staff for a long time.
Accompanying drawing explanation
Fig. 1: the microgram of traditional CSA clinker structure
Structure microgram after the calcining of Fig. 2: carbonate-free lime expansive clinker
Fig. 3: according to an embodiment of the invention calcium oxide with calcium sulfate according to 1:0.5 weight ratio,
The nucleocapsid structure sulfur calcium expansive clinker structure microgram obtained is calcined at about 1450 DEG C
Fig. 4: the nucleocapsid structure sulfur calcium expansive clinker surface shape prepared according to an embodiment of the invention
The elementary analysis figure of looks figure and near surface material
Fig. 5: imperfect according to nucleocapsid structure sulfur calcium expansive clinker prepared by an embodiment of the invention
The elementary analysis figure at clad surface shape appearance figure and this position
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing of the present invention,
Embodiment, is described further technical scheme.Obviously, described embodiment is this
A part of embodiment of invention rather than whole embodiments.Based on described embodiments of the invention,
The every other technical side that those of ordinary skill in the art are obtained on the premise of without creative work
Case, broadly falls into the scope of protection of the invention.Unless specifically stated otherwise, ratio herein refers generally to weight ratio.
Embodiment 1 CaO, CaSO4The determination of mixed proportion
With CaO for main expansion composition, CaSO4For liquid phase ingredient, according to CaO, CaSO4Difference
Part by weight, prepares to provide CaO, CaSO4Raw material, and be sufficiently mixed above-mentioned raw materials, mixed
Thing；By said mixture about 1450 DEG C of high-temperature calcinations 40 minutes, form CaSO4The core of cladding CaO
-shell structure sulfur calcium expansive clinker.In the case of keeping other condition constant, change CaO, CaSO4It
Between part by weight, test obtain grog in water/air in limited expansion rate (volume), obtain
Result such as following table:
Table 1
The determination of embodiment 2 calcining heat
According to CaO, CaSO4For the weight ratio of 1:0.50, prepare to provide CaO, CaSO4Raw material.
After being sufficiently mixed above-mentioned raw materials, obtain mixture；Said mixture is calcined about at different high-temperature
60 minutes, form CaSO4The nucleocapsid structure sulfur calcium expansive clinker of cladding CaO.Keep other condition not
In the case of change, change calcining heat, test obtain grog in water/air in limited expansion rate (body
Long-pending), obtain the result such as following table:
Table 2
The sign of embodiment 3 product pattern
With with the identical method of embodiment 1 and 2, difference be according to CaO, CaSO4For 1:0.50
Part by weight, at about 1450 DEG C calcine, obtain CaSO4The nucleocapsid structure sulfur calcium of cladding CaO is swollen
Swollen grog.The micro-knot of the expansive clinker that employing scanning electron microscope (NEC: JSM6510LV) obtains
Structure, as shown in Figure 3.As a comparison, Fig. 1 and Fig. 2 sets forth simultaneously traditional C/S A grog and
The microstructure of calcining CaO.From Fig. 1-3, traditional C/S A grog presents obvious six side's ribs
Rod structure, this is the typical structure of calcium sulphoaluminate, is then more smooth spheroid shape after carbonate-free lime calcining,
The CaSO of the present invention4The nucleocapsid structure sulfur calcium expansive clinker appearance of cladding CaO has bigger with the above two
Difference, first it does not have hexagonal prism structure, shows not exist calcium sulphoaluminate；Secondly granule it
Between adhesion more apparent, unlike carbonate-free lime calcine after form the granule being clearly separated, this is due to molten
Space between granule is filled by the calcium sulfate of state.EDS micro analysis shows nucleocapsid structure sulfur
In calcium expansive clinker, there is extender granule, grain diameter between 2-20 μm, the cladding of calcium sulfate
Thickness is about 0.35 μm.
