CN100352786C - Calcium silicate hardened article - Google Patents

Calcium silicate hardened article Download PDF

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CN100352786C
CN100352786C CNB038156857A CN03815685A CN100352786C CN 100352786 C CN100352786 C CN 100352786C CN B038156857 A CNB038156857 A CN B038156857A CN 03815685 A CN03815685 A CN 03815685A CN 100352786 C CN100352786 C CN 100352786C
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calcium silicate
aqueous slurry
cured calcium
solid mixture
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CN1780800A (en
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小川晃博
松山博圭
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Asahi Kasei Corp
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Asahi Kasei Kogyo KK
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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
    • C04B28/18—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 mixtures of the silica-lime type
    • 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
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00189—Compositions or ingredients of the compositions characterised by analysis-spectra, e.g. NMR
    • 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
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00267—Materials permeable to vapours or gases
    • 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
    • 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
    • C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
    • C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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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)
  • Building Environments (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)

Abstract

A calcium silicate hardened article which has a flexural strength of 0.05 MPa or more, a heat conductivity of 0.02 to 0.1 Wm<-1>K<-1>, and an air permeability of 5 X 10<-4> to 1 m<2>h<-1>Pa<-1> or less, and exhibits dynamic insulating property.

Description

Cured calcium silicate object and production method thereof
Technical field
The present invention relates to show the cured calcium silicate object of dynamic thermal insulating properties.More specifically, the present invention relates to cured calcium silicate object, it has minimum and is the flexural strength of 0.05MPa, and has 0.02-0.1 Wm -1K -1Thermal conductivity and 5 * 10 -4-1m 2h -1Pa -1Air penetrability, thereby show dynamic thermal insulating properties.Cured calcium silicate object of the present invention not only has light weight and high intensity, and it is non-combustible.In addition, cured calcium silicate object of the present invention shows high thermal insulating properties and high air penetrability simultaneously.Therefore, described cured calcium silicate object can be advantageously used for wall material for building that need show dynamic thermal insulating properties etc.In this article, " dynamically thermal insulating properties " is meant the performance that wherein realizes high air penetrability and insulation effect simultaneously.The wall material for building that shows dynamic heat-insulating property can be advantageously used in so-called " dynamically Thermo Isolation Technique ", wherein carries out planned ventilation (that is, constant or ventilation intermittently is used to keep the space air fresh) and reduces heat-energy losses simultaneously.In addition, the invention still further relates to the method for producing above-mentioned cured calcium silicate object.
Background technology
At present, because serious social concern, as the exhaustion of mineral fuel, use atmospheric pollution that mineral fuel cause and the carbonic acid gas that produces by mineral fuel to cause global warming in a large number, more and more need save energy.Particularly in the building of dwelling house and commercial use, the consumption of energy is along with hope provides the increase of comfortable living space tendency to increase by using air-conditioning.Therefore, attempt by making buildings be height adiabatic and highly air-locked save energy.Yet in becoming height adiabatic and highly air-locked enclosed space, the Air quality in room is by the activity variation in described space.Therefore,, used dehumidifier, humidifier, air purifier etc., yet this has reduced the energy-saving effect that above-mentioned enclosed space is realized in order to keep the space air cleaning.Therefore, in recent years, in having the buildings that becomes highly adiabatic and highly air-locked enclosed space, planned ventilation (promptly, constant or ventilation intermittently, be used to keep the space air fresh) necessitate, and therefore need architectural design and material of construction can be effective to heat insulation and ventilate.
Yet well-known, because the wall of buildings and the structure of top ceiling reduce its heat transfer coefficient and be restricted, therefore, the heat-energy losses that is reduced in wall and the top ceiling also is restricted.
In this case, mainly Northern European countries after deliberation so-called " dynamically Thermo Isolation Technique ", wherein carry out the loss that above-mentioned planned ventilation reduces heat energy simultaneously.Particularly, in dynamic Thermo Isolation Technique, outside air is incorporated into by the thermal insulation material that uses in wall and top ceiling indoor, thereby prevent that indoor heat from escaping into the open air by wall and top ceiling.In this technology, it is fresh being incorporated into indoor outside air by thermal insulation material, and be incorporated into indoor before, outside air preheating in the wall material.Therefore, the preheating that might carry out vent air (being incorporated into indoor outside air) reduces apparent heat transter coefficient simultaneously, thereby keeps high space air quality.
In order to put into practice dynamic Thermo Isolation Technique effectively, be necessary to use not only to have high thermal insulating properties, and have the material of high air penetrability.In addition, this bill of material of wishing to be used to implement dynamic Thermo Isolation Technique reveals excellent workability, excellent cost performance and high strength.In addition, from requiring the angle of resistivity against fire, wish that this material is non-flame properties.
Usually, as lagging material, used organic expansion type thermal insulation material.Yet organic expansion type thermal insulation material has high rate of closed hole, and therefore the air penetrability of performance is low.Therefore, organic expansion type thermal insulation material is not suitable for and is dynamically using in the Thermo Isolation Technique.In addition, organic expansion type thermal insulation material has the problem of resistivity against fire aspect.On the other hand, as inorganic thermal insulation material, can mention multicellular glass by the glass foaming is obtained.Yet multicellular glass costs an arm and a leg, and also has high rate of closed hole, and therefore the air penetrability that shows is low.Therefore, inorganic thermal insulation material also is not suitable for dynamically using in the Thermo Isolation Technique.In addition, the Japanese Patent Application Publication No.2001-122674 of WO 02/06693 and pending trial discloses the technology relevant with cured calcium silicate object.Yet the air penetrability of the cured calcium silicate object that obtains by the technology of describing in the above-mentioned patent document is low, and therefore, it can not play as the dynamically effect of thermal insulation material.
In the dynamic Thermo Isolation Technique of routine, the wall material of use obtains by the following method: the framework of the compartment with predetermined size is provided, and is full of compartment with thermal insulation material as pulp fragment and the inorganic fibre (for example asbestos) that derives from recycled writing paper.Yet this framework itself has the thermal conductivity higher than thermal insulation material in the compartment, and heat is conducted by framework.Therefore, there is above-mentioned wall material can not show the problem of gratifying dynamic insulation effect.In addition, in the dynamic Thermo Isolation Technique of routine, at framework with blow in the slit that forms inevitably between the thermal insulation material in the compartment of wall profile framework thermosteresis takes place.Therefore, conventional dynamic Thermo Isolation Technique has proposed other problem, in practice, is necessary to increase the thickness of wall material, to compensate the above-mentioned thermosteresis that takes place in the slit that forms between framework and thermal insulation material.
It is 0.5 apparent specific gravity that conventional material of construction such as Wood cement board and concrete fragment of brick have minimum, therefore shows high thermal conductivity.This high thermal conductivity causes the massive losses of energy inevitably.Therefore, the problem of conventional material of construction proposition is to obtain gratifying dynamic insulation effect.In addition, the Japanese Patent Application Publication No.2001-348283 of pending trial discloses the technology of using sound absorbent material.Yet the apparent specific gravity of disclosed sound absorbent material is about 0.35 in above-mentioned patent documentation, therefore shows high thermal conductivity.Therefore above-mentioned sound absorbent material is not suitable as dynamic thermal insulation material.
In addition, attempt to use asbestos plate and glass wool pad as dynamic thermal insulation material, every kind all has low thermal conductivity.Yet, use asbestos plate and glass wool pad to produce following problem as dynamic thermal insulation material: in fact asbestos plate and glass wool pad are not hard materials, on the contrary, be by cotton fibre or thin fiber being twined formation mutually, therefore having low flexural strength.Therefore, asbestos plate and glass wool pad all need by crossbeam or frame strengthening, to guarantee as the material of construction full intensity.Yet, the own heat conduction of crossbeam and framework.Therefore, the problem of using asbestos plate or glass wool pad to produce is to obtain gratifying dynamic insulation effect.In addition, when at construction site cutting asbestos plate or glass wool pad, produce deleterious primitive fiber, it disseminates and destroys constructor's health.In addition, asbestos plate and glass wool pad all have too high air penetrability, therefore can not be used as dynamic thermal insulation material independently.When attempting to use asbestos plate or glass wool pad as dynamic thermal insulation material, need to use plastics list with big metering-orifice, be used to cover the surface of each above-mentioned plate and pad, described surface is towards indoor.Therefore the construction process problem that trouble and thermal insulation material resistivity against fire generally reduce that becomes has appearred.
Summary of the invention
In this case, the inventor has carried out extensive research, to solve the aforementioned problems in the prior.The result is, find unexpectedly can to obtain by the method that may further comprise the steps being suitable for as the dynamic cured calcium silicate object with specified property of thermal insulation material: whipping agent is joined in the aqueous slurry that comprises solid mixture, and described solid mixture is made up of following material basically: the silicic acid material of specified quantitative, matrix material, at least aly be selected from the aluminum compound of Tai-Ace S 150 and hydrate thereof and be different from Tai-Ace S 150 and the sulphate cpd of hydrate and Calcareous material optionally; The aqueous slurry that obtains is poured in the mould; With make aqueous slurry pre-hardening, carry out autoclaved (autoclaving) then, condition is that the weight ratio of control Calcareous material and matrix material is up to 0.6, perhaps when above-mentioned weight ratio is higher than 0.6, add at least two kinds of additives that are selected from tensio-active agent, viscosity modifier and antifoams in hydrotropisms's slurry.Particularly, the flexural strength of above-mentioned cured calcium silicate object minimum is 0.05MPa, and thermal conductivity is 0.02-0.1 Wm -1K -1, air penetrability is 5 * 10 -4-1m 2h -1Pa -1Thereby, show dynamic thermal insulating properties.Above-mentioned cured calcium silicate object not only has light weight and high intensity, and is non-flame properties.In addition, cured calcium silicate object shows high thermal insulating properties and high air penetrability.Therefore, cured calcium silicate object can be advantageously used for wall material for building that need show dynamic thermal insulating properties etc.Finished the present invention according to these discoveries.
Therefore, the purpose of this invention is to provide cured calcium silicate object, it not only has light weight and high intensity, and is non-combustible, it shows high thermal insulating properties and high air penetrability, makes it can be advantageously used for wall material for building that need show dynamic thermal insulating properties etc.
Another object of the present invention provides the method for producing above-mentioned cured calcium silicate object effectively.
According to following detailed description, connection with figures, above and other objects of the present invention, feature and advantage are conspicuous.
The invention provides cured calcium silicate object, it is minimum for the flexural strength of 0.05MPa with have (2) 0.02-0.1Wm that it has (1) -1K -1Thermal conductivity and (3) 5 * 10 -4-1m 2h -1Pa -1Air penetrability, thereby show dynamic thermal insulating properties.
