CN109399942A - A kind of foam glass Ceramic Composite building heat preservation heat-barrier material and preparation method thereof - Google Patents
A kind of foam glass Ceramic Composite building heat preservation heat-barrier material and preparation method thereof Download PDFInfo
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- CN109399942A CN109399942A CN201811397495.0A CN201811397495A CN109399942A CN 109399942 A CN109399942 A CN 109399942A CN 201811397495 A CN201811397495 A CN 201811397495A CN 109399942 A CN109399942 A CN 109399942A
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- foam glass
- glass ceramic
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- composite building
- barrier material
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
- C03C11/007—Foam glass, e.g. obtained by incorporating a blowing agent and heating
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags
Abstract
The present invention relates to a kind of foam glass Ceramic Composite building heat preservation heat-barrier material and preparation method thereof, raw material includes hydrated glass matrix, crystal phase mineral and inorfil.Preparation process includes the preparation of wet chemistry method hydrated glass matrix, crystal phase mineral and inorfil blending, low-temp foaming and de-hydroxylated heat treatment.Material high specific surface area of the present invention has suitable open porosity and breathing humidity, reaches A grades of non-ignitable standards, and fire protecting performance is outstanding；Raw material types are extensive, at low cost, and preparation process is environmentally protective, the insulation suitable for construction wall.
Description
Technical field
The invention belongs to the field of building materials, in particular to a kind of foam glass Ceramic Composite building heat preservation heat-barrier material and
Preparation method.
Background technique
As energy shortage problem is increasingly serious, energy occupancy volume is only the firm practicing of China of world standard a quarter
" energy-saving and emission-reduction " policy.On the one hand, the consumption for reducing non-renewable energy resources to the greatest extent continually develops new cleaning fuel as replacing
Generation；On the other hand, it is dedicated to promoting effective utilization rate of energy.In national energy wastage in bulk or weight, building energy consumption accounting one third,
Huge consumption is so that Building Energy-saving gradually obtains social attention brought by refrigeration and heating.
As most important part is built, the quality that wall goes along with sb. to guard him thermal insulation material is its core, and research and development obtain wide
General concern.Currently, the biggish organic insulation material of occupation rate of market (polystyrene board etc.) obtains extensively because of light, good heat insulating
General application, but also caused because its fire protecting performance difference leads to accident (CCTV building and Shanghai Jing'an apartment event of fire etc.) for several times
The loss such as huge life, property；In addition, the promotion of national awareness of environment protection is so that the use of organic insulation material encounters bottleneck.
At the same time, the advantages that inorganic heat insulation material is because of itself and building same service life, ecological, environmental protective, fire protecting performance is excellent welcomes huge city
?.
Foam glass is a kind of inorganic heat insulation material light, thermal coefficient is low, and dominant mechanism is glass melt in high temperature
Lower package foaming agent decomposes the bubble formation porous system generated.Traditional preparation methods are powder sintering, with scrap glass etc.
For primary raw material, the additives such as a certain amount of foaming agent and fluxing agent, foam stabilizer, surfactant are mixed outside, are formed to obtain powder
Green body foams to obtain corresponding product according to certain thermal system.This method firing temperature is higher, commonly reaches 1200 DEG C or more,
Energy consumption is huge in process of production, improves the cost of material；Gained foam glass porosity of holding one's breath is excessively high simultaneously, in use process,
Droplet is also easy to produce in wet weather plate surface and influences to use, and breathable properties are poor.On the other hand, many scholars are with waterglass
For substrate, foaming agent is added, foams at moderate temperatures, can there must be the porous material for porosity of centainly holding one's breath, but there are binary
System stability is poor, and pore structure bubble diameter is different, the disadvantages of being unevenly distributed, and can not promote the use of.High beautiful (patent of invention: " one
Kind of cryogenic foam glass "), Liu Qi (patent of invention: " a kind of olivet rock and swelling product ") successively introduces in waterglass
B2O3、Al2O3As network intermediate, polynary network structure is formed in B, Al atom indentation waterglass system improves foaming and material
Expect durability, but there is the problems such as expansion ratio is lower, materials ' durability is poor in application process.Hu Binbing (patent of invention:
" a kind of cryogenic foam glass heat-insulating material of polymer modification ") in R2O-B2O3-SiO2It is introduced thereto on the basis of system poly-
Object lotion is closed, to improve the hydrophobicity and mechanical property of product, but performance is not substantially improved while cost raising.Meanwhile
Above-mentioned several modified methods are that will dry middle material progress low-temperature treatment, still containing 10% or so in gained foaming product
Hydroxyl, and the hydrophily of these hydroxyls is exactly to lead to the key factor of materials ' durability difference, the present invention is then directed to this and is changed
Into.
