CN108658485A - A kind of hydraulic cement clinker and preparation method thereof, hydraulic cement and its application - Google Patents
A kind of hydraulic cement clinker and preparation method thereof, hydraulic cement and its application Download PDFInfo
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- CN108658485A CN108658485A CN201810745427.2A CN201810745427A CN108658485A CN 108658485 A CN108658485 A CN 108658485A CN 201810745427 A CN201810745427 A CN 201810745427A CN 108658485 A CN108658485 A CN 108658485A
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- cement
- clinker
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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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/02—Phosphate cements
- C04B12/025—Phosphates of ammonium or of the alkali or alkaline earth metals
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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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
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- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
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- Thermal Sciences (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention provides a kind of hydraulic cement clinkers, with weight, including following mineral constituent：Phosphorus calcium aluminate 30%~95%；Calcium aluminate 1~50%；Calcium phosphate 1~50%；The molecular formula of vitreum 0.1~10%, the phosphorus calcium aluminate is Ca8Al12P2O31.Hydraulic cement clinker provided by the invention, net slurry compression strength can reach 60.1~86.7MPa within 1 day, compression strength can reach 66.9~103.9MPa within 3 days, compression strength can reach 82.1~115.4MPa within 28 days, compression strength can reach 96.9~133.8MPa within 90 days, have the characteristics that early strength height, long-term strength stable development.It is same to have the characteristics that early strength height, long-term strength stable development the present invention also provides a kind of hydraulic cement, it is suitable for load-bearing, reinforcement and the protection of ocean engineering.
Description
Technical field
The present invention relates to building material technical fields more particularly to a kind of hydraulic cement clinker and preparation method thereof and one
Kind hydraulic cement and its application.
Background technology
Developing marine economy needs the cement of anti-seawater corrosion for building ocean engineering and coastal energy infrastructure is built
And if carrying out reinforcement and protection to impaired ocean engineering.
Under marine environment, the chlorion radius in seawater is small, and electronegativity is strong, has higher diffusion and penetrating power, easily
In invading in armored concrete, rebar surface is reached, after running up to a certain concentration, rebar surface passivating film is destroyed, causes
Steel bar corrosion, on the one hand, corrosion product generates expansion, generates stress at concrete-reinforcing bar interface, causes concrete cracking broken
It is bad；On the other hand, steel bar corrosion makes reinforcing bar effective sectional area reduce, and causes reinforcing bar to weaken with grip of concrete, structural bearing
Power declines.Meanwhile cracking causes water and air to enter crack, accelerates the corrosion of reinforcing bar, forms vicious circle.In addition, ocean ring
Border can also cause sulfate attack.It, can be with the hydrogen in Behavior of Hardened Cement Paste after sulfate intrusion portland cement base concrete in seawater
Calcium oxide and drated calcium aluminate reaction generate entringite, and solid volume increases, and causes expansion, cracking, the disintegration of concrete.Cause
This, ocean engineering cement most importantly requires that curing of chloride ion by concrete ability is strong, resistance of chloride ion penetration is high, sulfate resistance
Corrosive nature is good.The prior art mainly adopts slag, flyash etc. that large dosage is added in portland cement improve anti-chlorine from
Sub- penetrating power and Sulfate corrosion resistance energy have that early strength is low although corrosion resistance is improved.
In addition, the reinforced concrete structure in ocean engineering, Service Environment is severe, the works such as is corroded, washes away by seawater
With, cause concrete structure impaired, durability declines, and structure even can not work normally, to the structure progress reinforcement of damage at
For economic and sustainable solution.Portland cement or concrete repairing material curing time are long, strength development
Slowly, the offshore engineering structures such as port facilities need to restore to use as early as possible after impaired, are repaired using conventional concrete, can shadow
The normal use of ocean engineering is rung, and can be by sulphate corrosion.
Invention content
The purpose of the present invention is to provide a kind of hydraulic cement clinker and preparation method thereof and a kind of hydraulic cement and
It is applied, hydraulic cement clinker and hydraulic cement provided by the invention, all has early strength height, long-term strength stablizes hair
Exhibition, curing of chloride ion ability strong, excellent corrosion resistance of chloride ion and Sulfate corrosion resistance energy.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of hydraulic cement clinkers, with weight, including following mineral constituent：
The molecular formula of the phosphorus calcium aluminate is Ca8Al12P2O31。
The present invention provides the preparation methods of the hydraulic cement clinker described in above-mentioned technical proposal, include the following steps：
Calcium oxide, phosphorus pentoxide and alundum (Al2O3) are mixed, mixture is obtained；It is described with weight
Mixture includes calcium oxide 30%~60%, phosphorus pentoxide 10%~35% and alundum (Al2O3) 30%~60%；
The mixture is calcined, hydraulic cement clinker is obtained.