Embodiment 4 nucleocapsid structure
With with the similar method of embodiment 1 and 2, according to CaO, CaSO4For the weight ratio of 1:0.25,
Calcine at the moon 1450 DEG C, obtain CaSO4The nucleocapsid structure sulfur calcium expansive clinker of cladding CaO.Will
The nucleocapsid structure sulfur calcium expansive clinker arrived is respectively to being coated with complete material surface parts and imperfect cladding
Material position carried out elemental analysis, field emission scanning electron microscope (NEC: JSM7100F)
Fig. 4-5 is shown in by photo and elementary analysis collection of illustrative plates.To the elementary analysis result being coated with complete material surface parts
See table:
Table 3
| Element | Line type | Apparent concentration | K ratio | Wt% | Wt%Sigma |
| O | K linear system | 15.22 | 0.05121 | 44.81 | 0.44 |
| Mg | K linear system | 0.23 | 0.00151 | 0.37 | 0.07 |
| Al | K linear system | 0.05 | 0.00033 | 0.07 | 0.05 |
| Si | K linear system | 0.27 | 0.00216 | 0.36 | 0.06 |
| S | K linear system | 4.24 | 0.03657 | 5.13 | 0.11 |
| Ca | K linear system | 40.28 | 0.35993 | 48.84 | 0.41 |
| Fe | K linear system | 0.27 | 0.00272 | 0.42 | 0.15 |
| Total amount | 100.00 |
The material surface position to CaO kernel with imperfect cladding carries out elementary analysis, and result sees below
Table:
Table 4
| Element | Line type | Apparent concentration | K ratio | Wt% | Wt%Sigma |
| O | K linear system | 10.20 | 0.03432 | 36.87 | 0.61 |
| Mg | K linear system | 0.21 | 0.00140 | 0.35 | 0.08 |
| Al | K linear system | 0.03 | 0.00022 | 0.05 | 0.06 |
| Si | K linear system | 0.02 | 0.00015 | 0.03 | 0.06 |
| S | K linear system | 1.88 | 0.01617 | 2.32 | 0.10 |
| Ca | K linear system | 48.79 | 0.43590 | 60.29 | 0.60 |
| Fe | K linear system | 0.06 | 0.00057 | 0.09 | 0.19 |
| Total amount | 100.00 |
The result of both the above table is analyzed and understands, from being coated with complete material surface to the completeest
The material position of whole cladding, Ca brings up to 60.29% from 48.84%, and O is down to 36.87% from 44.81%,
And S is down to 2.32% from 5.13%, thus it has been confirmed that calcium oxide core surface has wrapped up calcium sulphate layer,
The grog of the present invention is CaSO4The nucleocapsid structure of cladding CaO.
Embodiment 5 and the comparison of prior art extender
Following table is by the CaSO of the present invention4The nucleocapsid structure sulfur calcium expansive clinker of parcel CaO is (referred to as
It is right that the expansive agent for cement slurry existing with prior art such as calcium sulfur al proportion CCS), limited expansion rate have been carried out
Ratio:
Table 5
As shown above, prior art existing calcium sulphoaluminate type extender, raw material is required for add relatively
Substantial amounts of aluminum, as it was previously stated, the existence of a large amount of aluminum may cause the secondary ettringite in later stage to be formed, thus
Cause delayed expansion, cause the risk that there is concrete cracking.On the contrary, the CaSO of the present invention4Parcel
The nucleocapsid structure sulfur calcium expansive clinker of CaO is added without aluminum source, significantly reduces secondary ettringite and is formed
The hidden danger brought.From the point of view of expansion rate, the CaSO of the present invention4The nucleocapsid structure sulfur calcium of cladding CaO is swollen
During swollen grog 7 days, in water, limited expansion rate is 0.141%-0.173%, and in air, the restriction of 21 days expands
Rate is 0.05%-0.10%, all close to the data of HCSA (high-performance cement expansive agent), is significantly better than
(United Expansing Agent, writes a Chinese character in simplified form UEA to UEA, and it is with aluminum sulfate, aluminium oxide, aluminum sulfate
Potassium etc. are main multiple expansion sources) and CSA (calcium sulphoaluminate class extender).Therefore, the CaSO of the present invention4
Cladding CaO nucleocapsid structure sulfur calcium expansive clinker need not add aluminum source, not only eliminate raw material,
Reduce cost, simplify technological process, and the extender phase best with prior art can also be reached
Imitative expansion effect.