Foamed ceramics is a kind of high porosity, with 3 D stereo network skeleton and is mutually communicated the porous material of air hole structure
Material, is the third generation porous ceramics product after porous ceramics, ceramic honey comb.The porosity, the good machinery for having 70-80%
Performance, physicochemical property are stablized, and can be widely applied and the fields such as heat-exchange device, Industrial Waste Water Treatments, thermal and sound insulating materials.China
Carry out extensive work from early 1980s for foamed ceramics, the fields such as aviation, electronics, medical and building materials are covered in research,
But because starting late, technical level still more falls behind at present.Currently used technology of preparing include organic precursor infusion process,
Foamable reaction method, organic matter aggrade method and sol-gal process etc..Wherein, foaming can prepare the ceramic of high rate of closed hole, but
Ingredient requirement is high, firing process complexity is not easy to control；Pore creating material method simple process is added, but its pore size distribution of resulting product is poor, gas
Porosity is low；Gel injection-moulding method is a kind of novel preparation process, but how to prepare the suitable slurry of viscosity and ensure additive
In-situ chemical reaction go to explore there is still a need for a large amount of work etc..In conclusion foamed ceramics is as a kind of function admirable, application
The extensive functional material of prospect, mainly faces that higher cost of material, complex process, firing temperature be higher, energy consumption in production preparation
The problems such as big, causes to be difficult to realize commercial conversion, so that its application be made to be subject to certain restrictions.
Glass ceramics, also known as devitrified glass refer to the parent glass of specific composition, brilliant by control during heating
One kind prepared by change contains the polycrystalline solids material of a large amount of crystallite phases, is that a kind of glass phase of different proportion and crystal form
Inorganic complex.Current adoptable preparation method includes fusion method, sol-gal process, sintering process, float glass process etc., wherein melting
Method is most conventional methods, and glass ceramics combines the double grading of glass and ceramics, and resulting product not only has the more of ceramics
Brilliant feature, while again with the basic performance of glass, is a kind of special new material, high mechanical strength, and physicochemical property is steady
Fixed, thermostabilization is good, dimensionally stable, and preparation process is simple, performance can design, and can be used as structural material, optical material, electricity material
Material etc. is widely used in national defence, industry, building and other each fields, has a extensive future.
Wherein, three kinds of material property comparisons are as shown in the table
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of foam glass Ceramic Composite building heat preservation heat-barrier material and
Preparation method, the material firing temperature is lower, and physical and chemical stability is excellent, satisfactory mechanical property, has good breathing damping
Performance, uniform in foaming is preferable, reaches A grades of non-ignitable standards, and fire protecting performance is outstanding, can be used as building thermal insulation material use.
The present invention provides a kind of foam glass Ceramic Composite building heat preservation heat-barrier material, raw material include mass ratio be 80~
Hydrated glass matrix, crystal phase mineral and the inorfil of 90:10~20:0.1~0.5.
The hydrated glass matrix includes that the alkali metal silicate aqueous solution that mass ratio is 100:1-5 and glass matrix are modified
Agent is R2O-B2O3-Al2O3-SiO2It is glass phase.
The chemical formula of the alkali metal silicate aqueous solution is R2O·mSiO2·H2O；Wherein, modulus m range is 2.3-
One or more of 4.0, R Li, Na, K.
The glass matrix modifying agent is containing the reagent or mineral that can be used as glass network intermediate, such as boracic raw material
And/or aluminum-containing raw material.
The boracic raw material is boric acid, borax, containing one or more of boron mineral；Aluminum-containing raw material is bentonite, kaolinite
One or more of native (clay class mineral), alum.
The hydrated glass matrix is R2O-B2O3-Al2O3-SiO2It is glass phase.
The crystal phase mineral are one or more of quartz sand, shraff, feldspar, flyash；Crystal phase mineral
Granularity is 50 μm or less, it is therefore an objective to crystal phase is introduced into glass phase.
The inorfil is one or more of glass fibre, steel fibre, SiC fiber；The diameter of inorfil is
10-40 μm, length 2-8mm.
The present invention also provides a kind of preparation methods of foam glass Ceramic Composite building heat preservation heat-barrier material, comprising:
(1) it is dispersed in alkali metal silicate aqueous solution using wet chemistry method by glass matrix modifying agent is clipped, not
Hydrated glass matrix is obtained under the premise of gel；
(2) crystal phase mineral and inorfil are added in the hydrated glass matrix of step (1), are mixed after physical blending
Close colloidal sol；
(3) mixed sols of step (2) is poured into ceramic mold to move into batch-type furnace, is warming up to 200-400 DEG C and keeps the temperature
0.5-2h completes low-temp foaming；Furnace temperature is risen to 500-700 DEG C again, keeps the temperature 1-4h, completion high temperature is de-hydroxylated, in free nothing
Foam glass Ceramic Composite building heat preservation heat-barrier material is obtained under pressure condition.