In order to understand the present invention easily, essential characteristic of the present invention and a plurality of preferred embodiment is following enumerates.
1. cured calcium silicate object, it is minimum for the flexural strength of 0.05MPa with have (2) 0.02-0.1Wm that it has (1) -1K -1Thermal conductivity and (3) 5 * 10 -4-1m 2h -1Pa -1Air penetrability, thereby show dynamic thermal insulating properties.
2. to begin a project 1 cured calcium silicate object, it has 0.02-0.08Wm -1K -1Thermal conductivity.
3. to begin a project 1 cured calcium silicate object, it has 0.02-0.06Wm -1K -1Thermal conductivity.
4. to begin a project in 1 to 3 each cured calcium silicate object, it mainly comprises tobermorite, and its x-ray diffractogram of powder show (220) planar diffraction peak intensity Ib of tobermorite wherein and respectively in (220) plane of tobermorite and the peak-to-peak diffraction angle scope of two diffraction of (222) planar observed minimum diffracted intensity Ia satisfy relations I b/Ia 〉=3.
5. the production method of cured calcium silicate object, it comprises:
(1) provide the aqueous slurry that comprises water and solid mixture,
Described solid mixture is made up of following material basically: silicic acid material, matrix material, at least a aluminum compound that is selected from Tai-Ace S 150 and hydrate thereof, at least a sulphate cpd of the vitriol that is different from Tai-Ace S 150 and hydrate thereof and the Calcareous material optionally of being selected from
Wherein in the weight of solid mixture, the amount of contained at least a aluminum compound is with Al in the aqueous slurry 2O 3The conversion scale be shown 0.09-10 weight %; With the weight in solid mixture, the amount of contained at least a sulphate cpd is with SO in the aqueous slurry 3The conversion scale be shown 0.15-15 weight %, SO 3Amount be the SO that is equivalent at least a aluminum compound 3Amount and be equivalent to the SO of at least a sulphate cpd 3The summation of amount,
Wherein the weight ratio of water and solid mixture be 2.3 to 5.5 and
Wherein the weight ratio of Calcareous material and matrix material is 0.6 to the maximum;
(2) add whipping agent in hydrotropisms's slurry;
(3) aqueous slurry is poured in the mould; With
(4) make aqueous slurry pre-hardening, carry out autoclaved then.
6. to begin a project 5 method, wherein whipping agent is to be selected from aluminium powder and to contain at least a in the aluminium aqueous slurry and wherein in the weight of solid mixture, the consumption of whipping agent is expressed as 0.03-0.95 weight % with contained solid weight percentage in the whipping agent.
7. the production method of cured calcium silicate object, it comprises:
(1) provide the aqueous slurry that comprises water and solid mixture,
Described solid mixture is made up of following material basically: silicic acid material, matrix material, at least a aluminum compound that is selected from Tai-Ace S 150 and hydrate thereof, at least a sulphate cpd of the vitriol that is different from Tai-Ace S 150 and hydrate thereof and the Calcareous material optionally of being selected from
Wherein in the weight of solid mixture, the amount of contained at least a aluminum compound is with Al in the aqueous slurry 2O 3The conversion scale be shown 0.09-10 weight %; With the weight in solid mixture, the amount of contained at least a sulphate cpd is with SO in the aqueous slurry 3The conversion scale be shown 0.15-15 weight %, SO 3Amount be the SO that is equivalent at least a aluminum compound 3Amount and be equivalent to the SO of at least a sulphate cpd 3The summation of amount,
Wherein the weight ratio of water and solid mixture be 2.3 to 5.5 and
Wherein the weight ratio of Calcareous material and matrix material is greater than 0.6;
(2) add whipping agent in hydrotropisms's slurry;
(3) aqueous slurry is poured in the mould; With
(4) make aqueous slurry pre-hardening, carry out autoclaved then,
Wherein add at least two kinds of additives that are selected from tensio-active agent, viscosity modifier and antifoams in hydrotropisms's slurry, condition be the adding of viscosity modifier and antifoams be added in step (1) afterwards and step (2) is carried out before and being added in the step (2) of tensio-active agent carried out simultaneously with the adding of whipping agent.
8. to begin a project 7 method, wherein whipping agent is to be selected from aluminium powder and to contain at least a in the aluminium aqueous slurry and wherein be expressed as 0.03-0.95 weight % in the consumption of the weight whipping agent of solid mixture with contained solid weight percentage in the whipping agent.
9. to begin a project 7 or 8 method, wherein tensio-active agent is at least aly to be selected from the compound of higher alcohol sulfate, higher alcohol sulfate and Voranol EP 2001 and to be 0.01-200 weight % in the consumption of contained solid weight tensio-active agent in the whipping agent wherein.
10. to begin a project in 7 to 9 each method, wherein viscosity modifier is at least aly to be selected from the compound of methylcellulose gum and polyvinyl alcohol and to be 0.01-1 weight % in the consumption of the weight viscosity modifier of solid mixture wherein.
11. to begin a project in 7 to 10 each method, wherein antifoams is at least aly to be selected from the compound of siloxanes, aliphatic acid, aliphatic ester, pure and mild phosphoric acid ester and to be 0.001-3 weight % in the consumption of the weight antifoams of solid mixture wherein.
Description of drawings
Fig. 1 and Fig. 2 represent the x-ray diffractogram of powder of the cured calcium silicate object of production among the embodiment 13, have wherein also represented to obtain the method for Ia and Ib value, and wherein " CPS " is the abbreviation of per second counting;
Fig. 1 represents among the embodiment 13 x-ray diffractogram of powder of the cured calcium silicate object produced, wherein also represented Ia value (observed minimum diffracted intensity in (220) plane of tobermorite and the peak-to-peak diffraction angle scope of two diffraction of (222) planar respectively) and Ib value ((220) planar diffraction peak intensity of tobermorite);
Fig. 2 represents the x-ray diffractogram of powder of the cured calcium silicate object of production among the embodiment 13, has wherein represented the method for mensuration I (220) value [(220) planar diffraction peak intensity of tobermorite] and I (002) value [tobermorite (002) planar diffraction peak intensity]; With
The illustrative of example that Fig. 3 represents to be used to measure the device of the defined air penetrability of the present invention is shown and is attempted.
Nomenclature
1: sample
2: the sample holder that is equipped with rubber packing
3: vacuum pump
4: pressure regulator valve
5: the pressure regulating tank
6: differential pressure meter
7: under meter
Embodiment
Be described in more detail below the present invention.
In the present invention, " cured calcium silicate object " is the general name by the material that makes the various ways that the composition sclerosis that comprises calcium silicate compound produces.Usually, the example of cured calcium silicate object comprises concrete, hardened mortar, Autoclaved lightweight concrete (often being called hereinafter, " ALC ") and fiber reinforced calcium silicate board.
It is minimum for the flexural strength of 0.05MPa with have (2) 0.02-0.1Wm that cured calcium silicate object of the present invention has (1) -1K -1Thermal conductivity and (3) 5 * 10 -4-1m 2h -1Pa -1Air penetrability, thereby show dynamic thermal insulating properties.Therefore, cured calcium silicate object of the present invention can be advantageously used for dynamic thermal insulation material.In this article, " dynamically thermal insulation material " is meant the material that can be used in so-called " dynamically Thermo Isolation Technique ".For dynamic Thermo Isolation Technique, but " Analytical Investigation of the Steady-State Behavior of Dynamic andDiffusive Building Envelopes " (Building and Environment of people such as reference example such as B.J.Taylor, the 31st volume, the 6th phase, the 519-525 page or leaf, 1996) and " Takinogata Dannetsu Gijutu ni kansuruKenkyu (Research on Multifunctional Insulation Technologies) " (Searchreport, No.53, Hokkaido Prefectural Cold Region Building ResearchInstitute, Japan, 1993).In dynamic Thermo Isolation Technique, carry out planned ventilation and reduce heat-energy losses simultaneously.Particularly, in dynamic Thermo Isolation Technique, introduce indoor by the thermal insulation material that in wall material and top ceiling material, provides outside air.Therefore, dynamically the advantage of Thermo Isolation Technique is: outside air is introduced indoor before, make its preheating in the wall material, thereby prevent that indoor heat from escaping into the open air by wall and top ceiling.In addition, dynamic Thermo Isolation Technique is also advantageous in that it is fresh introducing indoor air.Therefore, might carry out the preheating of vent air (being incorporated into indoor outside air), reduce apparent heat transter coefficient simultaneously, thereby keep high-caliber Air quality in the room.
The flexural strength minimum of cured calcium silicate object of the present invention is 0.05MPa, and preferred minimum is 0.07MPa, and more preferably minimum is 0.1MPa.When the flexural strength of cured calcium silicate object during less than 0.05MPa, being difficult to keep cured calcium silicate object is the preferred plate shape of dynamic thermal insulation material institute, thereby reduces the workability of cured calcium silicate object.
The thermal conductivity of cured calcium silicate object of the present invention is 0.02-0.1Wm -1K -1, be preferably 0.02-0.08Wm -1K -1, 0.02-0.06Wm more preferably -1K -1When the thermal conductivity of cured calcium silicate object greater than 0.1Wm -1K -1The time, the thermal insulating properties of cured calcium silicate object reduces.Therefore, when using thermal conductivity greater than 0.1Wm -1K -1This cured calcium silicate object during as thermal insulation material, in order to obtain gratifying effect of heat insulation, need to increase the thickness of walls (wherein having used thermal insulation material), thereby reduced the workability of cured calcium silicate object.On the other hand, from practical angle, the following 0.02Wm that is limited to of the thermal conductivity of cured calcium silicate object -1K -1
The air penetrability of cured calcium silicate object of the present invention is 5 * 10 -4-1m 2h -1Pa -1, preferred 1 * 10 -3-0.5m 2h -1Pa -1, more preferably 5 * 10 -3-0.1m 2h -1Pa -1When the air penetrability of cured calcium silicate object is in above-mentioned scope, might use cured calcium silicate object as dynamic thermal insulation material, when ventilating, it can reduce heat transfer coefficient significantly.When the air penetrability of cured calcium silicate object less than 5 * 10 -4m 2h -1Pa -1The time, therefore the shortcoming that causes is that cured calcium silicate object can not introduce outside air indoorly, can not play the effect of dynamic thermal insulation material, the shortcoming that causes also is to have weakened draught capacity.For example, when producing cured calcium silicate object by the method for describing among the WO 02/06693 (as mentioned above), the air penetrability of cured calcium silicate object is less than 5 * 10 -4m 2h -1Pa -1, so it can not play as the dynamically effect of thermal insulation material.On the other hand, when the air penetrability of cured calcium silicate object greater than 1m 2h -1Pa -1The time, outside air becomes too high by the flow rate of cured calcium silicate object, therefore makes it be difficult to carry out the preheating of vent air (introducing indoor outside air).In addition, when cured calcium silicate object had too high air penetrability, the pressure difference between the wall both sides became too little, thereby made it can not cause gratifying air in the cured calcium silicate object internal flow, described air flowing be carry out dynamically adiabatic necessary.