Preferably, the temperature of the calcining is 1500~1650 DEG C, and the time of calcining is 0.5~6.5h.
The present invention also provides a kind of hydraulic cements, including the clinker described in above-mentioned technical proposal or above-mentioned technology
The clinker that preparation method described in scheme is prepared.
Preferably, by weight percentage, the cement includes following components：
Preferably, the gypsum is natural dihydrate gypsum, natural anhydrite, semi-hydrated gypsum, alpha type high-strength gypsum, desulfurization stone
It is one or more in cream, ardealite and fluorgypsum.
Preferably, the cement mixture is granulated blast-furnace slag, flyash, slag, iron tailings sand, lime stone, white clouds
It is one or more in stone sand rock, gangue and SILICA FUME.
Preferably, it is described adjust solidifying group of promoting the strong be divided into lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium sulfate,
Sodium sulphate, potassium sulfate, aluminum sulfate, lithium carbonate, boric acid, borax, sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, sodium metasilicate,
It is one or more in lithium chloride, citric acid, sodium citrate and sodium gluconate.
Preferably, the solidifying component of promoting the strong of the tune includes portland cement, sulphate aluminium cement, Portland clinker, sulphur
It is one or more in aluminate cement clinker, aluminate cement clinker and aluminate cement.
The present invention separately provides cement the answering in ocean engineering load-bearing, reinforcement and protection described in above-mentioned technical proposal
With.
The present invention provides a kind of hydraulic cement clinkers, with weight, including following mineral constituent：Phosphorus aluminium
Sour calcium 30~95%；Calcium aluminate 1~50%；Calcium phosphate 1~50%；Vitreum 0.1~10%；The molecular formula of the phosphorus calcium aluminate
For Ca8Al12P2O31.The hydrated product of clinker of the present invention is generated without calcium hydroxide, and calcium alum will not be generated after sulfate intrusion
Stone, therefore sulfate-resistant corrosion；Hydrated product generates drated calcium aluminate and a large amount of gels, chemosetting and physical solidification chlorion
Ability is strong, and the slurry that hydrated gel is formed is closely knit, and sulfate resistance and chloride permeability ability are excellent.Due in clinker
Phosphorus calcium aluminate and calcium aluminate hydration rate are very fast, and aquation generates a large amount of gels, form the block of interconnection, therefore can be early
Phase intensity provides safeguard；Calcium phosphate hydration rate is slow, and hydrated product hydroxyapatite staggeredly grows, is mutually interspersed, has and improves
The ability of hydration and hardening slurry intensity and toughness, provides safeguard for long-term strength.Embodiment the result shows that, water provided by the invention
Hydraulic cement clinker, 1 day net slurry compression strength can reach 60.1~86.7MPa, and 3 days compression strength can reach 66.9~
103.9MPa, 28 days compression strength can reach 82.1~115.4MPa, and compression strength can reach 96.9~133.8MPa within 90 days, say
Bright hydraulic cement clinker early strength height provided by the invention, long-term strength stable development.
In addition, embodiment result is also shown that hydraulic cement provided by the invention, 1 day compression strength can reach 73~
94MPa, 3 days compression strength can reach 77~108MPa, and 28 days compression strength can reach 94~119MPa, 90 days compression strength
108~139MPa is can reach, illustrating hydraulic cement provided by the invention equally, there is early strength height, long-term strength to stablize hair
The characteristics of exhibition, is suitable for load-bearing, reinforcement and the protection of ocean engineering.
Specific implementation mode
The present invention provides a kind of hydraulic cement clinkers, with weight, including following mineral constituent：
The molecular formula of the phosphorus calcium aluminate is Ca8Al12P2O31。
Hydraulic cement clinker provided by the invention includes 30~95% phosphorus calcium aluminate mine with weight
Object component, preferably 30~90%, more preferably 40~90%.In the present invention, the molecular formula of the phosphorus calcium aluminate is
Ca8Al12P2O31, preferably phosphorus calcium aluminate crystal.Hydration rate is fast at normal temperatures for phosphorus calcium aluminate of the present invention, is the hydraulic
The early strength of property clinker provides safeguard.