A kind of foam glass Ceramic Composite building heat preservation heat-barrier material proposed by the invention, wherein Mineral crystal phase and glass
Foaming at matrix combination interface forms open-celled structure, and foaming forms independent closed pore in glass matrix, so that material prepared exists
Guarantee also to contain certain aperture under the premise of rate of closed hole, to be effectively improved the breathing humidity of plate, structural schematic diagram
As shown in Figure 1.
A kind of foam glass Ceramic Composite building heat preservation heat-barrier material proposed by the invention, refers to using wet chemistry method,
Glass matrix modifying agent is added into alkali metal silicate aqueous solution and obtains hydrated glass matrix, adds crystal phase mineral additive
With inorfil is blended obtains that stable sol, last thermally treated so that glass matrix is obtained foam glass with crystal phase in conjunction with ceramic
Composite material.
On the one hand, the modifying agent such as boracic raw material, clay class mineral or alum are beaten through high speed dispersion or high shear layer structure
Open, be dispersed in alkali metal silicate aqueous solution, B (or Al) element captures free oxygen or Si element formed it is negatively charged
[BO4]-(or [AlO4]-) tetrahedron is to by the R in system+And H+Firmly attract, so that original R2O-SiO2Binary system structure
Tend to fine and close to improve stability, forms stable glass matrix.On the other hand, crystal phase mineral additive is in the blending process
It is dispersed in sol system, crystal phase is evenly distributed in three-dimensional glass network structure during low-temp foaming and and glass
Matrix is combined closely, while inorfil is also dispersed in mixed sols.
Calcium-base bentonite and a small amount of boric acid to be added into sodium silicate as glass matrix modifying agent, incorporation flyash is crystalline substance
For phase mineral additive and appropriate glass fibre, foam glass ceramic firing and mechanism of modification are illustrated:
Bentonite is a kind of aluminium silicate mineral with lamellar structure, and main component is montmorillonite, is one kind by two layers
Oxygen-octahedron layer presss from both sides the 2:1 type stratiform silicon with two-dimensional channel and Large pore molecular sieve structure that one layer of alumina octahedral sheet is constituted
Hydrochlorate, interlayer are combined with faint molecular force or hydrogen bond, structure relative loose, can be occurred under external force or polar molecule effect
Interlayer relative motion is even stripped and comes.Under high speed shear state, lamella is removed rapidly, in alkali metal silicate aqueous solution
Under excitation, Si-O key and Al-O key fracture therein forms oligomeric sial tetrahedron.Then, these oligomeric sial tetrahedrons
Polycondensation process is carried out, i.e., is reconfigured by medium of water, forms the network struture system of new Si-O-Al.Meanwhile B in system
Element captures free oxygen or Si element forms negatively charged [BO4]-Tetrahedron, the R in attraction system+, Si-O-Al network with
R-B-Si network is interweaved, and forms stable glass network structure, wherein Na2O-B2O3-SiO2It is the XRD object phase point of glass
Analysis is as shown in Fig. 2 (a).
Flyash is a kind of aluminosilicate of particle shape, mainly contains glass microballoon, magnet microballon, quartz and mullite
Etc. crystal phases, shown in XRD material phase analysis figure such as Fig. 2 (b), be dispersed in system in shear history, with its special ball
Shape structure changes mobility when dissolved adhesiveness increases.It is evenly distributed in foaming process in three-dimensional glass network structure, it is brilliant
It mutually combines closely with ternary hydrated glass matrix, forms stable foam glass ceramics, XRD material phase analysis such as Fig. 2 (c) institute
Show, gained sample macro morphology (a) and microporous structure (b) are as shown in Figure 3.
Preparation method of the present invention is that heat treatment process is divided into two sections: low-temp foaming (≤400 DEG C) and high temperature
De-hydroxylated (500 DEG C -700 DEG C) two processes.1. low-temp foaming: this process mainly completes the foaming of sample, and crystal phase will be added
The mixed sols of mineral additive, glass matrix modifying agent and glass fibre is program-controlled at a lower temperature to heat up and cools down with furnace,
Obtain the sample of uniform in foaming；2. high temperature is de-hydroxylated: this stage is the furnace that first foamed sample is placed directly within to higher temperature
Final product is kept the temperature to obtain through certain time in thorax, promotes stability of material again by further decreasing hydroxy radical content.This point
On the one hand the process system of section firing guarantees in lower temperature, mixed sols is basically completed foaming process under temperature programmed control,
The skeleton structure of foamed glass and ceramic is formed, the processing of higher temperature then further decreases the hydroxy radical content in system, do not breaking
The stability of material is obviously improved on the basis of bad good foamed state；On the other hand, simple process, connecting are high, can meet
Industrial Production line requirement.