Particularly, in the present invention, the air penetrability of cured calcium silicate object can be measured as follows.Right cylinder sample (the length: L of preparation cured calcium silicate object; Cross-sectional area: S), except the surface at right cylinder sample two ends, with the surface of epoxy sealing right cylinder sample.Use vacuum pump to regulate the pressure at right cylinder sample two ends (having unsealed surface) then, cause air flowing takes place in the sample, when the pressure difference at sample two ends becomes 1kPa, the flow rate of air in the calculation sample.The flow rate of air is calculated air penetrability by following equation (1) from the sample of measuring:
Air penetrability (m 2h -1Pa -1)=W * L/S/ Δ P (1)
Wherein:
W: the flow rate (m of air 3h -1);
L: sample length (m);
S: the cross-sectional area (m of sample 2); With
Δ P: pressure difference (Pa).
The measuring method of air penetrabilities is described with reference to figure 3 hereinafter.
Sample 1 is placed in the sample holder 2 that internal surface is equipped with rubber packing, and wherein said rubber packing can seal tightly the inside of sample holder 2 by the air compression.Then, the pressure of use vacuum pump 3, regulating in the pressure regulating tanks 5 by pressure regulator valve 4.When the pressure difference that measures by differential pressure meter 6 is 1kPa, by the flow rate of air under meter 7 measure sample.The flow rate of air from the sample of measuring is calculated air penetrability according to above equation (1).
Cured calcium silicate object of the present invention mainly comprises tobermorite (5CaO6SiO 25H 2O), in the x-ray diffractogram of powder of cured calcium silicate object, about (220) planar diffraction peak intensity Ib of tobermorite and observed minimum diffracted intensity Ia in (220) plane of tobermorite and the peak-to-peak diffraction angle scope of two diffraction of (222) planar respectively, preferred Ib/Ia minimum is 3, and more preferably minimum is 4.In the present invention, " x-ray diffractogram of powder " represents the x-ray diffractogram of powder that use CuK alpha-ray obtains as X ray.
In the present invention, the cross section by using the sem observation cured calcium silicate object also uses x-ray powder diffraction analysis, whether mainly comprises tobermorite to judge cured calcium silicate object.Particularly, judgement is as follows.
First, in the x-ray diffractogram of powder of cured calcium silicate object, the planar diffraction peak intensity is higher (promptly when (220) of the strength ratio tobermorite that does not have diffraction peak, higher than intensity the highest in each planar diffraction peak intensity of tobermorite) time, judge that cured calcium silicate object mainly comprises tobermorite.Yet, it is to be noted, when cured calcium silicate object comprises at least a high crystalline coexisting substances that is selected from crystalline silica, lime carbonate and gypsum in addition, even when cured calcium silicate object mainly comprises tobermorite, the diffraction peak intensity of coexisting substances (wherein, cured calcium silicate object comprises at least two kinds of coexisting substances, and the diffraction peak intensity of coexisting substances is meant intensity maximum in the diffraction peak intensity of coexisting substances) (220) planar diffraction peak intensity of surpassing tobermorite also is possible.Therefore, the second, using ratio of enlargement is the cross section of * 2,500 the following observation hardenite of scanning electronic microscope.In cross section, select 20 parts (area that has 35.4 μ m * 18.9 μ m separately) at random, wherein the various piece in 20 parts all is arranged in the matrix of hardenite, and described matrix is different from the thick bubble part (as described below) of using whipping agent to form.Using ratio of enlargement then is * 2, these 20 parts of 500 sem observation, with respect to these 20 parts (area that has 35.4 μ m * 18.9 μ m separately), obtain the ratio (%) that the tabular of tobermorite and bar shaped particle account for the area of described part, calculate the mean value of 20 area ratios that so obtain then.When the mean value of 20 area ratios more than or equal to 50% the time, judge that hardenite mainly comprises tobermorite.The mean value minimum of preferred 20 area ratios is 60%, and more preferably minimum is 80%.In this article, " thick bubble part " is meant that thick bubble itself adds that the about 5 μ m of the thick bubble of distance are with near interior part.Because thick bubble partly has the space, may in thick bubble part, form tobermorite.Even comprise above-mentioned at least a high crystalline coexisting substances and tobermorite and when the mean value minimum of above-mentioned 20 area ratios is 50% when cured calcium silicate object, (220) the planar diffraction peak intensity Ib of the preferred tobermorite of cured calcium silicate object in x-ray diffractogram of powder and the diffracted intensity Ic of high crystalline coexisting substances satisfy relations I c/Ib≤3, more preferably Ic/Ib≤2, wherein, when cured calcium silicate object comprised at least two kinds of coexisting substances, intensity I c was meant intensity maximum in the diffraction peak intensity of coexisting substances.When above-mentioned use ratio of enlargement was * 2,500 sem observation, " the tabular or bar shaped particle " of tobermorite was meant the particle with following feature.Using ratio of enlargement is that * 5,000 scanning electronic microscope is further observed the tobermorite particle.Distance between two surfaces parallel to each other basically of particulate equals particulate minimum length (hereinafter, the particulate minimum length often is called particulate " thickness ").When the particulate maximum length was at least 5 times of particle minimum length, defining this particle was the tabular of tobermorite or bar shaped particle.Certainly, particulate maximum length and thickness are meant the length of two-dimensional projection separately.There is not specific restriction for tobermorite particulate size.Yet preferred tobermorite particulate maximum length is several microns to 10 microns.
Usually, tobermorite and low-crystalline calcium silicate hydrate (being called hereinafter, " CSH ") coexistence.Known CSH has multiple different particle form.Because CSH exists with particulate form such as fibrous, granular or bulk form usually, can under the observation of electron microscope, clearly distinguish tobermorite particle and CSH.Only otherwise destroy the basic framework of tobermorite, cured calcium silicate object of the present invention can comprise this CSH.Yet in cured calcium silicate object, the existence of CSH can make multiple performance (as intensity, weathering resistance and the weather resistance) variation of the hardenite of material of construction needs.When in cured calcium silicate object, comprising a large amount of CSH, reduce in the dimensional stability that repeats dry and wetting cured calcium silicate object afterwards.In addition, when cured calcium silicate object was placed air for a long time, because CSH is easy and carbon dioxide in air generation carbonation reaction, CSH may resolve into lime carbonate and amorphous silicate.Carbonation reaction is attended by the volumetric shrinkage of cured calcium silicate object, so cured calcium silicate object produces the crack and recurring structure destroys.Therefore, even when the cross section that uses the sem observation cured calcium silicate object with use the powder x-ray diffraction analysis cured calcium silicate object to be judged as cured calcium silicate object when mainly comprising tobermorite, CSH content is as far as possible little in the also preferred cured calcium silicate object.
As mentioned above, can easily distinguish CSH particle and tobermorite particle by under electron microscope, observing.Yet,, under electron microscope, observe the coexisting substances that is difficult to clearly distinguish the CSH particle and is different from CSH sometimes, as the fibrous gypsum and the microgranular lime carbonate of denier existence because CSH has multiple particle form.Therefore, be difficult to determine CSH content by under electron microscope, observing.In the x-ray diffractogram of powder of cured calcium silicate object of CSH and tobermorite coexistence therein, in (220) plane of tobermorite and the peak-to-peak diffraction angle scope of two diffraction of (222) planar, observe the wide diffraction peak of CSH respectively.The diffraction peak of CSH appears in the angle of about 29.1 ° to 29.4 ° (2 θ) usually.When the amount of CSH during less than the amount of tobermorite, the diffraction peak of CSH is incorporated in the diffraction peak of tobermorite, can not measure the diffraction peak intensity of CSH usually.
Yet, on the other hand, when comprising a large amount of CSH in the cured calcium silicate object, the diffracted intensity in (220) plane of tobermorite and two peak-to-peak diffraction angle of diffraction of (222) planar is higher than background intensity respectively, can judge whether comprise a large amount of CSH in the cured calcium silicate object thus.When not comprising CSH in the cured calcium silicate object and mainly being made up of the high crystalline tobermorite, the minimum diffracted intensity in the above-mentioned angular region equals background intensity.
In addition, even when not comprising CSH in the cured calcium silicate object, when the degree of crystallinity of tobermorite was hanged down, the ratio of Ib/Ia diminished.Its reason is closer to each other in (220) plane and (222) planar diffraction peak of tobermorite respectively, makes two peaks overlapping at its baseline.When the degree of crystallinity of tobermorite was hanged down, the intensity of cured calcium silicate object and weathering resistance reduced.
Therefore, when not containing CSH in the cured calcium silicate object, Ib/Ia is than (promptly, (220) planar diffraction peak intensity Ib of tobermorite and the ratio of observed minimum diffracted intensity Ia in (220) plane of tobermorite and the peak-to-peak diffraction angle scope of two diffraction of (222) planar respectively) big more, then the degree of crystallinity of tobermorite is high more.When comprising CSH in the cured calcium silicate object, Ib/Ia is bigger than more, and then the content of CSH is more little in the high more and cured calcium silicate object of the degree of crystallinity of tobermorite.Each self-contained background intensity of the intensity of Ia and Ib.The example of Ia value and Ib value as shown in Figure 1.
Preferred cured calcium silicate object of the present invention (it has low proportion) is in its x-ray diffractogram of powder, and (002) planar diffraction peak intensity I (002) of tobermorite satisfies relations I (002)/I (220) 〉=0.25 with the ratio of (220) planar diffraction peak intensity I (220) of tobermorite.More preferably I (002)/I (220) 〉=0.30.In the tabular of tobermorite or bar shaped particle, think that particulate thickness direction (that is, perpendicular to the planar direction) is a crystalline C axle.Therefore, when the relative intensity of I (002)/I (220) increased, the regular relatively of crystalline C axle increased.Therefore, the tabular or bar shaped particulate thickness of tobermorite increases.In JCPDS (Joint Committee on PowderDiffraction Standard) card No.19-1364, ideal tobermorite crystalline I (002)/I (220) has been described than being 0.8.Along with the ratio of I (002)/I (220) near 0.8, the thickness of tobermorite increases, so crystalline intensity increases, and causes that the intensity of cured calcium silicate object increases.The method of calculating I (002) and I (220) as shown in Figure 2.I (002) is the true diffracted intensity by near the background linear-apporximation the diffraction angle of 6 ° to 9 ° (2 θ) is obtained.Similarly, I (220) is the true diffracted intensity by near the background linear-apporximation the diffraction angle of 20 ° to 40 ° (2 θ) is obtained.
