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CN109987900A - One kind is with building waste cementitious material as main component and preparation method thereof - Google Patents

One kind is with building waste cementitious material as main component and preparation method thereof Download PDF

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Publication number
CN109987900A
CN109987900A CN201910329593.9A CN201910329593A CN109987900A CN 109987900 A CN109987900 A CN 109987900A CN 201910329593 A CN201910329593 A CN 201910329593A CN 109987900 A CN109987900 A CN 109987900A
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CN
China
Prior art keywords
cementitious material
micro mist
building waste
cement
main component
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.)
Pending
Application number
CN201910329593.9A
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Chinese (zh)
Inventor
吴超凡
万署
张继森
孟凡威
李泉
黄倩
李行
周艺
温广香
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Yunzhong Regeneration Technology Co Ltd
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Hunan Yunzhong Regeneration Technology Co Ltd
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Publication date
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Priority to CN201910329593.9A priority Critical patent/CN109987900A/en
Publication of CN109987900A publication Critical patent/CN109987900A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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

Abstract

The invention discloses one kind with building waste cementitious material as main component and preparation method thereof, the material includes that brick mixes micro mist, concrete micro mist, slag micropowder, cement and sodium hydroxide, the additive combination of waterglass or one of calcium chloride and the additive combination of calcium hydroxide.Cementitious material setting time of the present invention all meets related cement standard to volume stability, and 3 days and 28 days compression strength, flexural strength reach PC32.5 rank intensity.Compared with using conventional cement, there is obvious price advantage, and large-scale application can alleviate the pressure that building waste generates urban environment significantly, social benefit is much larger than economic benefit.