Key of the invention is:
(1) firstly, constructing stable polynary hydrated glass matrix, crystallite phase or Nucleating Agent are then introduced in the base,
Guarantee that it can be uniformly distributed in the base；Secondly, certain thermal process condition, so that glass phase and ceramic crystal phase are combined into
The one of matter, meanwhile, special heat treatment process is further on the basis of guaranteeing glass ceramics foam characteristics and physical property
The hydroxy radical content of reduction system, removal influences the hydrophilic radical of materials ' durability, to promote the stability and mechanicalness of material
Energy.
(2) solution of volume contraction problem during hydroxyl is gone.It is low when waterglass foams under the invention thermal system
Temperature is lower to complete even foaming, but during removing hydroxyl, and as temperature increases, hydroxy radical content further decreases, tentatively foam sample
Product softening, internal pore structure support force deficiency are gradually collapsed, and become fine and close.Glass fibre is added in the stage of blending, through high speed point
It is evenly distributed in colloidal sol after dissipating, during de-hydroxylated, the pore structure that can effectively support first foaming to be formed strengthens glass
Glass network plays the role of physical support, avoids the densification of first foamed sample.Meanwhile the addition of glass fibre, increase material
The toughness of material, so that the compression strength of foam glass ceramic composite is obviously improved.
Beneficial effect
(1) foam glass ceramic composite firing temperature of the invention is lower, makes pottery well below foam glass and foam
The firing temperature of porcelain further saves energy consumption, reduces cost；Two sections of firing process are guaranteeing the good foamed state of glass ceramics
On the basis of further decrease hydroxy radical content in system, promote stability of material.
(2) foam glass ceramic composite of the invention is modified by physical-chemical, has both the spy of ceramics with glass
Point, performance are stablized, and durability is good.
(3) the foam glass ceramics of the invention introducing portion crystal phase in glass matrix, satisfactory mechanical property, as inorganic
Thermal insulation material, A grades of fire protecting performance non-ignitable, and with the building same service life, service life is longer than organic insulation material；Fibre is introduced simultaneously
Dimension is so that the tensile strength of composite material is obviously improved.
(4) foam glass ceramic composite of the invention guarantee it is higher hold one's breath porosity while contain suitable connection
Pore structure, so that having good breathing humidity when plate is used as construction material.Compared with foam glass, in reality
In, when bulk density is suitable, thermal insulation property is identical, foam glass plate surface in rainy days or wet weather has knot
Dew generate, so as to cause bulge, peeling, peel off situations such as, and foam glass ceramic composite of the invention because containing in right amount
Open porosity can avoid these situations.
(5) foam glass ceramic composite of the invention has the advantages that lightweight, thermal coefficient are low, with same volume
Foamed ceramics, which is compared, has lighter quality, and porosity of holding one's breath is significantly larger than foamed ceramics, so that thermal insulation property is significantly better than commonly
Foam ceramic material.
(6) foamed glass and ceramic composite material raw material sources of the invention are extensive, cheap, reduce production cost, system
Product bulk density is lower, sells according to volume, and profit margin is big.
(7) process flow of the invention is simple, and the technological operations such as wet chemistry method and free foaming are simple, is suitable for industrial production
It promotes.Overall process carries out under the conditions of wet-chemical simultaneously, and dust pollution is less, ecological, environmental protective.
(8) foamed glass and ceramic composite material bulk density of the invention can design, and can be produced according to specific requirement, market
Selectable range is wide.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention；
Fig. 2 is the XRD material phase analysis figure of different systems；
Fig. 3 is macro morphology (a) and microporous structure (b) of the invention.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
With the liquid sodium silicate waterglass that modulus is 2.4, solid content is 48.95%, boric acid, flyash (about 25 μ of partial size
M), it is tested for raw material for (16 μm of diameter, length 6mm) of glass fibre.Specific raw material proportioning and main component in formula 1,2,3
Mass fraction is as shown in the table.
(remarks: because glass fibre volume is too low, each chemical constituent content is lower, therefore does not embody in the table, similarly hereinafter)
By the raw material of each formula, simultaneously dispersion mixing is uniform by high speed shear 30min under 4000r/min revolving speed, in not gel
Under the premise of obtain the mixed sols of different viscosities；The colloidal sol of different formulations is poured into ceramic mold, is moved into high temperature furnace；It presses
Be heated to 400 DEG C from room temperature according to the heating rate of 3 DEG C/min and keep the temperature 0.5h, after be placed directly in 500 DEG C of burner hearths, keep the temperature
1-4h etc. obtain the foam glass ceramic of different hydroxy radical contents.