In the present invention, the apparent specific gravity of preferred cured calcium silicate object is 0.05 to 0.25, more preferably 0.05 to 0.2, more preferably 0.05 to 0.18.In the present invention, term " apparent specific gravity " is the apparent specific gravity of instigating cured calcium silicate object to be measured after 105 ℃ of dryings 24 hours, that is, and and over dry proportion.
Cured calcium silicate object of the present invention can comprise or not comprise a large amount of bubbles, yet preferred cured calcium silicate object comprises a large amount of bubbles.Term " bubble " is meant and uses aluminium powder as the bubble (described aluminium powder is generally used in the production of Autoclaved lightweight concrete) that whipping agent forms, perhaps is meant the bubble that uses tensio-active agent to form as the pre-frothing agent in the pre-frothing method that is used for the production Autoclaved lightweight concrete.
When cured calcium silicate object of the present invention comprised a large amount of bubbles, preferred cured calcium silicate object had been different from the part of bubble, is promptly forming in the part of skeleton (matrix) and have hole.In addition, the thickness of matrix is little between preferred bubble.
Cured calcium silicate object of the present invention can be advantageously used for wall material for building, as above-mentioned dynamic thermal insulation material, common thermal insulation material and sound absorbent material.When with cured calcium silicate object during as wall material for building, preferred cured calcium silicate object is a plate shape.As long as can keep tabular, there is not specific restriction for the size and the thickness of this plate.When cured calcium silicate object when being tabular, guarantee the resistance to air loss that dynamic Thermo Isolation Technique is required easily and simplify its construction.
The method of producing cured calcium silicate object of the present invention will be described hereinafter.
Cured calcium silicate object can arrive the method production of (4) by may further comprise the steps (1):
(1) provide the aqueous slurry that comprises water and solid mixture,
Described solid mixture is made up of following material basically: silicic acid material, matrix material, at least a aluminum compound that is selected from Tai-Ace S 150 and hydrate thereof, at least a sulphate cpd of the vitriol that is different from Tai-Ace S 150 and hydrate thereof and the Calcareous material optionally of being selected from
Wherein in the weight of solid mixture, the amount of contained at least a aluminum compound is with Al in the aqueous slurry 2O 3The conversion scale be shown 0.09-10 weight %; With the weight in solid mixture, the amount of the contained at least a sulphate cpd that is different from Tai-Ace S 150 and hydrate thereof is with SO in the aqueous slurry 3The conversion scale be shown 0.15-15 weight %, SO 3Amount be the SO that is equivalent at least a aluminum compound 3Amount and be equivalent to the SO of sulphate cpd 3The summation of amount,
Wherein the weight ratio of water and solid mixture be 2.3 to 5.5 and
Wherein the weight ratio of Calcareous material and matrix material is 0.6 to the maximum;
(2) add whipping agent in hydrotropisms's slurry;
(3) aqueous slurry is poured in the mould; With
(4) make aqueous slurry pre-hardening, carry out autoclaved then.
In the present invention, term " silicic acid material " is meant the SiO that comprises at least 70 weight % 2Be different from SiO 2Metal oxide such as aluminum oxide as the material of component.The example of silicic acid material comprises silica material; Silica sand; Quartzy; Have high-load silica material, silica sand or quartzy rock; Diatomite; Siliceous smog; Float dirt; Natural clay mineral; With diatomite, siliceous smog, the calcination product of floating dirt or natural clay mineral.This wherein, crystalline silicic acid material, silica sand, quartz and to have high-load silica material be crystallinity silicic acid material.Term " crystallinity silicic acid material " is meant the silicic acid material of the sharp-pointed diffraction peak feature of observing alpha-quartz, cristobalite etc. in x-ray diffractogram of powder.On the other hand, " amorphous silicic acid material " is meant the silicic acid material of not observing sharp-pointed diffraction peak in x-ray diffractogram of powder.The example of amorphous silicic acid material comprises diatomite, siliceous smog and floats dirt.
In the present invention, term " matrix material " is meant the cement of mainly being made up of silicate component and calcium component.The example of matrix material comprises common portland cement, early strong Portland cement and belite cement.Term " Calcareous material " is meant the Calcareous material that comprises at least 50 weight % unslaked limes (CaO), and it comprises the calcium carbonate component that is different from unslaked lime (CaO) in addition, as slaked lime (Ca (OH) 2) and lime carbonate (CaCO 3).
In addition, in the present invention, term " Tai-Ace S 150 " is meant and comprises by formula Al 2(SO 4) 3The material of shown compound.Term " hydrate of Tai-Ace S 150 " is meant the hydrated product of Tai-Ace S 150.The example of aluminum sulfate hydrate comprises the material of sulfur acid aluminium and crystal water, suc as formula Al 2(SO 4) 317H 2Material shown in the O.Can use every kind of Tai-Ace S 150 and hydrate thereof with the form of powder or slurry.In the present invention, in the weight of hydrate, need wherein from hydrate, to get rid of the Al in the aluminum sulfate hydrate after the weight of crystal water 2(SO 4) 3Amount minimum be 80 weight %.In the gross weight of solid material, the consumption of Tai-Ace S 150 or its hydrate is with Al 2O 3The conversion scale be shown O.09-10 weight %, preferred 0.2-10 weight %, more preferably 0.5-8 weight %.
As long as sulphate cpd comprises SO 3Or SO 4, the above-mentioned sulphate cpd that is different from Tai-Ace S 150 is not had specific restriction.The example of this sulphate cpd comprises sulfurous acid; Sulfuric acid; Dehydrated gyp-(CaSO 4); The parget water compound is as dihydrate gypsum (CaSO 42H 2O) and semi-hydrated gypsum (CaSO 41/2H 2O); Alkaline earth metal sulphate is as sal epsom; Alkali metal sulfates is as sodium sulfate; With the metal sulfate that is different from alkaline earth metal sulphate and alkali metal sulfates, as copper sulfate and Sulfuric acid disilver salt.Above-mentioned sulphate cpd can be used singly or in combination.Yet, preferably use dihydrate gypsum or its hydrate.In the gross weight of solid material, the amount SO of at least a sulphate cpd in the aqueous slurry 3The conversion scale be shown 0.15-15 weight %, be preferably 0.2-10 weight %, wherein SO 3Amount be the SO that is equivalent at least a aluminum compound 3Amount and be equivalent to the SO of at least a sulphate cpd 3The summation of amount.
In addition, in the method for the invention, the weight ratio of above-mentioned Calcareous material and matrix material is shown with the conversion scale of CaO and is 0.6 to the maximum, preferably is 0.4 to the maximum, more preferably is 0.3 to the maximum.Yet, even when the weight ratio of Calcareous material and matrix material greater than 0.6, also can be by at least two kinds of Additive Production cured calcium silicate objects of the present invention that are selected from tensio-active agent, viscosity modifier and antifoams of adding in above-mentioned aqueous slurry.For the adding of above-mentioned additive, the adding of viscosity modifier and antifoams be added in step (1) afterwards and step (2) carry out before, the adding of whipping agent is carried out simultaneously in the adding of tensio-active agent and the step (2).In addition, in the present invention, even be 0.6 to the maximum when the weight ratio of Calcareous material and matrix material, also can be to add above-mentioned additive greater than 0.6 o'clock identical mode with the weight ratio of above-mentioned Calcareous material and matrix material.
The example of tensio-active agent comprises aniorfic surfactant, as higher alcohol sulfate and higher alcohol sulfate; And nonionic surface active agent, as Voranol EP 2001.The consumption of tensio-active agent is counted 0.01-200 weight % with solid weight contained in the whipping agent, preferred 0.1-100 weight %.
Above-mentioned viscosity modifier is at least a compound that is selected from methylcellulose gum and polyvinyl alcohol.The consumption of viscosity modifier is counted 0.01-1 weight % with the weight of solid mixture, preferred 0.02-0.5 weight %.
The example of antifoams comprises siloxanes, as dimethyl siloxane and the alkyl-modified siloxanes that replaces the methyl of dimethyl siloxane to form with the hydrocarbon with at least two carbon atoms; Aliphatic acid, as have the aliphatic acid of glycerol skeleton; Aliphatic ester is as glycerine aliphatic acid ester and sucrose aliphatic acid ester; Higher alcohols is as octanol; Phosphoric acid ester is as aromatic phosphoric ester and aliphatic phosphate ester.In these antifoams,, preferably use siloxanes, particularly dimethyl siloxane and alkyl-modified siloxanes from giving cured calcium silicate object with hydrophobic angle.The consumption agent of antifoams is counted 0.001-3 weight % with the weight of solid mixture, preferred 0.005-2 weight %, more preferably 0.01-2 weight %.
In the method for the invention, the weight ratio of water and above-mentioned solid mixture (that is the solid of water/aqueous slurry ratio) is necessary for 2.3 to 5.5.When the water of aqueous slurry/solid than less than 2.3 the time, can not obtain the formed body (that is, cured calcium silicate object) of apparent specific gravity in scope required for the present invention, and the formed body that obtains has too high thermal conductivity easily.On the other hand, when the water of aqueous slurry/solid than greater than 5.5 the time, the solid mixture in the aqueous slurry and water have tendency separated from one another, so can not obtain formed body.
In the present invention, term " whipping agent " is meant aluminium powder during being used in Autoclaved lightweight concrete usually produces etc.Form for aluminium powder does not have specific restriction, can use the aluminium powder of any form of using in the ordinary method of production Autoclaved lightweight concrete.The example of the ordinary method of production Autoclaved lightweight concrete comprises the method that wherein aluminium powder itself is added as whipping agent; Wherein in advance aluminium powder and water (being used to prepare the part of the aqueous slurry institute water that contains raw material of Autoclaved lightweight concrete) are mixed, obtain the aluminium slurry, thereby improve the method for the dispersiveness of aluminium powder in comprising the aqueous slurry of raw material; Wherein add and be used for the method (referring to United States Patent (USP) 4,318,270) of the aluminum paste of production Autoclaved lightweight concrete as whipping agent.In this article, term " aluminium slurry " is meant the water dispersion of aluminium powder.The content of aluminium powder is counted 0.1-50 weight % with aqueous weight in the aluminium slurry in the above-mentioned aluminium slurry, preferred 1-30 weight %, more preferably 2-10 weight %.In the weight of solid mixture, the consumption of whipping agent is expressed as 0.03-0.95 weight % with contained solid weight percentage in the whipping agent, preferred 0.05-0.7 weight %, more preferably 0.08-0.5 weight %.The volume ratio of aqueous slurry before the aqueous slurry of foaming and the foaming is preferably 1.5 to 4.0, and more preferably 2.0 to 3.5, most preferably 2.5 to 3.5.