Claims (10)
1. the preparation method of a cement seif-citing rate expansive clinker, it is characterised in that mainly comprise the following steps:
A) according to CaO, CaSO4Weight ratio be 1:(0.15～0.67), it is provided that the raw material containing CaO and
Containing CaSO4Raw material, obtain mainly containing CaO raw material with containing CaSO4The mixture of raw material；
B) this mixture is interacted under flow forge at 1250 DEG C～1500 DEG C calcinings, preferred mixture
Burn, formed with CaO as core, CaSO4Nucleocapsid structure sulfur calcium expansive clinker for shell.
Method the most according to claim 1, it is characterised in that in step a), CaO, CaSO4
Weight ratio be 1:(0.45～0.55), preferred weight ratio is 1:0.48.
Method the most according to claim 1, it is characterised in that in step b), calcining heat is
1400～1450 DEG C, preferably 1450 DEG C.
Method the most according to claim 1, it is characterised in that in step b), calcination time 20-60
Minute, preferably 30-60 minute.
Method the most according to claim 1, it is characterised in that after step b), also includes cold
But through 30～60 minutes after step c), i.e. calcining kiln discharge, nucleocapsid structure sulfur calcium expansive clinker is cooled to
50～100 DEG C.
Method the most according to claim 5, it is characterised in that after step c), also includes powder
Mill step d), i.e. grinding are more than 180m to described agglomerate ratio surface area2/kg。
7. a cement seif-citing rate expansive clinker, wherein, this cement seif-citing rate expansive clinker is core-shell structure copolymer knot
Structure, with CaO as core, CaSO4For shell.
8. the expansive clinker of claim 7, wherein said expansive clinker includes crystal grain, described crystalline substance
A diameter of 2-20 μm of body granule, described crystal grain is by CaO kernel and CaSO4Shell forms,
Outer casing thickness is 0.1-5 μm.
Expansive clinker the most according to claim 7, wherein CaO kernel and CaSO4Shell is scaled CaO
And SO3After chemical composition be CaO >=80% weight, SO3>=10wt% weight, with extender grog
Total amount 100% weight meter, remaining is inevitable impurity.
Expansive clinker the most according to claim 7, wherein in expansive clinker, the content of CaO is 70-80
Weight %, CaSO4Content be 30-20 weight %, in water, the limited expansion rate of 7 days is
0.141-0.173%, in air, the limited expansion rate of 21 days is 0.05-0.10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510405039.6A CN106316184B (en) | 2015-07-10 | 2015-07-10 | Cement self-stress expansion clinker and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510405039.6A CN106316184B (en) | 2015-07-10 | 2015-07-10 | Cement self-stress expansion clinker and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106316184A true CN106316184A (en) | 2017-01-11 |
| CN106316184B CN106316184B (en) | 2018-08-28 |
Family
ID=57725779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510405039.6A Active CN106316184B (en) | 2015-07-10 | 2015-07-10 | Cement self-stress expansion clinker and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106316184B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018389A (en) * | 2019-12-09 | 2020-04-17 | 嘉华特种水泥股份有限公司 | Expanding agent clinker and production method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10251043A (en) * | 1997-03-10 | 1998-09-22 | Ryoko Sekkai Kogyo Kk | Modified calcium oxide composition and its production |
| CN102503210A (en) * | 2011-11-21 | 2012-06-20 | 天津豹鸣建筑工程材料有限责任公司 | High performance concrete expanding agent |
| CN102838308A (en) * | 2012-09-19 | 2012-12-26 | 重庆三圣特种建材股份有限公司 | Expanded clinker as well as expansion agent and preparation method thereof |
| CN103979816A (en) * | 2014-06-05 | 2014-08-13 | 马清浩 | Concrete expanding agent with triple expansion sources and preparation method of concrete expanding agent |