The foam glass ceramics obtained according to formula 1-3 are subjected to correlated performance test, as a result as shown in the table:
Foam glass ceramic performance after 500 DEG C of processing 1h:
Foam glass ceramic performance after 500 DEG C of processing 2h:
Foam glass ceramic performance after 500 DEG C of processing 3h:
Foam glass ceramic performance after 500 DEG C of processing 4h:
From in table it is found that boric acid be added after form stable Na2O-B2O3-SiO2Glass network, flyash introduce quartz
Etc. crystal phases, the two form stable foam glass ceramics.Hydroxyl process is gone by the high temperature of different time, foam glass ceramics hold
Have again and slightly increase, material compression strength is gradually increased.Three formulas are compared, be added the sample bulk density of flyash and boric acid compared with
Low, pore size distribution$ is uniform, and thermal and insulating performance is preferable；After inorganic glass fiber is added, it can be seen that material bulk density and thermally conductive system
For number not by larger impact, sample thermal insulation property is good, meanwhile, mechanical strength significantly rises, and compression strength increases, can
Guarantee plate in preparation and using high yield rate is guaranteed in work progress, reduces the requirement to construction.
Embodiment 2
With the liquid sodium silicate waterglass that modulus is 2.4, solid content is 48.95%, boric acid, flyash (about 25 μ of partial size
M), it is tested for raw material for (16 μm of diameter, length 6mm) of glass fibre.Specifically raw material proportioning and main group are formulated in 1,2,3,4
Divide mass fraction as shown in the table.
By the raw material of each formula, simultaneously dispersion mixing is uniform by high speed shear 30min under 4000r/min revolving speed, in not gel
Under the premise of obtain the mixed sols of different viscosities；The colloidal sol of different ratio is poured into ceramic mold, is moved into high temperature furnace；It presses
Be heated to 400 DEG C from room temperature according to the heating rate of 3 DEG C/min and keep the temperature 0.5h, after be placed directly in 500 DEG C of burner hearths, keep the temperature
1-4h etc. obtain the foam glass ceramic of different hydroxy radical contents.
The foam glass ceramics obtained according to formula 1-3 are subjected to correlated performance test, as a result as shown in the table:
Foam glass ceramic performance after 500 DEG C of processing 1h:
Foam glass ceramic performance after 500 DEG C of processing 2h:
Foam glass ceramic performance after 500 DEG C of processing 3h:
Foam glass ceramic performance after 500 DEG C of processing 4h:
By table it is found that with boric acid volume raising, sample mesoporous distribution consistency degree improves, and glass network is more steady
Fixed, mechanical strength is promoted therewith；But meanwhile boric acid volume improve, dissolved adhesiveness increase, under identical heat power, high boron
Volume makes foaming materials multiplying power decrease, and bulk density increased, and thermal coefficient has therewith slightly to be risen, therefore, excessively high
On the one hand boron volume improves cost, on the other hand little to Effect of Materials, therefore in actual production, selects suitable volume.
Embodiment 3
With the liquid sodium silicate waterglass that modulus is 2.8, solid content is 36%, boric acid, flyash (about 25 μm of partial size), glass
(16 μm of diameter, length 6mm) of glass fiber are tested for raw material.Specific raw material proportioning and main component matter in formula 1,2,3,4
It is as shown in the table to measure score.
By the raw material of each formula, simultaneously dispersion mixing is uniform by high speed shear 30min under 4000r/min revolving speed, in not gel
Under the premise of obtain the mixed sols of different viscosities；The colloidal sol of different ratio is poured into ceramic mold, is moved into high temperature furnace；It presses
Be heated to 400 DEG C from room temperature according to the heating rate of 3 DEG C/min and keep the temperature 0.5h, after be placed directly in 500 DEG C of burner hearths, keep the temperature
1-4h etc. obtain the foam glass ceramic of different hydroxy radical contents.
The foam glass ceramics obtained according to formula 1-4 are subjected to correlated performance test, as a result as shown in the table:
Foam glass ceramic performance after 500 DEG C of processing 1h:
Foam glass ceramic performance after 500 DEG C of processing 2h:
Foam glass ceramic performance after 500 DEG C of processing 3h:
Foam glass ceramic performance after 500 DEG C of processing 4h:
Compared with the waterglass system of modulus 2.4, the waterglass expansion ratio of low modulus is higher, and resulting product bulk density is opposite
It is lower.
Embodiment 4
With the liquid potassium silicate water glass that modulus is 2.4, solid content is 48.95%, boric acid, flyash (about 25 μ of partial size
M), it is tested for raw material for (16 μm of diameter, length 6mm) of glass fibre.Specifically raw material proportioning and main group are formulated in 1,2,3,4
Divide mass fraction as shown in the table.
By the raw material of each formula, simultaneously dispersion mixing is uniform by high speed shear 30min under 4000r/min revolving speed, in not gel
Under the premise of obtain the mixed sols of different viscosities；The colloidal sol of different ratio is poured into ceramic mold, is moved into high temperature furnace；It presses
Be heated to 400 DEG C from room temperature according to the heating rate of 3 DEG C/min and keep the temperature 0.5h, after be placed directly in 500 DEG C of burner hearths, keep the temperature
1-4h etc. obtain the foam glass ceramic of different hydroxy radical contents.