Description

One kind is with building waste cementitious material as main component and preparation method thereof
Technical field
Technical field is utilized the present invention relates to construction refuse regenerated, and in particular to a kind of as main component with building waste Cementitious material and preparation method thereof.
Background technique
According to statistics, China generates about 2,600,000,000 tons of building waste every year, and the year two thousand twenty is up to peak value, and construction refuse regenerated benefit It is not achieved 10% with rate, and the U.S., Japan, South Korea, Germany etc. are dealt into national building waste utilization rate and already exceed 90%.At present China handles building waste mainly based on landfill and air storage, serious harm public environment and its people's safety, and stacks and build Building refuse needs a large amount of soils, greatly restricts the sustainable development in city.As national environmental consciousness gradually increases, rivers and lakes river Sand is largely forced to shut down with natural stone ore, and market sandstone supplies the recycling benefit that building waste how is improved by being becoming tight With rate, solves the problems, such as to be brought by building waste to urban environment and be taken seriously extensively.Building waste is considered as misplacing position The resource set improves the research and development that construction refuse resource utilization rate key is reconstituted product and technology.
Currently, bulk solid waste is mainly crushed by construction refuse resource using method, and then pass through water The impurity such as the processes removal such as choosing, magnetic separation, comprehensive sorting sawdust, plastics, produce recycled aggregate and are used to prepare brick, wall, concrete With road foundation, bed course and base material etc..Due to China's building waste complicated component, the reconstituted product quality of production is difficult to To guarantee, thus reconstituted product popularization is more difficult.Building waste is constituted based on concrete block and brick, and concrete block and brick are broken After broken, the particle of 0~4.75mm partial size accounts for major part, this some materials is very difficult to utilize in engineering construction.In addition, China's cement output in 2017 is 23.2 hundred million tons, occupies the first in the world.Since a large amount of dioxy can be generated in cement production process Change carbon and other harmful substances, seriously threatens China's environment, moreover cement price continuous rise in recent years, engineering cost sharply increase Add.
In the prior art to reuse building waste, attempted to be used for preparation cementitious material, but it is being prepared During cementitious material, needing through high-temperature activation etc., activation process is long, and preparation method is complicated, and it is at high cost, and can not have Effect utilizes the building waste of 0~4.75mm partial size.
Summary of the invention
0~4.75mm partial size utilization rate is low after the present invention is directed to construction waste crushing, existing to prepare glue using building waste The method of gel material is complicated, the statuses such as higher cost, and cement consumption is excessive in combination China's building trade, causes engineering cost The problems such as excessively high, provides one kind with building waste cementitious material as main component, and preparation process is simple, at low cost.
Technical solution proposed by the present invention is to provide one kind with building waste cementitious material as main component, the material Micro mist, concrete micro mist, slag micropowder, cement and sodium hydroxide, the additive combination of waterglass or calcium chloride are mixed including brick It one of is combined with the additive of calcium hydroxide;Wherein, in terms of mass parts:
Brick mixes 20~40 parts of micro mist
20~40 parts of concrete micro mist
10~30 parts of slag micropowder
5~10 parts of cement
1~2 part of sodium hydroxide
2~4 parts of waterglass
2~4 parts of calcium chloride
0~2 part of calcium hydroxide
In above-mentioned cementitious material, it is that brick in building waste, mortar block and concrete block mixing are broken that the brick, which mixes micro mist, Afterwards, 0~4.75mm particles are chosen to be formed after ball milling, after concrete micro mist is crushed for concrete block in building waste, choosing 0~4.75mm particles are taken to be formed after ball milling, slag micropowder is blast furnace ironmaking slag gained, micro mist after levigate Specific surface area is both greater than 300m2/kg。
In the present invention, the raw material in cementitious material are carried out following preferred:
In above-mentioned cementitious material, the slag micropowder for Lianyuan of Hunan steel plant blast furnace ironmaking slag after levigate institute , specific surface area is greater than 300m2/kg。
The cement is preferably PC32.5 cement, and specific surface area is greater than 300m2/kg。
In above-mentioned cementitious material, sodium hydroxide is technical grade piece alkali, and purity is up to 98% or more.
Waterglass is liquid, and mass fraction is 30%~35%, and modulus of water glass is 2.9~3.1.
Calcium chloride and calcium hydroxide are powdered, and purity is up to 99% or more.
The above-mentioned preparation method with building waste cementitious material as main component, when additive group be combined into sodium hydroxide and It when waterglass, will first be added in micro mist after sodium hydroxide and sodium silicate dissolving, form cementitious material;When additive group is combined into chlorine When changing calcium and calcium hydroxide, additive and micro mist mixing and water adding are formed into cementitious material.
Beneficial effects of the present invention:
1, cementitious material of the invention only need all raw material be sufficiently mixed in certain period of time can be formed it is cementing Effect, simple process are not necessarily to other additional conditions.
The present inventor passes through a large amount of experimental exploring, dexterously devises formula for raw stock combination of the invention, And by the synergistic effect of each component, be obtained through combination good effect, specific synergistic effect is embodied in: levigate is mixed The calcium hydroxide that solidifying soil micro mist contains a certain amount of unhydrated cement, and generates in system containing aquation, therefore concrete micro mist Can occur hydration reaction, and provide for system excite other species activity ingredients needed for basic ion.Brick mixes in micro mist containing big Brick ground-slag is measured, brick ground-slag has pozzolanic activity, and hydration reaction occurs in alkaline environment, generates hydratable silicate gelation system, mentions The cementing power of high system, but since brick slag micro mist activity is low, hydration reaction is slow, to improve intensity cementitious material early period, institute Need to add a certain amount of high activity slag micropowder and cement, cement can improve system early strength, while it is anti-that aquation occurs Ying Houneng provides more basic ions for system.Chemical addition agent main function is that enough basic ions are provided for system, and brick is mixed Micro mist and slag micropowder can generate more silicate gels, in addition chlorine under sodium hydroxide and the common shooting condition of waterglass Changing calcium has dilatancy in the calcium salt that excitation pozzolanic activity substance generates simultaneously, can fill system hole, increase system intensity.
The acquisition of these synergies is that inventor gropes through a large number of experiments, is just obtained by trial and error repeatedly.
2, the present invention has obvious price excellent with building waste cementitious material as main component compared with conventional cement Gesture;It offers according to existing market, cement is greater than 500 yuan/ton, and brick mixes the cost of raw material of micro mist and concrete micro mist and is processed into This is altogether less than 80 yuan/ton, and 350 yuan/ton of slag micropowder, about 3000 yuan/ton of all kinds of chemical addition agents, therefore glue of the invention Gel material cost compares ordinary cement save the cost 50% less than 250 yuan/ton.It is noted that application of the invention can delay The pressure that solution building waste generates urban environment, social benefit are much larger than economic benefit.
3, cementitious material setting time of the present invention and volume stability all meet related cement standard, and 3 days and 28 Its compression strength, flexural strength reach PC32.5 rank intensity, have the function of substituting cement completely in engineering construction.
Specific embodiment
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention Protection scope.
Embodiment 1:
One kind is with building waste cementitious material as main component, and the cementitious material is mainly by the component of following mass fraction Mixing composition:
Brick mixes 40 parts of micro mist
30 parts of concrete micro mist
14 parts of slag micropowder
10 parts of cement
2 parts of sodium hydroxide
4 parts of waterglass
In above-mentioned cementitious material, brick mixes micro mist and concrete micro mist to take 0~4.75mm partial size after construction waste crushing Particle carries out ball milling, and micro mist specific surface area is greater than 300m after ball milling2/kg;Slag micropowder is that blast furnace practices the levigate gained of Iron-ore Slag;Brick Mixed micro mist, concrete micro mist, slag and cement should all be dried sufficiently.
Index of correlation test will be carried out to above-mentioned cementitious material below:
1, the condensation referring to JTG E30-2005 " highway engineering cement and cement concrete testing regulations " to cementitious material Time and volume stability are tested, and during specimen molding, are first put into chemical addition agent sodium hydroxide and waterglass In 100~120g water of pre-add, configured solution is poured into micro mist mixture and is sufficiently stirred, then continues to add water to glue Gel material reaches normal consistency, finally die-filling to be tested, test result are as follows: pre-hardening 216min, final set 403min, volume are stable Property it is qualified, fully meet the standard that jelling time is not more than 600min not less than 45min, final setting time;
2, referring again to JTG E30-2005 " highway engineering cement and cement concrete testing regulations " to cementitious material Resistance to compression, flexural strength are tested, and every group of test specimen watering quantity is water consumption when Mortar'S Flowability reaches 180mm ± 5mm, first will Chemical addition agent sodium hydroxide and waterglass are put into 100~120g water of pre-add, and configured solution is poured into mortar and is filled Divide stirring, then remaining water is added in mortar and be sufficiently stirred, last die-filling, rear test specimen, which demoulds, for 24 hours is conserved, when test specimen reaches It is tested after to certain age.Test result are as follows: 3d, 28d compression strength are respectively 22.5MPa, 38.4MPa, and 3d, 28d are anti- Folding intensity is respectively 4.1MPa, 6.5MPa, and PC32.5 strength of cement standard requirements are as follows: 3d, 28d compression strength is respectively 11MPa, 32.5MPa, 3d, 28d flexural strength are respectively 2.5MPa, 5.5MPa, and above-mentioned cementitious material intensity clearly fulfils PC32.5 strength of cement standard.
Embodiment 2:
One kind is with building waste cementitious material as main component, and the cementitious material is mainly by the component of following mass fraction Mixing composition:
Brick mixes 25 parts of micro mist
40 parts of concrete micro mist
25 parts of slag micropowder
7 parts of cement
1 part of sodium hydroxide
2 parts of waterglass
In above-mentioned cementitious material, brick mixes micro mist and concrete micro mist to take 0~4.75mm partial size after construction waste crushing Particle carries out ball milling, and micro mist specific surface area is greater than 300m after ball milling2/kg;Slag micropowder is that blast furnace practices the levigate gained of Iron-ore Slag;Brick Mixed micro mist, concrete micro mist, slag and cement should all be dried sufficiently.
Index of correlation test will be carried out to above-mentioned cementitious material below:
Relevant test method is same as Example 1, test result are as follows: pre-hardening 255min, final set 463min, volume stability Qualification fully meets cement standard requirement;3d, 28d compression strength are respectively 19.1MPa, 34.6MPa, 3d, 28d flexural strength Respectively 3.2MPa, 5.9MPa, above-mentioned cementitious material intensity equally meet PC32.5 strength of cement standard.
Embodiment 3:
One kind is with building waste cementitious material as main component, and the cementitious material is mainly by the component of following mass fraction Mixing composition:
Brick mixes 30 parts of micro mist
30 parts of concrete micro mist
24 parts of slag micropowder
10 parts of cement
2 parts of calcium hydroxide
4 parts of calcium chloride
In above-mentioned cementitious material, brick mixes micro mist and concrete micro mist to take 0~4.75mm partial size after construction waste crushing Particle carries out ball milling, and micro mist specific surface area is greater than 300m after ball milling2/kg;Slag micropowder is that blast furnace practices the levigate gained of Iron-ore Slag;Brick Mixed micro mist, concrete micro mist, slag and cement should all be dried sufficiently.
Index of correlation test will be carried out to above-mentioned cementitious material below:
1, the condensation referring to JTG E30-2005 " highway engineering cement and cement concrete testing regulations " to cementitious material Time and volume stability are tested, and during specimen molding, agitated kettle is added in cementitious material all raw material component In be stirred, then add water to cementitious material and reach normal consistency, it is last it is die-filling tested, test result are as follows: initial set 291min, final set 478min, volume stability are qualified, equally meet cement standard requirement;
2, referring again to JTG E30-2005 " highway engineering cement and cement concrete testing regulations " to cementitious material Resistance to compression, flexural strength are tested, and every group of test specimen watering quantity is water consumption when Mortar'S Flowability reaches 180mm ± 5mm, by glue All raw material component is put into agitated kettle together in gel material, and Jia Shui plus normal sand are sufficiently stirred, and the mortar being stirred is filled Mould, rear test specimen demoulding is conserved for 24 hours, is tested after test specimen reaches certain age.Test result are as follows: 3d, 28d resistance to compression Intensity is respectively 21.2MPa, 39.7MPa, and 3d, 28d flexural strength are respectively 3.9MPa, 6.6MPa, and it is strong to meet PC32.5 cement Scale is quasi-.
Embodiment 4:
One kind is with building waste cementitious material as main component, and the cementitious material is mainly by the component of following mass fraction Mixing composition:
Brick mixes 20 parts of micro mist
40 parts of concrete micro mist
26 parts of slag micropowder
10 parts of cement
4 parts of calcium chloride
In above-mentioned cementitious material, brick mixes micro mist and concrete micro mist to take 0~4.75mm partial size after construction waste crushing Particle carries out ball milling, and micro mist specific surface area is greater than 300m after ball milling2/kg;Slag micropowder is that blast furnace practices the levigate gained of Iron-ore Slag;Brick Mixed micro mist, concrete micro mist, slag and cement should all be dried sufficiently.
Index of correlation test will be carried out to above-mentioned cementitious material below:
Relevant test method is same as Example 3, test result are as follows: pre-hardening 314min, final set 525min, volume stability Qualification fully meets requirement of the cement products to cement setting time;3d, 28d compression strength be respectively 20.4MPa, 36.1MPa, 3d, 28d flexural strength are respectively 2.7MPa, 6.0MPa, and above-mentioned cementitious material intensity equally meets PC32.5 cement Strength criterion.
Comparative example 1
For convenient for comparing invention effect, for embodiment 1, this comparative example changes cement and brick mixes micro mist volume.Be gelled material Material is mainly made of the component mixing of following mass fraction:
Brick mixes 50 parts of micro mist
30 parts of concrete micro mist
14 parts of slag micropowder
2 parts of sodium hydroxide
4 parts of waterglass
In above-mentioned cementitious material, brick mixes micro mist and concrete micro mist to take 0~4.75mm partial size after construction waste crushing Particle carries out ball milling, and micro mist specific surface area is greater than 300m after ball milling2/kg;Slag micropowder is that blast furnace practices the levigate gained of Iron-ore Slag;Brick Mixed micro mist, concrete micro mist and slag should all be dried sufficiently.
Index of correlation test will be carried out to above-mentioned cementitious material below:
Relevant test method is same as Example 1, test result are as follows: pre-hardening 685min, final set 1086min, volume are stable Property it is qualified, fully meet cement standard requirement;3d, 28d compression strength are respectively 6.3MPa, 18.4MPa, 3d, 28d flexural strength Respectively 1.2MPa, 3.3MPa, above-mentioned cementitious material intensity are unsatisfactory for PC32.5 strength of cement standard.
Comparative example 2
For convenient for comparing invention effect, for embodiment 3, this comparative example brick mixes micro mist and concrete micro mist specific surface area is small In 300m2/kg.Cementitious material is mainly made of the component mixing of following mass fraction:
Brick mixes 30 parts of micro mist
30 parts of concrete micro mist
Slag micropowder 24
10 parts of cement
2 parts of calcium hydroxide
4 parts of calcium chloride
In above-mentioned cementitious material, brick mixes micro mist and concrete micro mist to take 0~4.75mm partial size after construction waste crushing Particle carries out ball milling, and micro mist specific surface area is respectively 210m after ball milling2/ kg and 232m2/kg;Slag micropowder is that blast furnace practices Iron-ore Slag Levigate gained;Brick mixes micro mist, concrete micro mist, slag and cement and should all sufficiently dry.
Index of correlation test will be carried out to above-mentioned cementitious material below:
Relevant test method is same as Example 3, test result are as follows: pre-hardening 579min, final set 893min, volume stability Qualification fully meets requirement of the cement products to cement setting time;3d, 28d compression strength are respectively 7.7MPa, 21.5MPa, 3d, 28d flexural strength are respectively 1.6MPa, 3.9MPa, and above-mentioned cementitious material intensity is unsatisfactory for PC32.5 strength of cement standard.

Claims (8)

1. one kind is with building waste cementitious material as main component, which is characterized in that the material includes that brick mixes micro mist, concrete Micro mist, slag micropowder, cement and sodium hydroxide, the additive combination of waterglass or the additive of calcium chloride and calcium hydroxide One of combination;Wherein, in terms of mass parts:
Brick mixes 20~40 parts of micro mist
20~40 parts of concrete micro mist
10~30 parts of slag micropowder
5~10 parts of cement
1~2 part of sodium hydroxide
2~4 parts of waterglass
2~4 parts of calcium chloride
0~2 part of calcium hydroxide
In above-mentioned cementitious material, it is choosing after brick in building waste, mortar block and concrete block mixing are crushed that the brick, which mixes micro mist, 0~4.75mm particles are taken to be formed after ball milling, after concrete micro mist is crushed for concrete block in building waste, selection 0~ 4.75mm particles are formed after ball milling, and slag micropowder is blast furnace ironmaking slag gained, micro mist specific surface after levigate Product is both greater than 300m2/kg。
2. according to claim 1 with building waste cementitious material as main component, which is characterized in that the slag is micro- Powder be Lianyuan of Hunan steel plant blast furnace ironmaking slag after levigate gained.
3. according to claim 1 or 2 with building waste cementitious material as main component, which is characterized in that the water Mud is PC32.5 cement.
4. according to claim 1 with building waste cementitious material as main component, which is characterized in that the hydroxide Sodium is technical grade piece alkali, and purity is 98% or more.
5. according to claim 1 with building waste cementitious material as main component, which is characterized in that the waterglass For liquid, mass fraction is 30%~35%.
6. according to claim 1 or 5 with building waste cementitious material as main component, which is characterized in that the water Glass modulus is 2.9~3.1.
7. according to claim 1 with building waste cementitious material as main component, which is characterized in that calcium chloride and hydrogen Calcium oxide is powdered, and purity is 99% or more.
8. the described in any item preparation methods with building waste cementitious material as main component of claim 1-7, feature It is, when additive group is combined into sodium hydroxide and waterglass, will be first added in micro mist after sodium hydroxide and sodium silicate dissolving, Form cementitious material;When additive group is combined into calcium chloride and calcium hydroxide, additive and micro mist mixing and water adding are formed and are gelled Material.
CN201910329593.9A 2019-04-23 2019-04-23 One kind is with building waste cementitious material as main component and preparation method thereof Pending CN109987900A (en)

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Cited By (6)

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CN111393057A (en) * 2020-03-12 2020-07-10 佛山市交通科技有限公司 Regeneration method of waste concrete and modified regenerated concrete
CN112390583A (en) * 2020-12-24 2021-02-23 蓝合智能科技研究院(苏州)有限公司 Solid waste cementing material for building 3D printing and preparation method and application thereof
CN112592077A (en) * 2021-01-24 2021-04-02 湖南科技大学 Brick-concrete construction waste slag cold recycling cementitious material and its use method
CN113264700A (en) * 2021-05-25 2021-08-17 深圳市和盛环保科技有限公司 Regenerated cementing material based on subway shield sludge
CN115124318A (en) * 2022-04-22 2022-09-30 广州大学 Preparation method of novel carbonized recycled powder-slag pressed brick
CN115677281A (en) * 2022-11-22 2023-02-03 湖南凯迪工程科技有限公司 A kind of sidewalk brick and preparation method thereof

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CN103319103A (en) * 2013-06-09 2013-09-25 河海大学 Regenerative hardened cement mortar gelling material and preparation method thereof
CN106082927A (en) * 2016-06-17 2016-11-09 南京德滨环保科技有限公司 A kind of alkali-activated slag system geopolymer concrete and preparation method thereof
CN106242327A (en) * 2016-07-21 2016-12-21 武汉源锦商品混凝土有限公司 Regenerated micropowder cement admixture and preparation method thereof

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CN103183483A (en) * 2011-12-27 2013-07-03 上海德滨环保科技有限公司 Environmental-friendly supplementary cementious material and preparation method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111393057A (en) * 2020-03-12 2020-07-10 佛山市交通科技有限公司 Regeneration method of waste concrete and modified regenerated concrete
CN111393057B (en) * 2020-03-12 2021-04-09 佛山市交通科技有限公司 Regeneration method of waste concrete and modified regenerated concrete
CN112390583A (en) * 2020-12-24 2021-02-23 蓝合智能科技研究院(苏州)有限公司 Solid waste cementing material for building 3D printing and preparation method and application thereof
CN112592077A (en) * 2021-01-24 2021-04-02 湖南科技大学 Brick-concrete construction waste slag cold recycling cementitious material and its use method
CN112592077B (en) * 2021-01-24 2022-06-28 湖南科技大学 Brick-concrete building waste residue cold-recycling cementing material and use method thereof
CN113264700A (en) * 2021-05-25 2021-08-17 深圳市和盛环保科技有限公司 Regenerated cementing material based on subway shield sludge
CN115124318A (en) * 2022-04-22 2022-09-30 广州大学 Preparation method of novel carbonized recycled powder-slag pressed brick
CN115677281A (en) * 2022-11-22 2023-02-03 湖南凯迪工程科技有限公司 A kind of sidewalk brick and preparation method thereof
CN115677281B (en) * 2022-11-22 2023-12-05 湖南凯迪工程科技有限公司 A kind of sidewalk brick and its preparation method

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Application publication date: 20190709