CaO and SiO in the aqueous slurry that provides first in the method for the invention 2Mol ratio (CaO/SiO 2Than), be preferably 0.5 to 1.1, more preferably 0.6 arrive less than 1.0.
In the production method of cured calcium silicate object of the present invention, the silicic acid material of preferred at least 50 weight % is a crystallinity silicic acid material.For crystallinity silicic acid material, preferably use the pulverizing powder of silica, to measure according to the Blaine osmose process, its specific surface area minimum is 5,000cm 2/ g, more preferably 7,000cm 2/ g.The very fine comminuted powder of silica material is disadvantageous, and reason is the silica material intractable of this form.Therefore, the specific surface area of the pulverizing powder of preferred silica is 300 to the maximum, 000cm 2/ g.
In the production method of cured calcium silicate object of the present invention, stirring comprises the aqueous slurry of solid mixture, and wherein said solid mixture is made up of following material basically: silicic acid material, matrix material, at least a aluminum compound that is selected from Tai-Ace S 150 and hydrate thereof, be different from the sulphate cpd of Tai-Ace S 150 and hydrate thereof and Calcareous material optionally.The temperature of aqueous slurry is preferably 40 ℃ to 100 ℃, more preferably 50 ℃ to 80 ℃.In addition, the time of stirring aqueous slurry is preferably the shortest to be 2 minutes, and more preferably the shortest is 10 minutes.The stirring that comprises the above-mentioned aqueous slurry of solid mixture can be undertaken by commercially available mixing machine.For this mixing machine, the preferred use is equipped with the mixing machine of the high speed rotating blade that can be used for the low viscosity mortar, as is equipped with the blade-paddle mixer of traverse baffle.
In the method for the invention, when whole Calcareous materials (its for optionally raw material) are mixed with silicic acid material and matrix material simultaneously, there is Calcareous material to make the danger of the initial water composition and division in a proportion reduction of matrix material.Therefore, when after aqueous slurry being poured in the mould, attempting to promote the pre-hardening of aqueous slurry, preferred aqueous slurry: (i) water is mixed with the solid mixture that does not comprise Calcareous material or with the solid mixture that comprises a part of Calcareous material by providing in the prepared the inventive method that may further comprise the steps, obtain the mixture of slurry form, wherein be blended under 40 ℃ to 100 ℃ the temperature and carry out 10 minutes to being less than 5 hours; (ii) whole Calcareous materials or remaining Calcareous material are joined in the resulting mixture of step (i), under 40 ℃ to 100 ℃ temperature, mixed 30 seconds to 1 hour more preferably 1 minute to 30 minutes then.The aqueous slurry that obtains is poured in the mould.Hereinafter, in step (i) feed intake and be called " first charging " of raw material, step (ii) in feeding intake of raw material be called " second feeds ".
In addition, preferably in above-mentioned steps (i), above-mentioned aluminum compound is mixed with water and the solid material that is different from aluminum compound, and under 40 ℃ to 100 ℃ temperature, stir the mixture that obtains and arrived less than 5 hours in 10 minutes.
As long as before adding whipping agent, add, there is not specific restriction for the selection of time that adds viscosity modifier and antifoams.Yet preferably after the feeding intake of solid mixture, add viscosity modifier and antifoams immediately.In addition, tensio-active agent and whipping agent are joined in the aqueous slurry simultaneously.
Preferably after feeding intake, solid mixture adds whipping agent.The time of stirring aqueous slurry after wherein adding whipping agent is preferably 10 seconds to 3 minutes, more preferably 20 seconds to 1 minute.When churning time was less than 10 seconds, whipping agent had and can not be evenly dispersed in the aqueous slurry, thereby caused that bubble merges into the tendency of thick bubble.On the other hand,, whipping agent generation adverse effect is arranged, cause the merging of bubble and the tendency of froth breaking when churning time during more than 3 minutes.
As selection, can also obtain cured calcium silicate object of the present invention by the method for pre-frothing.The example of preferred pre-frothing method comprise wherein air is incorporated into form foam materials in pre-frothing agent or its aqueous solution, then by with foam materials and above-mentioned aqueous slurry blended method (disclosing Sho 63-295487) referring to unexamined Japanese patent application; Wherein the pre-frothing agent is mixed with aqueous slurry, and make the method for the slurry foaming that obtains by the pre-frothing machine.In the pre-frothing method, do not use whipping agent.Yet, be necessary to add viscosity modifier and antifoams.In the pre-frothing method, can use every kind of identical viscosity modifier of amount in the method with above-mentioned use whipping agent and antifoams.Type to the pre-frothing agent does not have specific restriction, can use conventional pre-frothing agent used in the art.The example of pre-frothing agent comprises synthetic surfactant type pre-frothing agent, the pre-frothing agent of sodium resinate type and protein hydrolysate type pre-frothing agent.
In the present invention, preferred cured calcium silicate object comprises the water repellent agent of 0.1-3.0 weight %, thereby gives cured calcium silicate object with water repellency.There is not specific restriction for give the method for cured calcium silicate object by the use water repellent agent with water repellency.For example, preferably using so-called " vapor deposition method ", is 100 ° of high water contact angles thereby can realize reaching minimum.
Type for water repellent agent does not have specific restriction.The example of water repellent agent comprises silicone compounds, alkoxysilane compound containing trialkylsilyl group in molecular structure, lipid acid, soap and resin emulsion, and described resin emulsion comprises at least a resin that is selected from Resins, epoxy, urethane resin, silicone resin, vinyl acetate resin, acrylic resin and phenylethylene/butadiene resin.These water repellent agents can be used singly or in combination.In these water repellent agents, particularly preferably be silicone compounds, as silicone oil (as dimethione, wherein methyl can be by replacements such as hydrogen atom, phenyl, trifluoro propyls); And alkoxysilane compound containing trialkylsilyl group in molecular structure, as alkylalkoxy silane (as Union carbide A-162, ethyl triethoxysilane, propyl-triethoxysilicane and isobutyl-triethoxyl silane).The content of water repellent agent is preferably 0.1-3.0 weight %, more preferably 0.5-2 weight % in the cured calcium silicate object.When the content of water repellent agent is lower than 0.1 weight %, can not produce required water repellency.On the other hand, when the content of water repellent agent was higher than 3.0 weight %, the intensity of cured calcium silicate object reduced.
Only otherwise weaken the performance of cured calcium silicate object, cured calcium silicate object of the present invention also can comprise a spot of reinforcing fiber, aglite, resin etc.The use of reinforcing fiber helps improving the intensity of cured calcium silicate object.The example of reinforcing fiber comprises inorganic fibre, as alkali resistant glass fibre, carbon fiber, Stainless Steel Fibre, ceramic fiber and fibrous magnesium silicate; And organic fibre, as Kevlar, polyvinyl alcohol fiber, polypropylene fibre and pulp fibers.These reinforcing fibers can be used singly or in combination.In these reinforcing fibers, from obtaining the angle of required reinforcement ability, preferred aramid fiber, alkali resistant glass fibre and carbon fiber.In Kevlar, most preferably to aromatic polyamide fibre (paraaramid).In addition, from the angle of cost performance, also preferred pulp fibers.For pulp fibers, particularly preferably be the pulverizing pulp.Staple length for reinforcing fiber does not have specific restriction.Yet from the angle of reinforcement ability and formability, the staple length of reinforcing fiber is preferably 1mm to 20mm, and more preferably 3mm is to 10mm, and more preferably 5mm is to 8mm.In addition, the amount for cured calcium silicate object MR medium reinforcing fiber does not have specific restriction.The amount of hardenite MR medium reinforcing fiber is preferably 0.05 volume % to 3 volume % with the volumeter of cured calcium silicate object, and more preferably 0.1 volume % is to 2 volume %.Wherein the volume of hardenite comprises the volume of the bubble that wherein exists.When the amount of reinforcing fiber during less than 0.05 volume %, can not be satisfactory by the improvement of using the cured calcium silicate object intensity that reinforcing fiber obtains.On the other hand, when the amount of reinforcing fiber during greater than 3 volume %, when the raw material that will be used to produce cured calcium silicate object (comprising reinforcing fiber) mixed, fiber may form fibrous nodules by tied up in knots, makes reinforcing fiber be difficult to be evenly dispersed in the hardenite.In addition for aglite, can use in those aggregates that are generally used for reducing weight concrete any, as silicone rubber ball and perlite.Consumption for aglite in the cured calcium silicate object of the present invention does not have specific restriction.Yet the amount of aglite is preferably 0.1-30 weight %, more preferably 1-20 weight % in the weight of solid mixture.In addition, for resin, the preferred use has stable on heating resin, as resol and resole.Consumption for resin in the cured calcium silicate object of the present invention does not have specific restriction.Yet the amount of resin is preferably 0.1-30 weight %, more preferably 1-20 weight % in the weight of solid mixture.
In the aqueous slurry impouring mould that will obtain by mixing raw material and pre-hardening, carry out autoclaved then.If desired, can before being poured into aqueous slurry in the mould, above-mentioned water repellent agent and/or above-mentioned reinforcing fiber be joined in the aqueous slurry.If desired, described mould can have reinforcement iron bar or the reinforcement of weld net that is arranged in wherein.In this case, preferred above-mentioned reinforcement iron bar or reinforcement of weld net have passed through antirust processing.The heat that produces by aqueous slurry itself or make aqueous slurry pre-hardening the mould from the indirect heating aqueous slurry.The pre-hardening of preferred aqueous slurry was carried out 1 hour at least 48 hours at 40 ℃ to 100 ℃.For mould, can use and carry out autoclaved chamber etc.Preferably carry out the prevulcanized evaporation that suppresses moisture in the aqueous slurry simultaneously at aqueous slurry.By the pre-hardening of aqueous slurry, obtain the pre-hardening body.By autoclave the pre-hardening body that obtains is carried out high temperature and high pressure and carry out autoclaved.If desired, before the pre-hardening body carries out autoclaved, the pre-hardening body is cut into required shape.Can carry out the cutting of pre-hardening body by normally used any ordinary method in the production Autoclaved lightweight concrete.The example of this ordinary method comprises the process of chopping of using steel wire.Preferably the pre-hardening body carries out autoclaved 160 ℃ of (gauge pressures: about 5.3kgf/cm2) to 220 ℃ of (gauge pressures: carry out under the temperature about 22.6kgf/cm2).To press the hardenite drying that obtains by the pre-hardening body is steamed, thus the cured calcium silicate object that obtains.