The foam glass ceramics obtained according to formula 1-4 are subjected to correlated performance test, as a result as shown in the table:
Foam glass ceramic performance after 500 DEG C of processing 1h:
Foam glass ceramic performance after 500 DEG C of processing 2h:
Foam glass ceramic performance after 500 DEG C of processing 3h:
Foam glass ceramic performance after 500 DEG C of processing 4h:
Embodiment 5
With the liquid sodium silicate waterglass that modulus is 2.4, solid content is 48.95%, calcium-base bentonite, flyash (partial size
About 25 μm), (16 μm of diameter, length 6mm) of glass fibre are tested for raw material.In formula 1,2,3,4 specific raw material proportioning and
Main component mass fraction is as shown in the table.
By the raw material of each formula, simultaneously dispersion mixing is uniform by high speed shear 30min under 4000r/min revolving speed, in not gel
Under the premise of obtain the mixed sols of different viscosities；The colloidal sol of different ratio is poured into ceramic mold, is moved into high temperature furnace；It presses
Be heated to 400 DEG C from room temperature according to the heating rate of 3 DEG C/min and keep the temperature 0.5h, after be placed directly in 500 DEG C of burner hearths, keep the temperature
1-4h etc. obtain the foam glass ceramic of different hydroxy radical contents.
The foam glass ceramics obtained according to formula 1-4 are subjected to correlated performance test, as a result as shown in the table:
Foam glass ceramic performance after 500 DEG C of processing 1h:
Foam glass ceramic performance after 500 DEG C of processing 2h:
Foam glass ceramic performance after 500 DEG C of processing 3h:
Foam glass ceramic performance after 500 DEG C of processing 4h:
After calcium-base bentonite is added, montmorillonite lamella, which is stripped, after high speed shear comes, and Al atom enters Na2O-SiO2
Binary system forms stable Na2O-Al2O3-SiO2Ternary network structure is formed steady in conjunction with the crystal phase of introducing under heat treatment
Fixed foam glass ceramics.As doping quantity of fly ash improves, product bulk density is corresponding to be increased, and mechanical strength is promoted；Boric acid and calcium base
Bentonite can form stable TERNARY GLASS matrix as glass matrix modifying agent, but bentonitic addition can to a certain degree
Upper reduction expansion ratio, so that sample bulk density integrally increases.
Embodiment 6
With the liquid sodium silicate waterglass that modulus is 2.4, solid content is 48.95%, alum, flyash (about 25 μ of partial size
M), it is tested for raw material for (16 μm of diameter, length 6mm) of glass fibre.Specifically raw material proportioning and main group are formulated in 1,2,3,4
Divide mass fraction as shown in the table.
By the raw material of each formula, simultaneously dispersion mixing is uniform by high speed shear 30min under 4000r/min revolving speed, in not gel
Under the premise of obtain the mixed sols of different viscosities；The colloidal sol of different ratio is poured into ceramic mold, is moved into high temperature furnace；It presses
Be heated to 400 DEG C from room temperature according to the heating rate of 3 DEG C/min and keep the temperature 0.5h, after be placed directly in 500 DEG C of burner hearths, keep the temperature
1-4h etc. obtain the foam glass ceramic of different hydroxy radical contents.
The foam glass ceramics obtained according to formula 1-4 are subjected to correlated performance test, as a result as shown in the table:
Foam glass ceramic performance after 500 DEG C of processing 1h:
Foam glass ceramic performance after 500 DEG C of processing 2h:
Foam glass ceramic performance after 500 DEG C of processing 3h:
Foam glass ceramic performance after 500 DEG C of processing 4h:
After alum is added, the Al ion generated after hydrolysis enters Na2O-SiO2Binary system forms stable Na2O-
Al2O3-SiO2It is network structure glass matrix, forms stable foam glass pottery under heat treatment in conjunction with quartz, mullite crystalline phase
Porcelain.
Embodiment 7
With the liquid sodium silicate waterglass that modulus is 2.4, solid content is 48.95%, boric acid, calcium-base bentonite, flyash
(about 25 μm of partial size), (16 μm of diameter, length 6mm) of glass fibre are tested for raw material.Specific raw material is matched in formula 1,2,3,4
When main component mass fraction is as shown in the table.
By the raw material of each formula, simultaneously dispersion mixing is uniform by high speed shear 30min under 4000r/min revolving speed, in not gel
Under the premise of obtain the mixed sols of different viscosities；The colloidal sol of different ratio is poured into ceramic mold, is moved into high temperature furnace；It presses
Be heated to 400 DEG C from room temperature according to the heating rate of 3 DEG C/min and keep the temperature 0.5h, after be placed directly in 500 DEG C of burner hearths, keep the temperature
1-4h etc. obtain the foam glass ceramic of different hydroxy radical contents.
The foam glass ceramics obtained according to formula 1-4 are subjected to correlated performance test, as a result as shown in the table:
Foam glass ceramic performance after 500 DEG C of processing 1h:
Foam glass ceramic performance after 500 DEG C of processing 2h:
Foam glass ceramic performance after 500 DEG C of processing 3h:
Foam glass ceramic performance after 500 DEG C of processing 4h:
After calcium-base bentonite and boric acid are added, through high speed shear, montmorillonite lamella, which is stripped, to come, and Al atom enters
Na2O-SiO2Binary system forms stable Na2O-Al2O3-SiO2Ternary network structure, the B atom in boric acid also enter binary
Na is formed in system2O-B2O3-SiO2Three metanetworks, Na2O-Al2O3-SiO2With Na2O-B2O3-SiO2Network interweaves, and is formed and is stablized
Glass matrix, stable foam glass ceramics are formed under heat treatment with the crystal phase of introducing.
Embodiment 8
With the liquid sodium silicate waterglass that modulus is 2.8, solid content is 48.95%, boric acid, shraff (about 25 μ of partial size
M), it is tested for raw material for (16 μm of diameter, length 6mm) of glass fibre.Specifically raw material proportioning and main group are formulated in 1,2,3,4
Divide mass fraction as shown in the table.
By the raw material of each formula, simultaneously dispersion mixing is uniform by high speed shear 30min under 4000r/min revolving speed, in not gel
Under the premise of obtain the mixed sols of different viscosities；The colloidal sol of different ratio is poured into ceramic mold, is moved into high temperature furnace；It presses
Be heated to 400 DEG C from room temperature according to the heating rate of 3 DEG C/min and keep the temperature 0.5h, after be placed directly in 500 DEG C of burner hearths, keep the temperature
1-4h etc. obtain the foam glass ceramic of different hydroxy radical contents.
The foam glass ceramics obtained according to formula 1-4 are subjected to correlated performance test, as a result as shown in the table:
Foam glass ceramic performance after 500 DEG C of processing 1h:
Foam glass ceramic performance after 500 DEG C of processing 2h:
Foam glass ceramic performance after 500 DEG C of processing 3h:
Foam glass ceramic performance after 500 DEG C of processing 4h:
B atom in boric acid, which is dispersed to enter in binary system, forms Na2O-B2O3-SiO2Network forms stable glass
Matrix, meanwhile, after ceramic waste residue is added, the crystal phases such as quartz, mullite, feldspar are introduced, after heat treatment, form foam glass pottery
Porcelain.It compared with introducing crystal phase with flyash, introduces after ceramic waste residue, the uniform in foaming degree of product reduces, corresponding bulk density liter
Height, but ceramic waste residue is added and later the mechanical strength of material is promoted.
Embodiment 9
With the liquid sodium silicate waterglass that modulus is 2.4, solid content is 48.95%, boric acid, flyash (about 25 μ of partial size
M), it is tested for raw material for (40 μm of diameter, length 6mm) of glass fibre.Specifically raw material proportioning and main group are formulated in 1,2,3,4
Divide mass fraction as shown in the table.
By the raw material of each formula, simultaneously dispersion mixing is uniform by high speed shear 30min under 4000r/min revolving speed, in not gel
Under the premise of obtain the mixed sols of different viscosities；The colloidal sol of different ratio is poured into ceramic mold, is moved into high temperature furnace；It presses
Be heated to 400 DEG C from room temperature according to the heating rate of 3 DEG C/min and keep the temperature 0.5h, after be placed directly in 500 DEG C of burner hearths, keep the temperature
1-4h etc. obtain the foam glass ceramic of different hydroxy radical contents.
The foam glass ceramics obtained according to formula 1-3 are subjected to correlated performance test, as a result as shown in the table:
Foam glass ceramic performance after 500 DEG C of processing 1h:
Foam glass ceramic performance after 500 DEG C of processing 2h:
Foam glass ceramic performance after 500 DEG C of processing 3h:
Foam glass ceramic performance after 500 DEG C of processing 4h:
Comparative example 1
With the liquid sodium silicate waterglass that modulus is 2.4, solid content is 48.95%, flyash (about 25 μm of partial size), for original
Material is tested.Specific raw material proportioning and main component mass fraction are as shown in the table in formula 1,2,3,4.
By the raw material of each formula, simultaneously dispersion mixing is uniform by high speed shear 30min under 4000r/min revolving speed, in not gel
Under the premise of obtain the mixed sols of different viscosities；The colloidal sol of different formulations is poured into ceramic mold, is moved into high temperature furnace；It presses
Be heated to 400 DEG C from room temperature according to the heating rate of 3 DEG C/min and keep the temperature 0.5h, after be placed directly in 500 DEG C of burner hearths, keep the temperature
1-4h etc. obtain the foam glass ceramic of different hydroxy radical contents.
The foam glass ceramics obtained according to formula 1-4 are subjected to correlated performance test, as a result as shown in the table:
Foam glass ceramic performance after 500 DEG C of processing 1h:
Foam glass ceramic performance after 500 DEG C of processing 2h:
Foam glass ceramic performance after 500 DEG C of processing 3h:
Foam glass ceramic performance after 500 DEG C of processing 4h:
Comparative example 2
With the liquid sodium silicate waterglass that modulus is 2.4, solid content is 48.95%, boric acid, flyash (about 25 μm of partial size)
It is tested for raw material.Specific raw material proportioning and main component mass fraction are as shown in the table in formula 1,2,3,4.
By the raw material of each formula, simultaneously dispersion mixing is uniform by high speed shear 30min under 4000r/min revolving speed, in not gel
Under the premise of obtain the mixed sols of different viscosities；The colloidal sol of different ratio is poured into ceramic mold, is moved into high temperature furnace；It presses
Be heated to 400 DEG C from room temperature according to the heating rate of 3 DEG C/min and keep the temperature 0.5h, after be placed directly in 500 DEG C of burner hearths, keep the temperature
1-4h etc. obtain the foam glass ceramic of different hydroxy radical contents.
The foam glass ceramics obtained according to formula 1-4 are subjected to correlated performance test, as a result as shown in the table:
Foam glass ceramic performance after 500 DEG C of processing 1h:
Foam glass ceramic performance after 500 DEG C of processing 2h:
Foam glass ceramic performance after 500 DEG C of processing 3h:
Foam glass ceramic performance after 500 DEG C of processing 4h:
From in table it is found that boric acid be added after form stable Na2O-B2O3-SiO2It is glass network, flyash introduces stone
The crystal phases such as English, the two form stable foam glass ceramics.It can be seen that with the raising of doping quantity of fly ash, foam glass pottery
The bulk density of porcelain is gradually increased, and thermal coefficient decreases, and compression strength is corresponding to be improved；Meanwhile the addition of boric acid is so that material
The uniformity of foam characteristics and gas cell distribution is more preferably good, and the thermal coefficient of resulting materials is lower, has good thermal insulation property,
Sample is that A grades of fire prevention are non-ignitable simultaneously.
Claims (8)
1. a kind of foam glass Ceramic Composite building heat preservation heat-barrier material, it is characterised in that: raw material includes that mass ratio is 80~90:
Hydrated glass matrix, crystal phase mineral and the inorfil of 10~20:0.1~0.5.
2. a kind of foam glass Ceramic Composite building heat preservation heat-barrier material according to claim 1, it is characterised in that: described
Hydrated glass matrix includes the alkali metal silicate aqueous solution and glass matrix modifying agent that mass ratio is 100:1-5.
3. a kind of foam glass Ceramic Composite building heat preservation heat-barrier material according to claim 2, it is characterised in that: described
The chemical formula of alkali metal silicate aqueous solution is R2O·mSiO2·H2O；Wherein, modulus m range is 2.3-4.0, R Li, Na, K
One or more of.
4. a kind of foam glass Ceramic Composite building heat preservation heat-barrier material according to claim 2, it is characterised in that: described
Glass matrix modifying agent is boracic raw material and/or aluminum-containing raw material.
5. a kind of foam glass Ceramic Composite building heat preservation heat-barrier material according to claim 4, it is characterised in that: described
Boracic raw material is boric acid, borax, containing one or more of boron mineral；Aluminum-containing raw material is bentonite, kaolin, one in alum
Kind is several.
6. a kind of foam glass Ceramic Composite building heat preservation heat-barrier material according to claim 1, it is characterised in that: described
Crystal phase mineral are one or more of quartz sand, shraff, feldspar, flyash；The granularity of crystal phase mineral be 50 μm with
Under.
7. a kind of foam glass Ceramic Composite building heat preservation heat-barrier material according to claim 1, it is characterised in that: described
Inorfil is one or more of glass fibre, steel fibre, SiC fiber；The diameter of inorfil is 10-40 μm, length
For 2-8mm.
8. a kind of preparation method of foam glass Ceramic Composite building heat preservation heat-barrier material, comprising:
(1) it is dispersed in alkali metal silicate aqueous solution using wet chemistry method by glass matrix modifying agent is clipped, in not gel
Under the premise of obtain hydrated glass matrix；
(2) crystal phase mineral and inorfil are added in the hydrated glass matrix of step (1), obtain mixing after physical blending molten
Glue；
(3) mixed sols of step (2) is poured into ceramic mold to move into batch-type furnace, is warming up to 200-400 DEG C and keeps the temperature 0.5-
2h completes low-temp foaming；Furnace temperature is risen to 500-700 DEG C again, keeps the temperature 1-4h, completion high temperature is de-hydroxylated, in freedom without pressure shape
Foam glass Ceramic Composite building heat preservation heat-barrier material is obtained under state.
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