In the present invention, with weight, hydraulic cement clinker provided by the invention includes 1~50%
Calcium aluminate mineral component, preferably 3~45%.In the present invention, the calcium aluminate is by monocalcium aluminate (CaAl2O4), two aluminic acids one
Calcium (CaAl4O7), tricalcium aluminate (Ca3Al2O6) and C 12 A 7 (Ca12Al14O33) in one or more compositions.At this
In invention, the calcium aluminate is preferably calcium aluminate crystal.Hydration rate is fast at normal temperatures for calcium aluminate of the present invention, with aforementioned phosphorus
Calcium aluminate collective effect is that the early strength of the hydraulic cement clinker provides safeguard.
In the present invention, with weight, hydraulic cement clinker provided by the invention includes 1~50%
Calcium phosphate mineral component, preferably 3~45%.In the present invention, the calcium phosphate (Ca3P2O8) it is preferably calcium phosphate crystal.
Calcium phosphate water at normal temperature speed of the present invention is slow, and final hydrated product is staggeredly grown, mutually interspersed, high-strength with providing
The ability of the excellent mechanical property such as degree, high tenacity provides safeguard for the long-term strength of clinker.
In the present invention, with weight, hydraulic cement clinker provided by the invention includes 0.1~10%
Vitreous mineral component, preferably 1~8%.Vitreum of the present invention participates in early hydration reaction, with phosphorus of the present invention
Calcium aluminate and the calcium aluminate collective effect participate in providing early strength.
Chemically on composition, hydraulic cement clinker provided by the invention, with weight, including：Calcium oxide
30~60%；Phosphorus pentoxide 10~35%；Alundum (Al2O3) 30~60%, preferably calcium oxide 37~45%；Five oxidations two
Phosphorus 10~20%；Alundum (Al2O3) 35~52%.
The present invention provides the preparation methods of hydraulic cement clinker described in above-mentioned technical proposal, include the following steps：
Calcium oxide, phosphorus pentoxide and alundum (Al2O3) are mixed, mixture is obtained；It is described with weight
Mixture includes calcium oxide 30%~60%, phosphorus pentoxide 10%~35% and alundum (Al2O3) 30%~60%；
The mixture is calcined, hydraulic cement clinker is obtained.
The present invention mixes calcium oxide, phosphorus pentoxide and alundum (Al2O3), obtains mixture.In the present invention, with weight
Percentage composition meter is measured, the mixture includes calcium oxide 30%~60%, phosphorus pentoxide 10%~35% and alundum (Al2O3)
30%~60%.The present invention using above-mentioned percentage composition mixture be above-mentioned mineral composition in order to obtain hydraulic cement it is ripe
Material.The present invention does not have particular/special requirement to the mode of the mixing, can be mixed each component using well known to those skilled in the art
Close uniform mode.The present invention does not have particular/special requirement to the source of the calcium oxide, phosphorus pentoxide and alundum (Al2O3),
It is specific as commercially available using the calcium oxide, phosphorus pentoxide and alundum (Al2O3) in source known to those skilled in the art
Calcium oxide, phosphorus pentoxide and alundum (Al2O3), or calcium oxide, phosphorus pentoxide and three oxygen are prepared by chemical method
Change two aluminium.
In an embodiment of the present invention, calcium source, silicon source and phosphorus source are dissolved in water by the present invention, and evaporation forms gel, and heating is dry
It is dry to obtain the mixture of calcium oxide, phosphorus pentoxide and alundum (Al2O3).In the present invention, the calcium source, silicon source and phosphorus source
Dosage is determined according to the dosage of calcium oxide, phosphorus pentoxide and alundum (Al2O3) in aforementioned mixture.The present invention is to the water
Dosage does not have particular/special requirement, can all dissolve the calcium source, silicon source and phosphorus source.In the present invention, the calcium source is excellent
It is selected as four water-calcium nitrate, source of aluminium is preferably nine water aluminum nitrates, and phosphorus source is preferably phosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphoric acid
One kind in ammonium dihydrogen and diammonium hydrogen phosphate；The temperature of evaporation of the present invention be 60~95 DEG C, preferably 65~90 DEG C, more
Preferably 85 DEG C；The temperature of the heating is 600~1050 DEG C, preferably 750~950 DEG C；The time of the heating be 0.5~
7 hours, preferably 1.5~3 hours；The present invention does not have particular/special requirement to the embodiment of the heating and evaporation, using ability
Heating and evaporation mode known to field technique personnel.
In an embodiment of the present invention, the present invention is further preferably aoxidized by directly heating calcium source, silicon source and phosphorus source
The mixture of calcium, phosphorus pentoxide and alundum (Al2O3)；In the present invention, the calcium source is preferably calcium carbonate or calcium hydroxide,
Source of aluminium is preferably aluminium hydroxide, and phosphorus source is preferably ammonium dihydrogen phosphate or diammonium hydrogen phosphate；The temperature of the heating is excellent
It is selected as 600~1000 DEG C, more preferably 700~900 DEG C；The time of the heating is preferably 2~4 hours, and more preferably 3 is small
When；The present invention does not have particular/special requirement to the mode of the heating, using mode of heating well known to those skilled in the art.
After obtaining mixture, the present invention calcines the mixture, obtains hydraulic cement clinker.In the present invention, described
The temperature of calcining is preferably reached by the way of heating；The initial temperature of the heating is preferably room temperature；The rate of the heating
Preferably 5~25 DEG C/min, further preferably 10~20 DEG C/min.The temperature of the calcining is preferably 1500~1650 DEG C,
Further preferably 1500~1600 DEG C；The time of the calcining is preferably 0.5~6.5h, further preferably 1~5h, more excellent
It is selected as 2~3h；In terms of soaking time of the time of the calcining after the temperature for reaching calcining.Atmosphere of the present invention to the calcining
There is no particular/special requirement, preferably without using any protective atmosphere.The present invention is in the calcination process, calcium oxide, five oxidations two
Phosphorus and alundum (Al2O3) occur high temperature solid state reaction and generate phosphorus calcium aluminate, calcium aluminate, calcium phosphate and vitreum.
After obtaining mixture, before calcining the mixture, the present invention preferably further includes being pressed into the mixture
Type.In the present invention, the pressure of the compression moulding is preferably 7~120MPa, further preferably 30~80MPa；The pressure
The thickness that the blank obtained after type is made is preferably 1~50mm, further preferably 5~20mm.The present invention is pressed into described
The shape of type does not have particular/special requirement, can be pressed into any shape, can be specifically cylindrical or cube etc..Institute of the present invention
The density of blank can be improved by stating compression moulding, be conducive to each component preferably heat transfer and reaction when subsequent calcination.
The present invention also provides a kind of hydraulic cements, including the clinker described in above-mentioned technical proposal or above-mentioned technology
The clinker that preparation method described in scheme is prepared.
Cement provided by the invention includes 30~100% clinker by weight percentage, preferably 40~
90%, more preferably 42~85%.
By weight percentage, cement provided by the invention includes 0~20% gypsum, preferably 1~15%, more preferably
It is 1.5~13%.In the present invention, the gypsum is preferably that natural dihydrate gypsum, natural anhydrite, semi-hydrated gypsum, α types are high-strength
It is one or more in gypsum, desulfurated plaster, ardealite and fluorgypsum.The present invention does not have special want to the source of the gypsum
It asks, it is specific such as commercially available gypsum using the gypsum in source known to those skilled in the art.Gypsum of the present invention can be adjusted
The setting time of water-saving mud regulates and controls the early hydration speed of cement.
By weight percentage, cement provided by the invention includes 0~69.9% cement mixture, preferably 1~
55%, more preferably 2~51%.In the present invention, the cement mixture be preferably granulated blast-furnace slag, flyash, slag,
It is one or more in iron tailings sand, lime stone, dolomite sandstone, gangue and SILICA FUME.The present invention is to the cement mixing
The source of material does not have particular/special requirement, specific as commercially available using the cement mixture in source known to those skilled in the art
Cement mixture.Cement mixture of the present invention can reduce the dosage of clinker, and can adjust the anti-of the cement
Chloride Attack and sulphate-corrosion resistance energy.
By weight percentage, cement provided by the invention includes 0~5% solidifying component of promoting the strong of tune, preferably 0.1~
2.5%, more preferably 0.15~2%.In the present invention, the solidifying component of promoting the strong of the tune is preferably lithium hydroxide, sodium hydroxide, hydrogen
Potassium oxide, calcium hydroxide, lithium sulfate, sodium sulphate, potassium sulfate, aluminum sulfate, lithium carbonate, boric acid, borax, sodium carbonate, sodium bicarbonate,
It is one or more in potassium carbonate, saleratus, sodium metasilicate, lithium chloride, citric acid, sodium citrate and sodium gluconate.At this
It is described that solidifying component of promoting the strong is adjusted separately to preferably include portland cement, sulphate aluminium cement, Portland clinker, sulphur aluminium in invention
It is one or more in acid salt cement clinker, aluminate cement clinker and aluminate cement.The present invention adjusts solidifying group of promoting the strong to described
The source divided does not have particular/special requirement, specific such as city using the solidifying component of promoting the strong of the tune in source known to those skilled in the art
The solidifying component of promoting the strong of tune sold.It is of the present invention that solidifying component of promoting the strong is adjusted to have the function of improving the early strength of cement, while can
The setting time for adjusting cement, it can realize that the hydration rate of cement is controllable with aforementioned gypsum mating reaction.
The present invention does not have particular/special requirement to the preparation method of the hydraulic cement, and each component is mixed directly i.e.
It can.The present invention does not have particular/special requirement to the mode of the mixing, can be mixed each component using well known to those skilled in the art
Close uniform mode.
The present invention provides application of the cement described in above-mentioned technical proposal in ocean engineering load-bearing, reinforcement and protection.This
Invention does not have particular/special requirement to the embodiment of the application, using it is well known to those skilled in the art can implement by the way of i.e.
It can.
With reference to embodiment to hydraulic cement clinker provided by the invention and preparation method thereof, hydraulic cement and its
Using being described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
According to the raw material proportioning of table 1, four water-calcium nitrate, nine water aluminum nitrates and phosphoric acid are weighed respectively, are added in deionized water
Mixed solution is formed, mixed solution is heated to 85 DEG C, it is lasting to stir, until forming gel after moisture evaporation；
The gel is placed in corundum crucible, 850 DEG C are heated in resistance furnace, 3 hours is kept the temperature, naturally cools to room
Wen Hou is crushed using pulverizer, crosses 200 mesh molecular sieves, obtains the forerunner of calcium oxide, phosphorus pentoxide and alundum (Al2O3) composition
Body；
Using mold under 100MPa pressure, predecessor is pressed into the cylindrical blank of thickness 10mm, diameter 40mm；
The cylindrical blank is placed in resistance furnace, furnace temperature is risen to 1537 DEG C from room temperature with the heating rate of 16 DEG C/min,
Heat preservation 2 hours, the cylindrical blank after calcining is quickly removed, is cooled to room temperature, cementitious material clinker is obtained, by the chamotte powder
It is broken, and 200 mesh analysis sieve is crossed, obtain hydraulic cement clinker.
Embodiment 2~5
Hydraulic cement clinker is prepared according to the method for embodiment 1, raw materials used and calcination temperature is shown in Table 1.
Raw material proportioning and calcination temperature value in 1 Examples 1 to 5 of table
Embodiment 6
According to the raw material proportioning of table 2, calcium carbonate, aluminium hydroxide and diammonium hydrogen phosphate powder are weighed respectively, by the carbonic acid
Calcium, aluminium hydroxide and calcium monohydrogen phosphate are uniformly mixed and form mixture；
The mixture is placed in corundum crucible, 900 DEG C are heated in resistance furnace, keeps the temperature 3 hours, is used after cooling
Pulverizer crushes, and crosses 200 mesh molecular sieves, obtains the presoma of calcium oxide, phosphorus pentoxide and alundum (Al2O3) composition；
Using mold under 80MPa pressure, predecessor is pressed into the cylindrical blank of thickness 10mm, diameter 40mm；
The cylindrical blank is placed in resistance furnace, furnace temperature is risen to 1542 DEG C from room temperature with the heating rate of 18 DEG C/min,
Heat preservation 2 hours, the cylindrical blank after calcining is quickly removed, is cooled to room temperature, cementitious material clinker is obtained, by the chamotte powder
It is broken, and 200 mesh analysis sieve is crossed, obtain hydraulic cement clinker.
Embodiment 7~10
Hydraulic cement clinker is prepared according to the method for embodiment 6, raw materials used and calcination temperature is shown in Table 2.
Raw material proportioning and calcination temperature value in 2 embodiment 7~10 of table
Embodiment 11
According to the raw material proportioning of table 3, lime powder, alundum (Al2O3) powder and phosphorus pentoxide powder are weighed respectively,
It is uniformly mixed to form mixture；
Using mold under 70MPa pressure, the mixture is pressed into the cylindrical blank of thickness 10mm, diameter 40mm；
The cylindrical blank is placed in resistance furnace, furnace temperature is risen to 1546 DEG C from room temperature with the heating rate of 20 DEG C/min,
Heat preservation 2 hours, the cylindrical blank after calcining is quickly removed, is cooled to room temperature, cementitious material clinker is obtained, by the chamotte powder
It is broken, and 200 mesh analysis sieve is crossed, obtain hydraulic cement clinker.
Embodiment 12~15
Hydraulic cement clinker is prepared according to the method for embodiment 11, raw materials used and calcination temperature is shown in Table 3.
Raw material proportioning and calcination temperature value in 3 embodiment 11~15 of table
1~15 gained clinker of embodiment is analyzed respectively using X-ray diffraction quantitative analysis method, mine is calculated
Object ingredient and chemical composition are shown in Table 4.
The mineralogical composition and chemical composition of 4 embodiment of table, 1~15 gained clinker
The hydraulic cement clinker that embodiment 1~15 obtains is tested for the property respectively, according to GB/T 1346-2011
《Cement normal consistency water consumption, setting time, the stability method of inspection》Setting time is tested, compression strength is net slurry
Compression strength, compression area are 10mm × 10mm, height 10mm, the ratio of mud 0.33.Test result is shown in Table 5.
The performance for the hydraulic cement clinker that 5 embodiment 1~15 of table obtains
In addition, as a comparison, the present invention also carries out the net slurry intensity of the portland cement PII42.5R of identical size
Test, 1 day compression strength are 23.1MPa, and 3 days compression strength is 29.7MPa, and 28 days compression strength are 71.5MPa.
As can be seen from Table 5,1 day net slurry compression strength of hydraulic cement clinker provided by the invention can reach 60.1~
86.7MPa, 3 days compression strength can reach 66.9~103.9MPa, and 28 days compression strength can reach 82.1~115.4MPa, 90 days
Compression strength can reach 96.9~133.8MPa, illustrate that hydraulic cement clinker early strength provided by the invention is high, long-term strong
The characteristics of spending stable development.
In addition, as can also be seen from Table 5, presetting period of hydraulic cement clinker provided by the invention 170~
245min is adjustable, and final setting time is adjustable in 230~375min.
Embodiment 16~25 be using the hydraulic cement clinker provided in embodiment 1, with the gypsum of different proportion ingredient,
Cement mixture and/or the hydraulic cement for adjusting solidifying component preparation of promoting the strong, concrete composition are shown in Table 6.
The proportioning of each raw material in 6 embodiment 16~20 of table
The cement obtained respectively to embodiment 16~25 is tested for the property, according to GB/T 1346-2011《Cement standard
Consistency water consumption, setting time, the stability method of inspection》Setting time is tested, compression strength be net slurry compression strength,
Compression area is 10mm × 10mm, height 10mm, the ratio of mud 0.33.Test result is shown in Table 7.
The physical property and mechanical property of the cement of 7 embodiment 16~25 of table
As can be seen from Table 7, hydraulic cement provided by the invention, 1 day compression strength can reach 73~94MPa, 3 days
Compression strength can reach 77~108MPa, and 28 days compression strength can reach 94~119MPa, and compression strength can reach 108 within 90 days
~139MPa, illustrating hydraulic cement provided by the invention equally has the characteristics that early strength height, long-term strength stable development.
In addition, as can also be seen from Table 7, the hydraulic cement presetting period provided by the invention can in 100~250min
It adjusts, final setting time is adjustable in 160~370min.
As seen from the above embodiment, the present invention provides a kind of hydraulic cement clinkers, with weight, including
Following mineral constituent：Phosphorus calcium aluminate 30%~95%；Calcium aluminate 1~50%；Calcium phosphate 1~50%；Vitreum 0.1~10%.
Hydraulic cement clinker provided by the invention, 1 day net slurry compression strength can reach 60.1~86.7MPa, and compression strength is reachable within 3 days
To 66.9~103.9MPa, 28 days compression strength can reach 82.1~115.4MPa, and 90 days compression strength can reach 96.9~
133.8MPa illustrates that hydraulic cement clinker early strength provided by the invention is high, long-term strength stable development.