| CN104671689A (en) * | 2015-02-05 | 2015-06-03 | 江苏苏博特新材料股份有限公司 | Modified calcium oxide expanding clinker as well as preparation method and application thereof |
-
2015
- 2015-07-10 CN CN201510405039.6A patent/CN106316184B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10251043A (en) * | 1997-03-10 | 1998-09-22 | Ryoko Sekkai Kogyo Kk | Modified calcium oxide composition and its production |
| CN102503210A (en) * | 2011-11-21 | 2012-06-20 | 天津豹鸣建筑工程材料有限责任公司 | High performance concrete expanding agent |
| CN102838308A (en) * | 2012-09-19 | 2012-12-26 | 重庆三圣特种建材股份有限公司 | Expanded clinker as well as expansion agent and preparation method thereof |
| CN103979816A (en) * | 2014-06-05 | 2014-08-13 | 马清浩 | Concrete expanding agent with triple expansion sources and preparation method of concrete expanding agent |
| CN104671689A (en) * | 2015-02-05 | 2015-06-03 | 江苏苏博特新材料股份有限公司 | Modified calcium oxide expanding clinker as well as preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018389A (en) * | 2019-12-09 | 2020-04-17 | 嘉华特种水泥股份有限公司 | Expanding agent clinker and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106316184B (en) | 2018-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101917017B1 (en) | Rapid-setting and hardening, high-belite sulfoaluminate cement clinker as well as application and production process thereof | |
| Aïtcin | Portland cement | |
| FI115298B (en) | The cementitious composition | |
| AU2014317429B2 (en) | Calcium sulfoaluminate composite binders | |
| CN101367629B (en) | Manufacture of sulphur aluminate cements with electrolytic manganesium residue and method of manufacturing the same | |
| AU2014317428B2 (en) | Binder comprising calcium sulfoaluminate cement and a magnesium compound | |
| CN102249568B (en) | Low-alkali expansive moderate heat silicate cement and production method thereof | |
| CN101353231A (en) | High-magnesium moderate-heat portland cement and production method thereof | |
| CN103880310A (en) | Portland blast furnace slag cement and preparation method thereof | |
| US10450232B2 (en) | Cement formulation based on aluminium sulphate with a specific proportion of Ye'elimite systems | |
| CN112479609A (en) | All-solid-waste aluminum ferrite cement clinker for prefabricated parts and preparation method thereof | |
| US11111180B2 (en) | Building elements made from binders hardening by combined hydration and carbonation | |
| CN100515974C (en) | Three expansion source concrete anti-cracking agent (CMA) | |
| CN104310812B (en) | green ecological cement and production method thereof | |
| CN109153610A (en) | The blast-furnace cinder base of calcium chloride is added without cement bond material | |
| KR100498760B1 (en) | An expanding agent, a self-stressing cement mixed with an expanding agent, and a method for allowing self-stress to cement | |
| CN106316184A (en) | Cement self-stress expansion clinker and preparation method thereof | |
| CN111943549A (en) | Magnesium oxide composite expanding agent and preparation method thereof | |
| CN103951302A (en) | Multipurpose high-calcium expansion clinker and preparation method thereof | |
| KR101746518B1 (en) | Crack Repair Performance | |
| CN111454036B (en) | Low thermal expansion concrete and admixture | |
| DE102009005610B3 (en) | Process for the preparation of a hydraulic binder | |
| CN110981257A (en) | Alkali-free and chlorine-free concrete accelerator based on magnesium carbonate trihydrate | |
| Na et al. | Application of precast concrete products of non-sintered cement mortar based on industrial by-products | |
| KR20010102815A (en) | An expanding agent, a self-stressing cement mixed with an expanding agent, and a method for allowing self-stress to cement |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |