CN1358687A - Calcium silicate board and making method thereof - Google Patents
Calcium silicate board and making method thereof Download PDFInfo
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- CN1358687A CN1358687A CN 01125549 CN01125549A CN1358687A CN 1358687 A CN1358687 A CN 1358687A CN 01125549 CN01125549 CN 01125549 CN 01125549 A CN01125549 A CN 01125549A CN 1358687 A CN1358687 A CN 1358687A
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Abstract
The production method of calcium silicate plate is characterized by that 5-30 wt% of calcium silicate hydrate slurry, 17-50 wt% of calcarious raw material, 13-45 wt% of siliceous raw material, 2-8 wt% of fibrous raw material and 5-40% of inorganic filling material are used as raw material, and formed by emans of conventional process, then the formed product is undergone the process of hydrothermal reaction in pressure container so as to the invented product which possesses reduced specific weight and raised strength, and its bulk density is about 0.5-0.8.
Description
The present invention relates to the manufacture method and the calcium silicate board obtained by this method of calcium silicate board.
In the past, calcium silicate board was because amount was light and have good processibility and features such as dimensional stability and flame retardant resistance, and was widely used as material of construction, was mainly used in interior finish.
The moulding method of the calcium silicate board that uses as this material of construction, usually utilize and copy slurry method, compression moulding and individual layer moulding method, to contain the molding that the raw slurry mold pressing of inorganic filling materials such as calcareous raw material, silicic acid raw material, fortifying fibre and light weight aggregate etc. forms, and in pressurized vessel, react and solidify and make with saturated vapor.The loose density of this calcium silicate board is usually in 0.7～1.2 scope.
Yet the purposes of calcium silicate board is inner decoration materials such as smallpox sheet material, wall material, wishes further lightweight, but uses aforesaid method, reaches about 0.5～0.8 for lightweight makes loose density, must cooperate considerable light weight compaction material.The problem that exists specific tenacity to reduce.
Particularly in copying the slurry method, when for example making the light weight calcium silicate board of loose density below 1.0, the weak strength and the water content of molding are many before the hydro-thermal reaction, thereby surplus water produces thermal expansion in the hydro-thermal reaction, vapour pressure raises, and also often produces the problem of splitting or explosion.
In order to prevent these problems, adopt and after shaping, compress, carry out hydro-thermal reaction thereafter, and the method for in hydro-thermal reaction, reinforcing with parbuckle screw, but the shortcoming of these methods is loose density height, labor intensive during manufacturing.
Disclose the method for removing surplus water in the Te Kaiping 6-287083 communique, but owing to needed special pressurized vessel or vapor superheater, the general method of therefore can not saying so.
So far, also having by heat the former slip that contains calcareous raw material and uncrystalline silicon acid starting material under normal pressure makes its gelation seek light-weighted method, but can not avoid intensity to reduce with this method, and the material softness, be ground easily when grinding, therefore the fluffiness of cellulose-type fiber etc. becomes seriously, impairs the problem of surface smoothing doing to decorate existence when using.
As other method, open clear 52-105926 communique and the spy opens in the clear 52-135330 communique the spy, disclosing by adding as calcium silicate hydrate a kind of is that xonotlite slip or crystalline calcium slip are to obtain the calcium silicate board of good strength.But,, require to improve therefore from the manufacturing cost viewpoint because this method productivity is low.
Present inventors open flat 5-213657 communique and the spy opens in the flat 7-41354 communique the spy, disclose to add the gelation slip be made up of calcareous raw material and uncrystalline silicon acid starting material and the method for crystalline calcium silicate hydrate.Yet, even in the method for adding this gel, with copying the problem that also can have splitting or explosion when the slurry method is made veneer sheet.
A kind of method of making the Calucium Silicate powder molding is disclosed in the public clear 58-30259 communique of spy, it is characterized in that silicic acid raw material and lime raw material are dispersed in respect to these raw material solid state components is to obtain mixture in the water more than 15 times of weight, this mixture is made it reaction in the temperature more than 130 ℃ heating adding to depress, with 15cm
3The above settling volume of/g forms the water-based slip that contains the Calucium Silicate powder of being made up of C-S-H or tobermorite, adds asbestos then in this water-based slip, after dehydration is shaped, further makes the calcium silicate hydrate transfer adding to depress by the water vapor maintenance.Yet Calucium Silicate powder molding obtained by this method uses as lagging material or thermal insulation material, and according to the embodiment of this communique, its loose density is 0.1～0.2g/cm
3About be a kind of low-density material, openly not can be used as the manufacture method of the Calucium Silicate powder molding that material of construction uses with calcium silicate board.
Therefore, first purpose of the present invention is to provide a kind of can not reduce productivity, but can obtain manufacture method and calcium silicate board obtained by this method that density reduces the calcium silicate board with 0.5～0.8 left and right sides loose density of effect and matrix strength rising effect.
Second purpose of the present invention is to provide the reactive good raw material of a kind of use with calcareous raw material, before hydro-thermal reaction, carry out 1 maintenance, solve above-mentioned shortcoming by the intensity that improves molding (not slaking plate), can not produce the loose density of peeling off explosion in hydro-thermal reaction is the manufacture method of the calcium silicate board below 1.0.
It is in the manufacture method of the calcium silicate board below 0.70 in the loose density of using the gel of being made up of with the silicic acid raw material with calcareous raw material and gelation gelation that the 3rd purpose of the present invention is to provide a kind of, by before hydro-thermal reaction, carrying out 1 maintenance, the intensity that improves molding solves above-mentioned shortcoming, and can not produce in hydro-thermal reaction and peel off or explosion, thereby the apparent density with good interlaminar strength is calcium silicate board and manufacture method thereof below 0.70.
That is to say, the present invention relates to the manufacture method of calcium silicate board, it is characterized in that, after will being shaped by customary way by the former slip that solid conversion amount contains silicic acid hydrate of calcium slip 5～30 weight %, calcareous raw material 17～50 weight %, silicic acid raw material 13-45 weight %, cellulose raw material 2-8 weight % and inorganic fillings 5～40 weight %, the gained molding being placed on carrying out hydro-thermal reaction (to call " the 1st invention " in the following text) in the pressurized vessel.
The invention still further relates to a kind of calcium silicate board, it is characterized in that, it is the calcium silicate board that makes with aforesaid method, and its loose density is in 0.5～0.8 scope and abrasion index (to call " the 2nd invention " in the following text) in 0.3～2 scope.
" abrasion index " is to carry out according to JISK7204, is continuous 1000 gravimetric minimizings with loading 1000g, abrasion wheels kind CS-10, test number (TN) during test, calculates abrasion index by following formula:
The weight of abrasion index=minimizing (g)/loose density
And then, the present invention relates to the manufacture method of light weight calcium silicate board (following simply be called " calcium silicate board "), the former slip that will contain calcareous raw material 17～50 weight %, silicic acid raw material 15～45 weight %, cellulose raw material 2-8 weight % and inanimate matter packing material 5～40 weight % as solids component is in accordance with regulations behind the shape die forming, in the manufacture method of the light weight calcium silicate board that the gained molding is carried out hydro-thermal reaction and form in pressurized vessel, it is characterized in that, as the part of silicic acid raw material, use specific surface area to be 1m by 2～20 weight %
2Uncrystalline silicon acid starting material or more than a kind or 2 kinds of silicate starting materials that/g is above, and before molding is carried out hydro-thermal reaction, molding is carried out 1 maintenance (to call the 3rd invention in the following text) under the condition more than (curing temperature-15) * curing time=120 ℃ hour.
That is to say, the present invention relates to the manufacture method that loose density is the calcium silicate board below 0.70, to contain calcareous raw material 5～35 weight % as solids component, silicic acid raw material 5-40 weight %, cellulose raw material 2-8 weight %, inanimate matter packing material 5～40 weight % and the former slip of using the gel of silicic acid raw material 3～25 weight % acquisition by gelation with calcareous raw material 2～20 weight % and gelation, after copying slurry method laminating molding, the gained molding is carried out hydro-thermal reaction and form in the manufacture method of calcium silicate board in pressurized vessel, it is characterized in that, as the part of silicic acid raw material, use specific surface area to be 1m by 2～20 weight %
2Uncrystalline silicon acid starting material or more than a kind or 2 kinds of silicate starting materials that/g is above, and before molding was carried out hydro-thermal reaction, molding is carried out 1 maintenance under the condition more than (curing temperature-15) * curing time=120 ℃ hour to make the flexural strength of this molding under wetting regime be 7kg/cm
2More than and be more than 1.3 times of flexural strength (to call " the 4th invention " in the following text) before 1 maintenance.
The invention still further relates to the manufacture method that loose density is the calcium silicate board below 0.70, to contain calcareous raw material 5～35 weight % as solids component, silicic acid raw material 5～40 weight %, cellulose raw material 2-8 weight %, inanimate matter packing material 5～40 weight % and the former slip that contains gel that obtains with silicic acid raw material 3-25 weight % with calcareous raw material 2-20 weight % and gelation by gelation, after copying slurry method laminating molding, the gained molding is carried out hydro-thermal reaction and form in the manufacture method of calcium silicate board in pressurized vessel, it is characterized in that, as the part of silicic acid raw material, press 2-20 weight % and use specific surface area to be 1m
2Uncrystalline silicon acid starting material or more than a kind or 2 kinds of silicate starting materials that/g is above, and then, former slip contains the solidifying agent that is selected from portland cement, alundum cement and blast furnace granulated slag with the amount below the 20 weight %, and before making molding carry out hydro-thermal reaction, molding is carried out 1 maintenance under the condition more than (curing temperature-10) * curing time=120 ℃ hour to make the flexural strength of this molding under wetting regime be 7kg/cm
2More than and be more than 1.3 times of flexural strength (to call " the 5th invention " in the following text) before 1 maintenance.
The invention still further relates to the manufacture method that loose density is the calcium silicate board below 0.70, to contain calcareous raw material 5～35 weight % as solids component, silicic acid raw material 5～40 weight %, cellulose raw material 2-8 weight %, inanimate matter packing material 5～40 weight % and the former slip that contains gel that obtains with silicic acid raw material 3-25 weight % with calcareous raw material 2～20 weight % and gelation by gelation, after copying slurry method laminating molding, the gained molding is carried out hydro-thermal reaction and form in the manufacture method of calcium silicate board in pressurized vessel, it is characterized in that, former slip contains with the amount below the 20 weight % and is selected from portland cement, the solidifying agent of alundum cement and blast furnace granulated slag, and before making molding carry out hydro-thermal reaction, molding is carried out 1 maintenance under the condition more than (curing temperature-10) * curing time=120 ℃ hour to make the flexural strength of this molding under wetting regime be 7kg/cm
2More than and be more than 1.3 times of flexural strength (to call " the 6th invention " in the following text) before 1 maintenance.
The invention still further relates to loose density and be the calcium silicate board below 0.70, it is characterized in that, it is to be calcium silicate board below 0.7 with the loose density that aforesaid method makes, and its interlaminar strength is more than 3% of flexural strength (to call " the 7th invention " in the following text).
The manufacture method of the calcium silicate board that relates in the present invention's the 1st invention is characterised in that, the calcium silicate hydrate slip that uses, be by being that 0.3～0.8 calcareous raw material and the slip that adds water in crystalline silicic acid raw material are depressed at saturation steam and carried out amorphousness that hydro-thermal reaction the obtains calcium silicate hydrate slip as main body in the scope of reactivity 40～80% that makes crystalline silicic acid raw material with Ca/ (Si+Al) mol ratio, this slip has the settling volume of 5～14ml/g.
Use in the 1st method that relates to of invention with the present invention with the calcium silicate hydrate slip of amorphousness as main body, be to be that the slip that adds water in 0.3～0.8 calcareous raw material, the crystalline silicic acid raw material is depressed at saturation steam, carried out hydro-thermal reaction in water than 10～20, under 120～200 ℃ of the temperature, the condition in 3～8 hours reaction times, make the reactivity of crystalline silicic acid raw material reach 40～80% slip Ca/ (Si+Al) mol ratio.
,, for example can use slaked lime, unslaked lime etc. herein,, for example can use silica sand, burn till diatomite etc. as crystalline silicic acid raw material as calcareous raw material.If the Ca/ of above-mentioned slip (Si+Al) mol ratio less than 0.3, then to lower the last ascending effect of effect and matrix strength little for the few thereby density of the calcium silicate hydrate of Sheng Chenging.If surpass 0.8 then, water ratio is uprised, produce rate variance thereby be disadvantageous because settling volume increases.
During the reactivity less than 40% of crystalline silicic acid raw material, the calcium silicate hydrate of generation less therefore density to reduce the last ascending effect of effect and matrix strength little; If surpass 80% settling volume increase, water ratio is uprised, produce rate variance thereby be disadvantageous.And the crystallization phases of crystalline silicic acid raw material is quartz or cristobalite, and reactivity can be measured by powder x-ray diffraction according to standard addition method, and crystallization phases is used (101) under the situation of quartz, uses the peak value of (101) face under the situation of cristobalite.
Make as stated above with the calcium silicate hydrate slip of amorphousness as main body, settling volume is in the scope of 5～14ml/g, when this calcium silicate hydrate slip is used as the calcium silicate board raw material, productivity is reduced, can obtain the effect that density lowers effect and matrix strength rising.Settling volume, by get solid form based on the calcium silicate hydrate slip 7g of amorphousness in the measurement tube of 200ml, become 200ml after adding water, measure and leave standstill the settling volume after 3 hours and try to achieve.
The essentially consist of the former slip that uses in the calcium silicate board manufacture method that the present invention's the 1st invention relates to, contain with calcium silicate hydrate slip 5～30 weight %s, calcareous raw material 17～50 weight %s, silicic acid raw material 13～45 weight %s, cellulose raw material 2-8 weight % and inanimate matter packing material 5～40 weight %s of above-mentioned amorphousness by solids component conversion amount as main body, carry out hydro-thermal reaction in the pressurized vessel with being placed on behind the former slip press forming, can make calcium silicate board through habitual operation thereafter.Hydro-thermal reaction can be in pressurized vessel, temperature is 150～200 ℃ under the saturated vapor, and preferred 170～190 ℃, time are 5～20 hours, carry out under preferred 8～12 hours condition.
Herein, with the use level of amorphousness as the calcium silicate hydrate slip of main body, when pressing solids component conversion less than 5 weight %, density lowers effect and reduces; Loose density was fallen lowly excessively when this use level surpassed 30 weight % by solids component conversion amount, and therefore the calcium silicate board insufficient strength is disadvantageous when using as building materials.
As calcareous raw material, for example can use slaked lime, unslaked lime etc.The use level less than 17 weight % of calcareous raw material, or when surpassing 50 weight %, flexural strength reduces, and is disadvantageous because therefore the size changing rate that suction causes increases.
As the silicic acid raw material, for example can use silica sand, cigarette ash, diatomite, silica flour, white carbon, zeolite, montmorillonite etc.The use level less than 15 weight % of silicic acid raw material, or when surpassing 45 weight %, flexural strength reduces, and is disadvantageous because therefore the size changing rate that suction causes increases.
As cellulose raw material, for example can use cellulosic fibre, polypropylene, vinylon, glass fibre, carbon fiber.If the use level deficiency of cellulose raw material 2 weight %, then flexural strength reduces thereby is disadvantageous; If surpass 8 weight % then do not have flame retardant resistance thereby also be disadvantageous.When using polypropylene, vinylon, glass fibre, carbon fiber etc., its use level is preferably in below the 5 weight %.
As the inanimate matter packing material, for example can use halite, wollastonite, mica, talcum, lime carbonate, gypsum etc.If the use level deficiency of inanimate matter packing material 5 weight % are then because therefore the size changing rate that suction causes increase is disadvantageous; If surpass 40 weight % then therefore flexural strength reduces is disadvantageous.
As manufacturing process, copy and anyly in the conventional processes such as slurry method, compression molding and individual layer moulding method all can use, no matter its kind how.
The 2nd calcium silicate board that relates to of invention of the invention described above, although loose density in 0.5～0.8 scope, its matrix strength and wear-resistant degree are also very high.
The essentially consist of the former slip that uses in the calcium silicate board manufacture method that the present invention's the 3rd invention relates to is the habitual composition that contains calcareous raw material 17-50 weight %, silicic acid raw material 15～45 weight %, cellulose raw material 2～8 weight % and inanimate matter packing material 5～40 weight % as solids component.
Herein, as calcareous raw material, can use and above-mentioned same material.The use level less than 17 weight % of calcareous raw material or when surpassing 50 weight % flexural strength reduce be disadvantageous because therefore the size changing rate that suction causes increases.
As the silicic acid raw material, for example can use silica sand, cigarette ash etc., the use level less than 15 weight % of silicic acid raw material or when surpassing 45 weight % flexural strength reduce because the size changing rate that suction causes increases so is disadvantageous.
As cellulose raw material, can use material same as described above.If the use level deficiency of cellulose raw material 2 weight %, therefore flexural strength reduces is disadvantageous; If therefore surpass 8 weight % then do not have flame retardant resistance is disadvantageous.When using polypropylene, vinylon, glass fibre, carbon fiber etc., its use level must be below 5 weight %.
As the inanimate matter packing material, can use material same as described above.If the use level deficiency of inanimate matter packing material 5 weight %, then the size changing rate that causes owing to suction increases thereby is disadvantageous; If surpass 40 weight %, then flexural strength reduces so is disadvantageous.
The 1st of the method that the present invention's the 3rd invention relates to is characterised in that, as having the part of the silicic acid raw material of the former slip of components matching as described above, uses specific surface to be 1m
2Uncrystalline silicon acid starting material or silicate starting materials that/g is above.Herein, " specific surface area " put down in writing in this specification sheets is meant and passes through N
2The specific surface area that gas adsorption method is measured.If the not enough 1m of the specific surface area of uncrystalline silicon acid starting material or silicate starting materials
2/ g, then reactive poor, therefore can not give before hydro-thermal reaction and give enough intensity without the plate of slaking is disadvantageous.
Specific surface area 1m
2The uncrystalline silicon acid starting material that/g is above or the use level of silicate starting materials are in 2～20 weight % scopes.During this use level less than 2 weight %, manifesting property of intensity is bad so be disadvantageous; If surpass 20 weight %, drainability reduces, and therefore productivity is low is disadvantageous.Use specific surface area at 1～10m
2During raw material in the/g scope, its use level is preferably in more than the 10 weight %; Use 10～100m
2During raw material in the/g scope, its use level is preferably in more than the 5 weight %; Use 100m
2During the above raw material of/g, its use level is preferably in more than the 2 weight %.
As specific surface is 1m
2The uncrystalline silicon acid starting material that/g is above for example can be enumerated diatomite, silica flour, cigarette ash, white carbon etc.As specific surface area is 1m
2The silicate starting materials that/g is above for example can be enumerated zeolite, pyrophanite, malthacite, montmorillonite mineral, chlorite mineral, attapulgite etc.These raw materials also can more than 2 kinds and be used.
The 2nd of the present invention's the 3rd method that relates to of invention is characterised in that, cooperates the former slip that forms for example to use to copy the slurry method to be configured as the shape of regulation above-mentioned raw materials and the plate without slaking (molding) that obtains, does not directly react, but carries out 1 maintenance.1 maintenance is to carry out under the condition more than (curing temperature-15) * curing time=120 ℃ hour.1 curing condition less than is in the time of 120 ℃ hours, and can not provide enough intensity to the plate without slaking because maintenance is insufficient therefore be disadvantageous.1 maintenance need surpass 15 ℃ curing temperature, preferably carries out 1 maintenance under the curing temperature in 30～80 ℃ of scopes, the condition more than 240 ℃ hours.
Carried out after above-mentioned 1 maintenance without the slaking plate, can under habitual hydrothermal reaction condition, carry out hydro-thermal reaction, make calcium silicate board through habitual operation thereafter.Hydro-thermal reaction can be in pressurized vessel, and temperature is 150～200 ℃, preferred 170～190 ℃, 5～20 hours under the saturated vapor, carries out under preferred 8～12 hours condition.
Invent the manufacture method that relates to according to the 3rd of the present invention, can make calcium silicate board with 1.0 following loose densitys.
Secondly, the essentially consist of the former slip that uses in the calcium silicate board manufacture method that the 4th of the present invention～6th invention relates to is to contain calcareous raw material 5～35 weight %, silicic acid raw material 5～40 weight %, cellulose raw material 2-8 weight %, inanimate matter packing material 5～40 weight % and be made up of with the habitual of gel of silicic acid raw material 3～25 weight % acquisition with calcareous raw material 2～20 weight % and gelation gelation.The above-mentioned raw materials slurry also can contain the solidifying agent that is up to 20 weight %.
As calcareous raw material, can use material same as described above herein.The use level less than 5 weight % of calcareous raw material, or when surpassing 35 weight %, flexural strength reduces, and is disadvantageous because therefore the size changing rate that suction causes increases.