The cured calcium silicate object of the present invention that so obtains shows high thermal insulating properties and high air penetrability simultaneously.Therefore, cured calcium silicate object of the present invention can be advantageously used for dynamic thermal insulation material.In addition, cured calcium silicate object of the present invention not only has workability, cost performance and high-intensity excellent properties, and is non-combustible.Therefore, cured calcium silicate object of the present invention is suitable for as dynamic thermal insulation material.
Preferred embodiment
Hereinafter, will the present invention be described in more detail with reference to following examples and comparing embodiment, but should be with following examples and comparing embodiment as limitation of the scope of the invention.
In following examples and comparing embodiment, carry out various measurements and analysis by the following method.
(thermal conductivity)
Use heat flowmeter to measure thermal conductivity according to JIS A-1412, wherein the cold drawing temperature is that 5 ℃ of hot plate temperatures are 35 ℃.The specimen size of using is 200mm * 200mm * 25mm (thickness), it has been kept the constant weight up to sample under 20 ℃ and 60% humidity.
(air penetrability)
Use measurement device air penetrability shown in Figure 3.Particularly, air penetrability is measured as follows.Preparation right cylinder sample 1 (cross-sectional area (S)=50mm φ; Length (L)=50mm) except the surface at right cylinder sample two ends, is sealed the surface of right cylinder sample with Resins, epoxy.Then, sample 1 is placed in the sample holder 2 that internal surface is equipped with rubber packing, wherein said rubber packing can seal tightly the inside of sample holder 2 by the air compression.Then, the pressure of use vacuum pump 3, regulating in the pressure regulating tanks 5 by pressure regulator valve 4.When the pressure difference of measuring by differential pressure meter 6 is 1kPa, by the flow rate of air under meter 7 measure sample.The flow rate of air from the sample of measuring is calculated air penetrability according to following equation (1).
Air penetrability (m 2h -1Pa -1)=W * L/S/ Δ P (1)
Wherein:
W: the flow rate (m of air 3h -1);
L: sample length (m);
S: the cross-sectional area (m of sample 2); With
Δ P: pressure difference (Pa).
Measuring sample 1 is kept constant weight up to sample under 20 ℃ and 60% humidity.
(flexural strength and compressive strength)
With cured calcium silicate object remain in the climatic chamber (wherein temperature and relative humidity (RH) remain on 20 ℃ and 60% respectively) up to the water content (in the weight of the hardenite of absolute dry condition) of hardenite become 10 ± 2%.The hardenite that obtains is used as the sample of measuring flexural strength and compressive strength.Sample size is 40mm * 40mm * 160mm.Measure the flexural strength and the compressive strength of cured calcium silicate object according to JIS R5201.Particularly, make sample through the flexural strength test, wherein span is 100mm.In the flexural strength test, the sample applying load up to being destroyed, it is two portions.Use to destroy to be one in two portions sample, it is as follows to measure compressive strength.Measuring maximum load, and is the compressive strength of cured calcium silicate object with the maximum load value defined that obtains to the sample applying load of 40mm * 40mm area.
(apparent specific gravity)
From the cured calcium silicate object that carries out autoclaved take off with the test of above-mentioned flexural strength the sample of same size.Sample was descended dry 24 hours at 105 ℃, then the weight of calculation sample and size (volume).Apparent specific gravity from the measured value calculation sample of example weight and volume.
(measurement of powder X-ray diffractometry: Ia and Ib)
Use mortar that the sample substantially the same with the sample of use in the above-mentioned flexural strength test pulverized, obtain being used for the sample of powder X-ray diffractometry.By X-ray diffraction device (trade(brand)name: RINT 2000; Rigaku Corporation by Japan produces and sells), use the K alpha-ray of Cu to measure diffraction peak intensity Ib and minimum diffracted intensity Ia.Measure and to carry out under the following conditions, wherein acceleration voltage is 40kV, and the acceleration electric current is 200mA, and the slit-widths of light-receiving slit is 0.15mm, and sweep velocity is that 4 °/minute and sample are 0.02 °.After by the graphite monochromator monochromatization, count the X ray of diffraction.
Ia is defined as respectively observed minimum diffracted intensity in (220) plane of tobermorite and the peak-to-peak diffraction angle scope of two diffraction of (222) planar, and wherein said intensity comprises background intensity.Ib is defined as tobermorite (220) planar diffraction peak intensity, and wherein said intensity comprises background intensity.(220) plane of tobermorite and (222) planar diffraction ray are respectively that diffraction angle is the diffraction ray of about 29.0 ° and about 30.0 ° (2 θ).Fig. 1 represents how to obtain the value of Ia and Ib.
(measurement of powder X-ray diffractometry: I (002) and I (220))
The sample and the measuring condition that use are substantially the same with the measurement of above-mentioned Ia and Ib.I (002) is the true diffracted intensity by near the background linear-apporximation the diffraction angle of 6 ° to 9 ° (2 θ) is obtained.Similarly, I (220) is the true diffracted intensity by near the background linear-apporximation the diffraction angle of 20 ° to 40 ° (2 θ) is obtained.Tobermorite (002) planar diffracted ray is that diffraction angle is the diffracted ray of about 7.7 ° (2 θ).The method representation of measuring I (220) and I (002) is in Fig. 2.
(sawing)
Use Carpenter's saw cutting cured calcium silicate object, be used to estimate the sawing of cured calcium silicate object.Particularly, according to the easy degree of cured calcium silicate object cutting and the sawing of cutting the ocular estimate cured calcium silicate object of the cross section that obtains.
Embodiment 1 to 13
In each embodiment of embodiment 1 to embodiment 13, use solid mixture and aquatic product cured calcium silicate object.The various type of material of solid mixture and the scale of consumption and water are shown in the table 1.Particularly, in embodiment 1 to embodiment 13, use following material preparation solid mixture.For the silicic acid material, and the pulverizing powder of use silica (the Blaine specific surface area: 11,000cm 2/ g) and siliceous smog (produce and sell) by the EFACO of Egypt.For matrix material, in embodiment 1 to embodiment 8, use early strong Portland cement, in embodiment 9 to embodiment 13, use common portland cement.For Calcareous material, use unslaked lime (purity: 98%).For aluminum compound, use Patent alum.For the sulphate cpd that is different from Tai-Ace S 150 and hydrate thereof, use dihydrate gypsum.For tensio-active agent, in embodiment 1 to embodiment 5, use Voranol EP 2001 (nonionic surface active agent), in embodiment 6 to embodiment 13, use EMAL 20T (the Kao Corporation by Japan produces and sells) (aniorfic surfactant).For viscosity modifier, use methylcellulose gum, for antifoams, use alkyl-modified siloxanes (by the Shin-Etsu Chemical Co. of Japan, Ltd. production and selling).For organic fibre, in embodiment 10 and 13, use the pulp of pulverizing form.For every kind of Patent alum and dihydrate gypsum, its amount of representing in table 1 is the weight part of its anhydrous form.In addition, for tensio-active agent, its amount of representing in table 1 is expressed as weight % in solid weight contained in the whipping agent.The water of expression/solid is than the weight ratio for solid mixture and water in table 1.
In each embodiment 1 to embodiment 8, use the following production cured calcium silicate object of above-mentioned solid mixture.First charging (definition as above) for raw material, it is that described stainless steel was bathed and comprised 50 ℃ water during 15 liters stainless steel was bathed that the pulverizing powder of silica, siliceous smog, unslaked lime, early strong Portland cement, Patent alum and dihydrate gypsum, viscosity modifier and antifoams are dosed into volume.By agitator (ultra stirrer DC-CHRM25, by Japanese IuchiSeieido Co., Ltd. produce and sell) with 1, the rotating speed of 200rpm stirs the content that stainless steel is bathed, under barometric point, stirred two hours, moisture evaporation during bath of heating stainless steel and inhibition stainless steel are bathed under 50 ℃ simultaneously, thus mixture obtained.Then, only in embodiment 4 and embodiment 5, the mixture that obtains is cooled to 40 ℃, adds second charging (definition as above) of unslaked lime as raw material then in the stainless steel bath, the content in 40 ℃ the stirring stainless steel is bathed down is 1 minute then.In the mixture that obtains, add whipping agent (to the aluminium powder that wherein adds tensio-active agent), stir 20 seconds then, thereby obtain aqueous slurry.The aqueous slurry impouring that obtains is of a size of in the mould of 30cm * 30cm * 20cm and aqueous slurry is foamed in mould.After being poured into aqueous slurry in the mould, aqueous slurry suppresses moisture simultaneously and evaporates from aqueous slurry immediately 60 ℃ of following pre-hardening, thereby obtains the pre-hardening body of Calucium Silicate powder.
In each embodiment of embodiment 9 to embodiment 13, except to use common portland cement be 60 ℃ water as matrix material, use temperature and stir the stainless steel content and simultaneously 60 ℃ the heating stainless steel is bathed down after first charging, with the method production cured calcium silicate object substantially the same with embodiment 1.In addition, in embodiment 13, unslaked lime is put in the stainless steel bath as second charging of raw material, stirred 1 minute down at 60 ℃ then.
With Calucium Silicate powder pre-hardening the body demoulding and high temperature and carried out autoclaved 4 hours in saturation steam atmosphere, carrying out high pressure under 190 ℃ from mould, dry then, thus obtain formed body (cured calcium silicate object).
The multiple performance of the formed body (cured calcium silicate object) that obtains in each embodiment of embodiment 1 to embodiment 13 is as shown in table 3.The x-ray diffractogram of powder of the cured calcium silicate object that obtains in embodiment 13 as depicted in figs. 1 and 2.
Embodiment 14
In embodiment 14, as shown in table 1 and do not use tensio-active agent and the antifoams except the consumption of raw material, with embodiment 9 in substantially the same method produce formed body (cured calcium silicate object).The multiple performance of the formed body that obtains is as shown in table 3.
Embodiment 15
In embodiment 15, as shown in table 1 and do not use tensio-active agent and the antifoams except the consumption of raw material, with embodiment 11 in substantially the same method produce formed body (cured calcium silicate object).The multiple performance of the formed body that obtains is as shown in table 3.
Comparing embodiment 1 and comparing embodiment 2
In comparing embodiment 1 and comparing embodiment 2, except not using tensio-active agent, binding agent and antifoams, respectively with embodiment 4 and 13 in substantially the same method produce formed body (cured calcium silicate object).The multiple performance of the formed body that obtains is as shown in table 4.
Comparing embodiment 3
In comparing embodiment 3, use the raw material shown in the table 2, with comparing embodiment 2 in substantially the same method produce formed body (cured calcium silicate object).The multiple performance of the formed body that obtains is as shown in table 4.