The present invention also provides a kind of hydraulic cement, 1 day compression strength can reach 73~94MPa, 3 days compression strength
77~108MPa is can reach, 28 days compression strength can reach 94~119MPa, and compression strength can reach 108~139MPa within 90 days,
Illustrating hydraulic cement provided by the invention equally has the characteristics that early strength height, long-term strength stable development.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of hydraulic cement clinker, with weight, including following mineral constituent：
The molecular formula of the phosphorus calcium aluminate is Ca8Al12P2O31。
2. the preparation method of hydraulic cement clinker described in claim 1, includes the following steps：
Calcium oxide, phosphorus pentoxide and alundum (Al2O3) are mixed, mixture is obtained；With weight, the mixing
Object includes calcium oxide 30%~60%, phosphorus pentoxide 10%~35% and alundum (Al2O3) 30%~60%；
The mixture is calcined, hydraulic cement clinker is obtained.
3. preparation method according to claim 2, which is characterized in that the temperature of the calcining is 1500~1650 DEG C, is forged
The time of burning is 0.5~6.5h.
4. a kind of hydraulic cement, including being made described in clinker described in claim 1 or claim 2~3 any one
The clinker that Preparation Method is prepared.
5. cement according to claim 4, which is characterized in that by weight percentage, the cement includes following components：
6. cement according to claim 5, which is characterized in that the gypsum is natural dihydrate gypsum, natural anhydrite, half
It is one or more in water gypsum, alpha type high-strength gypsum, desulfurated plaster, ardealite and fluorgypsum.
7. cement according to claim 5, which is characterized in that the cement mixture be granulated blast-furnace slag, flyash,
It is one or more in slag, iron tailings sand, lime stone, dolomite sandstone, gangue and SILICA FUME.
8. cement according to claim 5, which is characterized in that it is described adjust solidifying group of promoting the strong be divided into lithium hydroxide, sodium hydroxide,
Potassium hydroxide, calcium hydroxide, lithium sulfate, sodium sulphate, potassium sulfate, aluminum sulfate, lithium carbonate, boric acid, borax, sodium carbonate, bicarbonate
It is one or more in sodium, potassium carbonate, saleratus, sodium metasilicate, lithium chloride, citric acid, sodium citrate and sodium gluconate.
9. the cement according to claim 5 or 8, which is characterized in that the solidifying component of promoting the strong of tune includes portland cement, sulphur
One kind in aluminate cement, Portland clinker, sulphoaluminate cement clinker, aluminate cement clinker and aluminate cement
Or it is a variety of.
10. application of the cement in ocean engineering load-bearing, reinforcement and protection described in claim 5~9 any one.
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| CN109608069A (en) * | 2018-12-29 | 2019-04-12 | 山东永正水泥有限公司 | 42.5 grades of slow setting cement of one kind and its preparation method and application |
| CN109608069B (en) * | 2018-12-29 | 2020-07-17 | 山东永正水泥有限公司 | 42.5-grade retarding cement and preparation method and application thereof |
| CN110372240A (en) * | 2019-06-13 | 2019-10-25 | 湖南科技大学 | A kind of room temperature conserves the preparation and application of cheap alkali-excited cement |
| CN110451827A (en) * | 2019-06-13 | 2019-11-15 | 湖南科技大学 | A kind of preparation and application of steam-cured alkali-excited cement |
| CN110451827B (en) * | 2019-06-13 | 2020-12-11 | 湖南湘楚先路环保科技有限责任公司 | Preparation and use method of steam-cured alkali-activated cement |
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| CN111233417A (en) * | 2020-02-29 | 2020-06-05 | 北京古运混凝土有限公司 | Preparation process of high-strength concrete |
| CN112010618A (en) * | 2020-09-03 | 2020-12-01 | 安徽理工大学 | Plastering mortar using waste gypsum as cementing material and preparation method thereof |
| CN113264699A (en) * | 2021-04-14 | 2021-08-17 | 济南大学 | Q/P phase cement clinker containing calcium aluminate |
| CN115710095A (en) * | 2022-12-13 | 2023-02-24 | 中国建筑材料科学研究总院有限公司 | Boron-phosphorus composite modified high belite sulphoaluminate cement clinker and preparation method thereof |
| CN115710095B (en) * | 2022-12-13 | 2024-05-24 | 中国建筑材料科学研究总院有限公司 | Boron-phosphorus composite modified high belite sulphoaluminate cement clinker and preparation method thereof |
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