CN108083698A - A kind of inorganic non-metallic solid buoyant material of low-density grade and preparation method thereof - Google Patents
A kind of inorganic non-metallic solid buoyant material of low-density grade and preparation method thereof Download PDFInfo
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- CN108083698A CN108083698A CN201711223883.2A CN201711223883A CN108083698A CN 108083698 A CN108083698 A CN 108083698A CN 201711223883 A CN201711223883 A CN 201711223883A CN 108083698 A CN108083698 A CN 108083698A
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/40—Porous or lightweight materials
- C04B2111/42—Floating materials
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The present invention relates to a kind of inorganic non-metallic solid buoyant materials of low-density grade and preparation method thereof.The invention belongs to technical field of composite materials.The inorganic non-metallic solid buoyant material of low-density grade, each component mass fraction be 400 parts of waterglass, 50 70 parts of sodium hydroxide, 100 200 parts of metakaolin, 1 10 parts of silane coupling agent, 10 150 parts of foaming agent, 100 200 parts of light filler.Preparation method：(1) 2 4h are calcined under the conditions of kaolin being put 600 900 DEG C, are sieved into the metakaolin powder that granularity is less than 190 mesh；(2) waterglass and sodium hydroxide are mixed, stirred evenly；(3) metakaolin powder, water glass solution and silane coupling agent are added in mixer and stirred, added in foaming agent, add hollow glass micropearl, stir evenly；(4) material takes out, extrusion forming；(5) it is dry；(6) green body calcines 1 3h, furnace cooling at 300 600 DEG C.The present invention has simple for process, product high temperature resistant, corrosion-resistant without high-temperature calcination, the advantages that meeting the application needs in shallow sea field.
Description
Technical field
The invention belongs to technical field of composite materials, are floated more particularly to a kind of inorganic non-metallic solid of low-density grade
Dead-wood material and preparation method thereof.
Background technology
At present, the main developmental research both at home and abroad and more mature solid buoyancy material product of production technology is by hollow glass
The organic composite material system of glass microballon and resin matrix composition.Although organic solid buoyancy material is low, mechanical with density
The advantages that intensity is high, water absorption rate is low, corrosion-resistant, but it is limited in the special item such as high temperature the characteristics of easy to aging, non-refractory
Application under part.Therefore, it is necessary to develop the inorganic solid buoyancy material that can be used under the high temperature conditions.At present, China is special
Sharp CN200710015641.4 describes a kind of mud that gives up that polished using ceramics factory as raw material, and using dry-pressing, injection molding, room temperature is burnt
Knot, ceramic material prepared by high Temperature Chemical Foaming method technique is as matrix, using epoxy resin as the buoyancy for strengthening outer wall preparation
Material, the buoyant material density after epoxy resin modification are 0.52g/cm3When, compression strength >=20MPa.Such buoyant material
Shortcoming is non-complete inorganic system, and preparation process is more complicated.Document《The development of inorganic non-metallic solid buoyant material》With《It is hollow
The influence of glass microballoon species and addition to inorganic non-metallic solid buoyant material performance》Describe it is a kind of with metakaolin,
Slag and the ground polymers of sodium silicate reaction generation are basis material, the density prepared by filling a large amount of hollow glass micropearls
The inorganic non-metallic solid buoyant material low, intensity is high, density 0.78-0.9g/cm3, compression strength >=17MPa.Such buoyancy
Although material is inorganic system, but density is higher, is not suitable for the application of shallow sea field.
The content of the invention
The present invention provides a kind of inorganic non-metallic of low-density grade to solve technical problem present in known technology
Solid buoyancy material and preparation method thereof.
The present invention is that the gelling generated according to active metakaolin under appropriate alkali-activated carbonatite can be by loose material
Or bulk material is bonded to the whole principle contrived experiment formula with some strength, and on this basis, it is light by adding
Matter filler and the method for comprehensively utilizing chemical blowing process pore-creating achieve the purpose that reduce product density.
Metakaolin be by kaolin after the calcining of (500-900 DEG C) of lower temperature, be dehydrated the anhydrous aluminium silicate of formation, instead
Answer formula as follows：
2n(Si2O5,Al2(OH)4)→2(Si2O5,Al2O3)n+4nH2O
The reaction makes the ligancy of Al be converted into 4 or 5 from 6, and kaolin is converted into the metakaolin of undefined structure, former
Son arrangement is irregular, and the steady state of thermodynamics Jie is presented, has higher pozzolanic activity.The amorphous silicon aluminiums such as metakaolin
Compound is under the action of alkali, silicon-oxygen, aluminium-oxygen chain fracture, and in the poly- cement polymerisation process of soil, sieve and silica-sesquioxide experienced by solving
Gather the process polymerizeing again, ultimately form [the SiO being alternately bonded by sharing oxygen4]4-[AlO4]5-The polymerization of tetrahedron composition
Aluminium-oxygen-silicate network shape structure.The tetrahedron of exactly oxygen bridge connection forms the hole cage or cavity of three-dimensional framework, and makes soil
Polywater mud becomes a kind of firm structure.
The present invention adjusts sample rate using hollow glass micropearl as first kind light filler, this is because it has weight
The features such as amount is light, volume is big, thermal conductivity factor is low, compression strength is high, good fluidity.In the depolymerization and again of alkali-metakaolin system
In polymerization process, hollow glass micropearl is filled in polymeric aluminum-oxygen-silicate network structure, so not only improves reduction product
Density, while also advantageously improve the compression strength of cementitious material entirety.
The method of present invention comprehensive utilization chemical blowing process pore-creating, adds B2O3And CaCO3As the second class foaming agent, system
The inorganic non-metallic solid buoyant material of standby low-density grade.This is because add in B in alkali-activated carbonatite metakaolin system2O3Powder
Last, with the water reaction generation boric acid in system, at a certain temperature, boric acid is changed into metaboric acid, while acceptable and body
CaCO in system3Powder chemically reacts, and the bubble of generation can stablize pore-forming in the base, continues to raise with temperature,
CO in bubble2Gas is discharged, and forms a large amount of stomatas in the base, and so as to further reduce product density, reaction equation is as follows：
B2O3+3H2O→2H3BO3
B2O3+H2O→2HBO2
2H++CaCO3=H2O+CO2+Ca2+
An object of the present invention, which is to provide one kind, has good high temperature resistant, corrosion resistance, can be processed into a variety of shapes
The component of shape, the inorganic non-metallic solid buoyant material of the low-density grade for the features such as application needs in shallow sea field can be met.
The inorganic non-metallic solid buoyant material of low-density grade is adopted the technical scheme that in the present invention：
A kind of inorganic non-metallic solid buoyant material of low-density grade, its main feature is that：The inorganic non-gold of low-density grade
Belong to solid buoyancy material each component mass fraction for 400 parts of waterglass, 50-70 parts of sodium hydroxide, 100-200 parts of metakaolin,
1-10 parts of silane coupling agent, 10-150 parts of foaming agent, 100-200 parts of light filler.
The inorganic non-metallic solid buoyant material of low-density grade can also adopt the following technical scheme that in the present invention：
The inorganic non-metallic solid buoyant material of the low-density grade, its main feature is that：Silane coupling agent for KH-550,
One or more of KH-560, KH-570.
The inorganic non-metallic solid buoyant material of the low-density grade, its main feature is that：Foaming agent is B2O3、CaCO3In
One or two.
The inorganic non-metallic solid buoyant material of the low-density grade, its main feature is that：Light filler is hollow glass
Microballon, 15-120 microns a diameter of, density 0.20-0.38g/cm3, compressive resistance >=6MPa.
A kind of simple for process the second object of the present invention is to provide, without high-temperature calcination, a large amount of energy saving and resources are dirty
Contaminate small, product has the characteristics that good high temperature resistant, the inorganic non-metallic solid buoyancy material of the low-density grade of corrosion resistance
The preparation method of material.
The technical solution that the preparation method of the inorganic non-metallic solid buoyant material of low-density grade is taken in the present invention
It is：
A kind of preparation method of the inorganic non-metallic solid buoyant material of low-density grade, it is characterized in that：Low-density grade
Inorganic non-metallic solid buoyant material preparation method include following technical process：
(1) 2-4h is calcined under the conditions of kaolin being put 600-900 DEG C, is sieved into the metakaolin powder that granularity is less than 190 mesh
End；
(2) waterglass and sodium hydroxide are mixed, stirred evenly；
(3) metakaolin powder, water glass solution and silane coupling agent are added in mixer and stirred, in the item of stirring
Under part, foaming agent is added in, after stirring evenly, hollow glass micropearl is added, stirs evenly；
(4) material in mixer is taken out, extrusion forming；
(5) green body after shaping is dried；
(6) dried green body calcines 1-3h at 300-600 DEG C, then cools to room temperature with the furnace and comes out of the stove.
It will be cut, polished by the sample obtained after above-mentioned steps, be put into microcomputer-control full-automatic pressure testing
Machine carries out compression strength measurement.
The preparation method of the inorganic non-metallic solid buoyant material of low-density grade can also use following skill in the present invention
Art scheme：
The preparation method of the inorganic non-metallic solid buoyant material of the low-density grade, its main feature is that：After shaping
When green body is dried, drying temperature is 60-80 DEG C, drying time 2-4h.
The invention has the advantages and positive effects that：
Inorganic non-metallic solid buoyant material of low-density grade and preparation method thereof is as a result of of the invention brand-new
Technical solution, compared with prior art, the present invention have following superiority and technique effect：
Alkali-activated carbonatite cementitious material with it without high-temperature calcination, production process is simple, can be largely energy saving and provides
The advantages that source, small pollution, become a kind of high performance cementitious material of new green environment protection.Using alkali-activated carbonatite cementitious material as buoyancy
The matrix of material is conducive to save mass energy and reduce environmental pollution, makes energy resource and harmonious development.
Compared with organic solid buoyancy material, compression strength height that inorganic non-metallic material has, high temperature resistant, water absorption rate
The low, performance advantages such as elasticity modulus is small, make inorganic non-metallic solid buoyant material can be applied in the particular surroundings such as high temperature.
The document and patent report on solid buoyancy material have much both at home and abroad, but most of is for organic buoyancy
Material expansion research, such as the buoyancy material introduced in United States Patent (USP) No.4829094,4916173 and Chinese patent CN85106037A
Material is using cenosphere as packing material, is bonded with epoxy resin；Japan Patent No.3141304 is proposed at one
Glass microballoon silica filled organopolysiloxane oil is added in closed container, buoyant material is made；Chinese patent CN200410030821.6 is situated between
Continued a kind of solid buoyancy material being made of core and plane materiel, and core is the polyurethane-asphalt mixtures modified by epoxy resin prepared with chemical blowing process
Fat rigid foam, plane materiel are matched somebody with somebody by epoxy resin, polysulfide rubber, phosphorus laminal filter, light filler, coupling agent and curing agent
Into water blocking layer；Chinese patent CN200910230160.4 describes one kind
Core and the ultra-low density solid buoyant material that material water-proof material is plane materiel composition.And on inorganic buoyant material document and specially
Profit report is then seldom, and Chinese patent CN200710015641.4 describes a kind of preparation side of ceramic base lightweight high intensity buoyancy material
Method, but need to be using ceramic material as matrix, using epoxy resin as outer wall is strengthened, for non-fully inorganic system, preparation process
It is more complicated.And the present invention is only with the addition of a small amount of silane coupling agent (quality accounting is less than 3%), obtained solid in preparation process
Buoyant material is complete inorganic system.Document《The development of inorganic non-metallic solid buoyant material》With《Hollow glass micropearl species
And influence of the addition to inorganic non-metallic solid buoyant material performance》It describes a kind of using ground polymers as basis material and hollow
Glass microballoon is the inorganic non-metallic solid buoyant material that density prepared by light filler is low, intensity is high, although inorganic body
System, but density is higher, is not suitable for the application of shallow sea field.And consolidated by low-density grade inorganic non-metallic prepared by the present invention
Body buoyant material density 0.36-0.41g/cm3, compression strength 3.1-5.9MPa, water absorption rate≤2%, have good high temperature resistant,
Corrosion-resistant and processing performance, makes that it is suitable for carried for the underwater instrument equipment of investigation and underwater hiding-machine and associated uses under shallow sea water
For buoyancy.
Specific embodiment
In order to further understand the content, features and effects of the present invention, the following examples are hereby given, and it is described in detail
It is as follows：
Embodiment 1
A kind of inorganic non-metallic solid buoyant material of low-density grade, each component mass fraction be 400 parts of waterglass, hydrogen
60 parts of sodium oxide molybdena, 150 parts of metakaolin, 5 parts of KH-550 silane coupling agents, B2O3100 parts of foaming agent, 150 parts of light filler, gently
Matter filler be hollow glass micropearl, a diameter of 70 microns, density 0.35g/cm3, compressive resistance >=15MPa.
Embodiment 2
A kind of inorganic non-metallic solid buoyant material of low-density grade, each component mass fraction be 400 parts of waterglass, hydrogen
60 parts of sodium oxide molybdena, 200 parts of metakaolin, 10 parts of KH-570 silane coupling agents, CaCO3100 parts of foaming agent, 200 parts of light filler,
Light filler is hollow glass micropearl, a diameter of 100 microns, density 0.20g/cm3, compressive resistance >=6MPa.
Embodiment 3
A kind of preparation method of the inorganic non-metallic solid buoyant material of low-density grade, including following technical process：
Kaolin is put to the metakaolin powder formed in Muffle furnace through 800 DEG C after calcining 3h and crosses 190 mesh sieves, it is spare；It takes
400 parts of waterglass and 60 parts of sodium hydroxides, stir evenly in mixer, spare；Take 120 parts of metakaolin powder and 5 parts of silicon
Alkane coupling agent kh-570 is added in spare water glass solution, is stirred in mixer, is uniformly mixed it；In above-mentioned material
Add in 10 parts of B2O3With 15 parts of CaCO3, continue to stir；After stirring evenly, then 180 parts of light fillers are added in thereto, continue to stir
It mixes；The mixed material extrusion forming that will be stirred evenly；By the green body after shaping in 70 DEG C of dry 3h；Dried green body is 500
DEG C calcining 2h, then cool to room temperature with the furnace；Sample is processed by standard it is suitably sized, to it into line density and pressure resistance
Degree test.Performance parameter is as follows：Density 0.36g/cm3, compression strength 3.1MPa.
Embodiment 4
A kind of preparation method of the inorganic non-metallic solid buoyant material of low-density grade, including following technical process：
Kaolin is put to the metakaolin powder formed in Muffle furnace through 800 DEG C after calcining 3h and crosses 190 mesh sieves, it is spare；It takes
400 parts of waterglass and 60 parts of sodium hydroxides, stir evenly in mixer, spare；Take 120 parts of metakaolin powder and 5 parts of silicon
Alkane coupling agent kh-570 is added in spare water glass solution, is stirred in mixer, is uniformly mixed it；In above-mentioned material
Add in 45 parts of B2O3With 15 parts of CaCO3, continue to stir；After stirring evenly, then 180 parts of light fillers are added in thereto, continue to stir
It mixes；The mixed material extrusion forming that will be stirred evenly；By the green body after shaping in 70 DEG C of dry 3h；Dried green body is 500
DEG C calcining 2h, then cool to room temperature with the furnace；Sample is processed by standard it is suitably sized, to it into line density and pressure resistance
Degree test.Performance parameter is as follows：Density 0.41g/cm3, compression strength 5.9MPa.
The present embodiment is simple for process, and without high-temperature calcination, a large amount of energy saving and resources, pollution is small, and product has good
High temperature resistant, corrosion resistance, the components of various shapes can be processed into, application needs in shallow sea field etc. can be met and actively imitated
Fruit.
Claims (6)
1. a kind of inorganic non-metallic solid buoyant material of low-density grade, it is characterized in that：The inorganic non-metallic of low-density grade
Solid buoyancy material each component mass fraction be 400 parts of waterglass, 50-70 parts of sodium hydroxide, 100-200 parts of metakaolin, silicon
1-10 parts of alkane coupling agent, 10-150 parts of foaming agent, 100-200 parts of light filler.
2. the inorganic non-metallic solid buoyant material of low-density grade according to claim 1, it is characterized in that：It is silane coupled
Agent is one or more of KH-550, KH-560, KH-570.
3. the inorganic non-metallic solid buoyant material of low-density grade according to claim 1, it is characterized in that：Foaming agent is
B2O3、CaCO3One or both of.
4. the inorganic non-metallic solid buoyant material of low-density grade according to claim 1, it is characterized in that：Light filler
It is 15-120 microns a diameter of for hollow glass micropearl, density 0.20-0.38g/cm3, compressive resistance >=6MPa.
5. the preparation method of the inorganic non-metallic solid buoyant material of low-density grade according to claim 1, feature
It is：The preparation method of the inorganic non-metallic solid buoyant material of low-density grade includes following technical process：
(1) 2-4h is calcined under the conditions of kaolin being put 600-900 DEG C, is sieved into the metakaolin powder that granularity is less than 190 mesh；
(2) waterglass and sodium hydroxide are mixed, stirred evenly；
(3) metakaolin powder, water glass solution and silane coupling agent are added in mixer and stirred, in the condition of stirring
Under, foaming agent is added in, after stirring evenly, hollow glass micropearl is added, stirs evenly；
(4) material in mixer is taken out, extrusion forming；
(5) green body after shaping is dried；
(6) dried green body calcines 1-3h at 300-600 DEG C, then cools to room temperature with the furnace and comes out of the stove.
6. the preparation method of the inorganic non-metallic solid buoyant material of low-density grade according to claim 5, feature
It is：When green body after shaping is dried, drying temperature is 60-80 DEG C, drying time 2-4h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128098A (en) * | 2019-06-26 | 2019-08-16 | 胡姣 | A kind of buoyant material and preparation method effectively improving binding performance between system |
| CN113233847A (en) * | 2021-06-24 | 2021-08-10 | 杭州申华混凝土有限公司 | Lightweight concrete and preparation method thereof |
| CN114057509A (en) * | 2021-10-22 | 2022-02-18 | 中建六局(天津)绿色建筑科技有限公司 | Foamed ceramic with polished brick mud as main raw material and preparation method thereof |
| CN114193588A (en) * | 2021-11-29 | 2022-03-18 | 天津大学（青岛）海洋工程研究院有限公司 | Preparation method of high-temperature-resistant inorganic buoyancy material |
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Application publication date: 20180529 |