Comparing embodiment 4 and comparing embodiment 5
In each embodiment of comparing embodiment 4 and comparing embodiment 5, except not using tensio-active agent, antifoams and pulverizing pulp, with embodiment 13 in substantially the same method produce formed body (cured calcium silicate object).The multiple performance of the formed body that obtains is as shown in table 4.
Comparing embodiment 6
In comparing embodiment 6, except not using tensio-active agent and antifoams, with embodiment 13 in substantially the same method produce formed body (cured calcium silicate object).The multiple performance of the formed body that obtains is as shown in table 4.
Comparing embodiment 7
In comparing embodiment 7, except the consumption of raw material is as shown in table 4, and do not use outside viscosity modifier and the aluminium powder, with embodiment 14 in substantially the same method produce formed body (cured calcium silicate object).
Comparing embodiment 8
In comparing embodiment 8, prepared commercially available adiabatic ALC (HEBELD  MMPLATTE is produced and sold by German Hebel) sample.For sample, measured its multiple performance.The result is as shown in table 4.
Comparing embodiment 9
With 78 weight part temperature 45 ℃ water, 0.5 weight part tensio-active agent (EMAL20T; Produce and sell by Japanese Kao Corporation), 0.8 weight part viscosity modifier (0.4 weight part methylcellulose gum and 0.4 weight part melamine-type viscosity-depression agent), 0.4 weight part antifoams (alkyl-modified silicone oil) (produced and sold by Japanese Shin-Etsu Chemical Co.) and 0.12 weight part whipping agent (aluminium powder) join, and to comprise 51 weight part median sizes be the SiO 2 powder of about 20 μ m, the early strong Portland cement of 42 weight parts, in the solid mixture of 5 weight part unslaked limes and 2 weight part dihydrate gypsums.The mixture that obtains was stirred 2 minutes, thereby obtain the wherein mixed uniformly aqueous slurry of component.The aqueous slurry that obtains is heated to 43 ℃, is poured in the mould then and remains on 45 ℃, semi-harden up to aqueous slurry.With hardenite (the Calucium Silicate powder pre-hardening body) demoulding that obtains and and in saturation steam atmosphere, carrying out autoclaved 4 hours under the 10atm under 180 ℃ through high pressure, dry then, thus obtain formed body (cured calcium silicate object).For the formed body that obtains, measure its multiple performance.The result is as shown in table 4.
Comparing embodiment 10
Prepare commercially available sound-absorbing ALC (Shizukalite; By Japanese CLION Co., Ltd. produces and sells) sample.For sample, measure its multiple performance.The result is as shown in table 4.
Comparing embodiment 11
Prepare commercially available rock wool (Homemat; Produce and sell by Japanese NICHIAS Corporation) sample.For sample, measure its multiple performance.The result is as shown in table 4.Sample can not carry out the measurement of flexural strength and compressive strength to sample, because can not keep its shape.In addition, also be impossible to the evaluation of the sawing of sample, because the fiber of sample is mixed sawtooth, therefore can not cut sample.
Comparing embodiment 12
Prepare commercially available glass wool (MAT-ACE; Produce and sell by Japanese ASAHI FIBER GLASS Co.) sample.For sample, measure its multiple performance.The result is as shown in table 4.Sample can not carry out the measurement of flexural strength and compressive strength to sample, because can not keep shape.In addition, also be impossible to the evaluation of the sawing of sample, because the fiber of sample is mixed sawtooth, therefore can not cut sample.
Table 1
Raw material Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Cement First charging (weight part) 123.2 123.2 123.2 61.8 61.8
Unslaked lime First charging (weight part) 24.6 24.6 24.6 20.9 20.9
Second charging (weight part) 0.0 0.0 0.0 48.8 48.8
Crystallized silicon stone flour flour First charging (weight part) 60.0 60.0 60.0 69.8 69.8
Siliceous smog First charging (weight part) 40.0 40.0 40.0 46.5 46.5
Gypsum First charging (weight part) 11.7 11.7 11.7 11.7 11.7
Tai-Ace S 150 First charging (weight part) 10.8 10.8 10.8 10.8 10.8
Water (weight part) 878.5 878.5 878.5 878.5 878.5
Pulverize pulp (weight part) 0.0 0.0 0.0 0.0 0.0
Aluminium powder (weight part) 1.19 1.19 1.19 1.14 1.14
Tensio-active agent (weight %) 2 10 100 10 100
Viscosity modifier (weight part) 0.18 0.18 0.18 0.18 0.18
Antifoams (weight part) 0.00 0.00 0.00 0.00 0.00
CaO/SiO 2 (mol ratio) 0.93 0.93 0.93 0.93 0.93
Water/solid ratio (weight ratio) 3.25 3.25 3.25 3.25 3.25
CaO/ cement (weight ratio) 0.2 0.2 0.2 1.1 1.1
The amount of Tai-Ace S 150 is (with Al 2O 3Meter) (weight %) 1.2 1.2 1.2 1.2 1.2
The total amount of Tai-Ace S 150 and sulphate cpd is (with SO 3Meter) (weight %) 3.5 3.5 3.5 3.5 3.5
Table 1 (continuing)
Raw material Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10
Cement First charging (weight part) 123.2 123.2 123.2 127.1 127.1
Unslaked lime First charging (weight part) 24.6 24.6 24.6 25.4 25.4
Second charging (weight part) 0.0 0.0 0.0 0.0 0.0
Crystallized silicon stone flour flour First charging (weight part) 60.0 60.0 60.0 60.0 60.0
Siliceous smog First charging (weight part) 40.0 40.0 40.0 40.0 40.0
Gypsum First charging (weight part) 11.7 11.7 11.7 10.6 10.6
Tai-Ace S 150 First charging (weight part) 10.8 10.8 10.8 11.0 11.0
Water (weight part) 878.5 878.5 878.5 755.6 755.6
Pulverize pulp (weight part) 0.0 0.0 0.0 0.0 2.8
Aluminium powder (weight part) 1.19 1.19 1.19 1.15 1.15
Tensio-active agent (weight %) 4 40 100 0.10 0.10
Viscosity modifier (weight part) 0.18 0.18 0.18 0.15 0.15
Antifoams (weight part) 0.28 0.28 0.28 0.03 0.03
CaO/SiO 2 (mol ratio) 0.93 0.93 0.93 0.93 0.93
Water/solid ratio (weight ratio) 3.25 3.25 3.25 2.7 2.7
CaO/ cement (weight ratio) 0.2 0.2 0.2 0.2 0.2
The amount of Tai-Ace S 150 is (with Al 2O 3Meter) (weight %) 1.2 1.2 1.2 1.2 1.2
The total amount of Tai-Ace S 150 and sulphate cpd is (with SO 3Meter) (weight %) 3.5 3.5 3.5 3.2 3.2
Table 1 (continuing)
Raw material Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15
Cement First charging (weight part) 127.0 127.0 53.8 127.1 127.0
Unslaked lime First charging (weight part) 25.4 25.4 18.3 25.4 25.4
Second charging (weight part) 0.0 0.0 42.5 0.0 0.0
Crystallized silicon stone flour flour First charging (weight part) 60.0 60.0 60.0 60.0 60.0
Siliceous smog First charging (weight part) 40.0 40.0 40.0 40.0 40.0
Gypsum First charging (weight part) 11.1 10.6 9.0 10.6 11.1
Tai-Ace S 150 First charging (weight part) 23.0 11.0 9.4 11.0 23.0
Water (weight part) 1008.2 1089.9 642.0 755.6 1008.2
Pulverize pulp (weight part) 0.0 0.0 7.2 0.0 0.0
Aluminium powder (weight part) 1.53 0.99 0.98 1.15 1.53
Tensio-active agent (weight %) 0.10 0.10 0.10 0 0
Viscosity modifier (weight part) 0.21 0.22 0.13 0.15 0.21
Antifoams (weight part) 0.03 0.03 0.02 0.00 0.00
CaO/SiO 2 (mol ratio) 0.93 0.93 0.93 0.93 0.93
Water/solid ratio (weight ratio) 3.5 4.0 2.7 2.7 3.5
CaO/ cement (weight ratio) 0.2 0.2 1.1 0.2 0.2
The amount of Tai-Ace S 150 is (with Al 2O 3Meter) (weight %) 2.4 1.2 1.2 1.2 2.4
The total amount of Tai-Ace S 150 and sulphate cpd is (with SO 3Meter) (weight %) 4.2 3.2 3.2 3.2 4.2
Table 2
Raw material Comparing embodiment 1 Comparing embodiment 2 Comparing embodiment 3 Comparing embodiment 4 Comparing embodiment 5 Comparing embodiment 6 Comparing embodiment 7
Cement First charging (weight part) 61.8 53.8 53.8 53.9 53.9 53.9 127.1
Unslaked lime First charging (weight part) 20.9 18.3 18.2 18.2 18.2 18.2 25.4
Second charging (weight part) 48.8 42.5 42.6 42.5 42.5 42.5 0.0
Crystallized silicon stone flour flour First charging (weight part) 69.8 60.0 60.0 70.0 70.0 70.0 100.0
Siliceous smog First charging (weight part) 46.5 40.0 40.0 30.0 30.0 30.0 0.0
Gypsum First charging (weight part) 11.7 9.0 9.4 8.0 8.0 8.0 9.4
Tai-Ace S 150 First charging (weight part) 10.8 9.4 19.6 9.4 9.4 9.4 11.0
Water (weight part) 878.5 642.0 1229.6 640.0 640.0 640.0 765.3
Pulverize pulp (weight part) 0.0 7.2 0.0 0.0 0.0 6.6 0.0
Aluminium powder (weight part) 1.140 0.976 0.744 0.477 0.353 0.353 0.0
Viscosity modifier (weight part) 0.0 0.0 0.0 0.13 0.13 0.13 0.0
CaO/SiO 2 (mol ratio) 0.93 0.93 0.93 0.93 0.93 0.93 0.93
Water/solid ratio (weight ratio) 3.3 2.7 5.0 2.8 2.8 2.7 2.8
CaO/ cement ratio (weight ratio) 1.1 1.1 1.1 1.1 1.1 1.1 0.2
The amount of Tai-Ace S 150 is (with Al 2O 3Meter) (weight %) 1.2 1.2 2.4 1.2 1.2 1.2 1.2
The total amount of Tai-Ace S 150 and sulphate cpd is (with SO 3Meter) (weight %) 3.5 3.2 4.2 3.0 3.0 3.0 3.0
Annotate: in each comparing embodiment of comparing embodiment 6, the aluminium powder that uses is aluminium slurry form in comparing embodiment 1, and wherein the content of aluminium powder of aluminium slurry is counted 5 weight % with the weight of water contained in the aluminium slurry.
Table 3
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Apparent specific gravity (g/cm 3) 0.12 0.14 0.15 0.16 0.15
The Ib/Ia of x-ray diffractogram of powder 3.5 3.3 3.4 4.2 4.1
The I of x-ray diffractogram of powder (002)/I (220) 0.32 0.33 0.33 0.36 0.35
Flexural strength (N/mm 2) 0.13 0.14 0.15 0.20 0.21
Compressive strength (N/mm 2) 0.31 0.38 0.44 0.57 0.57
Thermal conductivity (W/mK) 0.048 0.052 0.053 0.055 0.054
Air penetrability (m 2/hPa) 6.1×10 -3 1.3×10 -2 1.3×10 -2 8.3×10 -3 8.7×10 -3
Sawing Visual observation Well Well Well Well Well
Table 3 (continuing)
Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10
Apparent specific gravity (g/cm 3) 0.11 0.16 0.11 0.11 0.11
The Ib/Ia of x-ray diffractogram of powder 3.5 3.3 3.4 3.7 3.7
The I of x-ray diffractogram of powder (002)/I (220) 0.33 0.32 0.33 0.30 0.31
Flexural strength (N/mm 2) 0.15 0.14 0.16 0.13 0.15
Compressive strength (N/mm 2) 0.38 0.39 0.37 0.27 0.30
Thermal conductivity (W/mK) 0.047 0.055 0.046 0.046 0.045
Air penetrability (m 2/hPa) 3.8×10 -3 1.1×10 -2 9.5×10 -3 3.4×10 -3 2.3×10 -3
Sawing Visual observation Well Well Well Well Well
Table 3 (continuing)
Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15
Apparent specific gravity (g/cm 3) 0.083 0.094 0.11 0.11 0.082
The Ib/Ia of x-ray diffractogram of powder 4.0 3.3 4.0 3.7 4.1
The I of x-ray diffractogram of powder (002)/I (220) 0.40 0.39 0.34 0.31 0.32
Flexural strength (N/mm 2) 0.074 0.081 0.15 0.14 0.073
Compressive strength (N/mm 2) 0.12 0.14 0.35 0.28 0.12
Thermal conductivity (W/mK) 0.042 0.043 0.045 0.045 0.041
Air penetrability (m 2/hPa) 5.4×10 -3 3.3×10 -3 6.5×10 -4 1.8×10 -3 4.0×10 -3
Sawing Visual observation Well Well Well Well Well
Table 4
Comparing embodiment 1 Comparing embodiment 2 Comparing embodiment 3 Comparing embodiment 4 Comparing embodiment 5 Comparing embodiment 6
Apparent specific gravity (g/cm 3) 0.11 0.11 0.11 0.14 0.21 0.22
The Ib/Ia of x-ray diffractogram of powder 4.0 4.1 4.22 4.25 4.51 4.6
The I of x-ray diffractogram of powder (002)/I (220) 0.33 0.33 0.342 0.33 0.29 0.31
Flexural strength (N/mm 2) 0.15 0.14 0.13 0.27 0.52 0.49
Compressive strength (N/mm 2) 0.32 0.31 0.23 0.75 1.4 1.39
Thermal conductivity (W/mK) 0.046 0.046 0.045 0.054 0.068 0.070
Air penetrability (m 2/hPa) 3.1×10 -5 1.1×10 -4 1.9×10 -5 9.8×10 -6 1.8×10 -6 2.2×10 -6
Sawing Visual observation Well Well Well Well Well Well
Table 4 (continuing)
Comparing embodiment 7 Comparing embodiment 8 Comparing embodiment 9 Comparing embodiment 10 Comparing embodiment 11 Comparing embodiment 12
Apparent specific gravity (g/cm 3) 0.36 0.12 0.380 0.350 0.024 0.020
The Ib/Ia of x-ray diffractogram of powder 4.2 4.4 3.4 3.6 - -
The I of x-ray diffractogram of powder (002)/I (220) 0.29 0.35 0.35 0.44 - -
Flexural strength (N/mm 2) 1.59 0.17 0.420 0.440 - -
Compressive strength (N/mm 2) 5.4 0.51 1.30 1.50 - -
Thermal conductivity (W/mK) 0.106 0.043 0.132 0.121 0.042 0.04
Air penetrability (m 2/hPa) 11×10 -8 1.5×10 -4 9.4×10 -3 2.1×10 -2 0.13 0.15
Sawing Visual observation Well Produce a large amount of sawdust Well Well Can not cut Can not cut
Industrial applicibility
Cured calcium silicate object of the present invention not only has light weight and high intensity, and does not fire. In addition, cured calcium silicate object of the present invention shows high thermal insulating properties and high air penetrability simultaneously. Therefore, described cured calcium silicate object can be advantageously used for and build wall material for building (that is, dynamic heat-insulating material) and the sound-absorbing material that need to show dynamic thermal insulating properties.
Conventional dynamic heat-insulating material does not fire fully. On the other hand, cured calcium silicate object of the present invention is fully non-flame properties, and it is preferably tabular to may be molded to dynamic heat-insulating material, therefore, when hardenite of the present invention when being tabular, is easy to simplify its operation and guarantees air-tightness required in the dynamic Thermo Isolation Technique.

Claims (11)

1. cured calcium silicate object, it is minimum for the flexural strength of 0.05MPa with have (2) 0.02-0.1Wm that it has (1) -1K -1Thermal conductivity and (3) 5 * 10 -4-1m 2h -1Pa -1Air penetrability, thereby show dynamic thermal insulating properties.
2. the cured calcium silicate object of claim 1, it has 0.02-0.08Wm -1K -1Thermal conductivity.
3. the cured calcium silicate object of claim 1, it has 0.02-0.06Wm -1K -1Thermal conductivity.
4. each cured calcium silicate object in the claim 1 to 3, it mainly comprises tobermorite, and in its x-ray diffractogram of powder, (220) planar diffraction peak intensity Ib of tobermorite and respectively in (220) plane of tobermorite and the peak-to-peak diffraction angle scope of two diffraction of (222) planar observed minimum diffracted intensity Ia satisfy relations I b/Ia 〉=3.
5. the production method of cured calcium silicate object, it comprises:
(1) provide the aqueous slurry that comprises water and solid mixture,
Described solid mixture is made up of following material basically: silicic acid material, cement, at least a aluminum compound that is selected from Tai-Ace S 150 and hydrate thereof, at least a sulphate cpd of the vitriol that is different from Tai-Ace S 150 and hydrate thereof and the Calcareous material optionally of being selected from
Wherein in the weight of described solid mixture, the amount of the described at least a aluminum compound that comprises in the described aqueous slurry is with Al 2O 3The conversion scale be shown 0.09-10 weight %; With the weight in described solid mixture, the amount of the described at least a sulphate cpd that comprises in the described aqueous slurry is with SO 3The conversion scale be shown 0.15-15 weight %, described SO 3Amount be the SO that is equivalent to described at least a aluminum compound 3Amount and be equivalent to the SO of described at least a sulphate cpd 3The summation of amount,
Wherein the weight ratio of water and solid mixture be 2.3 to 5.5 and
Wherein the weight ratio of Calcareous material and matrix material is 0.6 to the maximum;
(2) in described aqueous slurry, add whipping agent;
(3) described aqueous slurry is poured in the mould; With
(4) make described aqueous slurry pre-hardening, carry out autoclaved then.
6. the method for claim 5, wherein said whipping agent is to be selected from aluminium powder and to contain at least a in the aluminium aqueous slurry and wherein be expressed as 0.03-0.95 weight % in the consumption of the described whipping agent of weight of described solid mixture with contained solid weight percentage in the whipping agent.
7. the production method of cured calcium silicate object, it comprises:
(1) provide the aqueous slurry that comprises water and solid mixture,
Described solid mixture is made up of following material basically: silicic acid material, cement, at least a aluminum compound that is selected from Tai-Ace S 150 and hydrate thereof, at least a sulphate cpd of the vitriol that is different from Tai-Ace S 150 and hydrate thereof and the Calcareous material optionally of being selected from
Wherein in the weight of described solid mixture, the amount of the described at least a aluminum compound that comprises in the described aqueous slurry is with A1 2O 3The conversion scale be shown 0.09-10 weight %; With the weight in described solid mixture, the amount of the described at least a sulphate cpd that comprises in the described aqueous slurry is with SO 3The conversion scale be shown 0.15-15 weight %, described SO 3Amount be the SO that is equivalent to described at least a aluminum compound 3Amount and be equivalent to the SO of described at least a sulphate cpd 3The summation of amount,
Wherein the weight ratio of water and solid mixture be 2.3 to 5.5 and
Wherein the weight ratio of Calcareous material and matrix material is greater than 0.6;
(2) in described aqueous slurry, add whipping agent;
(3) described aqueous slurry is poured in the mould; With
(4) make described aqueous slurry pre-hardening, carry out autoclaved then,
Wherein in described aqueous slurry, add at least two kinds of additives that are selected from tensio-active agent, viscosity modifier and antifoams, condition be the adding of viscosity modifier and antifoams be added in that described step (1) is carried out before with described step (2) afterwards and being added in the described step (2) of tensio-active agent carried out simultaneously with the adding of described whipping agent.
8. the method for claim 7, wherein said whipping agent is to be selected from aluminium powder and to contain at least a in the aluminium aqueous slurry and wherein be expressed as 0.03-0.95 weight % in the consumption of the described whipping agent of weight of described solid mixture with contained solid weight percentage in the whipping agent.
9. the method for claim 7, wherein said tensio-active agent is at least aly to be selected from the compound of higher alcohol sulfate, higher alcohol sulfate and Voranol EP 2001 and to be 0.01-200 weight % in the consumption of the described tensio-active agent of the contained solid weight of described whipping agent wherein.
10. the method for claim 7, wherein said viscosity modifier are at least aly to be selected from the compound of methylcellulose gum and polyvinyl alcohol and to be 0.01-1 weight % in the consumption of the described viscosity modifier of weight of described solid mixture wherein.
11. the method for claim 7, wherein said antifoams are at least aly to be selected from the compound of siloxanes, aliphatic acid, aliphatic ester, pure and mild phosphoric acid ester and to be 0.001-3 weight % in the consumption of the described antifoams of weight of described solid mixture wherein.
CNB038156857A 2002-07-03 2003-07-03 Calcium silicate hardened article Expired - Fee Related CN100352786C (en)

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DE202008017703U1 (en) * 2008-09-15 2010-05-12 Xella Technologie- Und Forschungsgesellschaft Mbh cellular concrete material
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