As the silicic acid raw material, for example can use silica sand, cigarette ash etc.The use level less than 5 weight % of silicic acid raw material, or when surpassing 40 weight %, flexural strength reduces, and is disadvantageous because therefore the size changing rate that suction causes increases.
As cellulose raw material, can use material same as described above.If during the use level deficiency of cellulose raw material 2 weight %, therefore flexural strength reduces is disadvantageous; If surpass 8 weight %, then not having flame retardant resistance therefore is disadvantageous.When using polypropylene, vinylon, glass fibre, carbon fiber etc., its use level must be below 5 weight %.
As the inanimate matter packing material, can use material same as described above.If the use level deficiency of inanimate matter packing material 5 weight %, then the size changing rate that causes owing to suction will increase so be disadvantageous; If surpass 40 weight % then therefore flexural strength reduces is disadvantageous.
In the method that the 4th of the present invention～the 6th invention relates to,, can use the specific surface area identical to be 1m with above-mentioned the 3rd invention as having the part of the silicic acid raw material of the former slip of components matching as described above
2Uncrystalline silicon acid starting material or silicate starting materials that/g is above.
Specific surface area is 1m
2The uncrystalline silicon acid starting material that/g is above or the use level of silicate starting materials are invented in the scope of 2～20 weight % that coexist mutually with the above-mentioned the 3rd.
As specific surface area is 1m
2The uncrystalline silicon acid starting material that/g is above can use and the identical material of above-mentioned the 3rd invention.
In the method that the 4th of the present invention～the 6th invention relates to, must use in the former slip with the gelation of 2-20 weight % with the gelation of calcareous raw material and 3～25 weight % with the silicic acid raw material in advance for example under 75～95 ℃ temperature, for example in 1.5～4 hours, carry out gelation and the gel that obtains.Be used for making the former slip of calcium silicate board,, then can make loose density at an easy rate and be the calcium silicate board below 0.70 if use above-mentioned the sort of gel.All do not have special qualification with calcareous raw material and gelation with the silicic acid raw material for gelation, can use habitual any.As the gelation calcareous raw material, for example can use slaked lime, unslaked lime etc.; As gelation silicic acid raw material, for example can use diatomite, silica flour, cigarette ash, white carbon etc.
And then, in the method that in the 4th of the present invention～the 6th invention, relates to, can in former slip, cooperate solidifying agent.Solidifying agent is the material that improves flexural strength by 1 maintenance, for example can use portland cement, alundum cement, blast furnace granulated slag etc.Cooperate under the situation of solidifying agent, its use level is below the 20 weight %, preferably in the scope of 3～20 weight %.The loose density of calcium silicate board uprises if the use level of solidifying agent surpasses 20 weight %, and can not to make loose density be the calcium silicate board 0.70 below so be disadvantageous.And often can not get additive effect during use level less than 3 weight %.
According to the method that the 4th of the present invention～the 6th invention relates to, will contain or not contain specific surface area is 1m
2Uncrystalline silicon acid starting material or silicate starting materials that/g is above, and then, contain or do not contain solidifying agent, use the above-mentioned this former slip of gel as the part of former slip, utilize and copy the postforming of slurry method lamination.In the methods of the invention, thisly copy the slurry method there is no particular limitation, can adopt habitual any means.
The method that the 4th of the present invention～the 6th invention relates to is characterised in that, is not that the molding that will make as stated above directly carries out hydro-thermal reaction, but invents identical 1 maintenance of carrying out with the above-mentioned the 3rd.Herein, former slip does not contain under the situation of solidifying agent, and 1 maintenance is to carry out under the condition more than (curing temperature-15) * curing time=120 ℃ hour.If the condition deficiency of 1 maintenance 120 ℃ hours then can not provide enough intensity thereby is disadvantageous because maintenance is not enough to molding.And 1 maintenance must be to surpass 15 ℃ curing temperature, preferably carries out 1 maintenance under the curing temperature in 30～80 ℃ scope, the condition more than 240 ℃ hours.Contain when former slip under the situation of solidifying agent, 1 maintenance can be carried out under the condition more than (curing temperature-10) * curing time=120 ℃ hour.This be because with calcareous raw material and silicic acid raw material, especially with the reacting phase ratio of uncrystalline silicon acid starting material, silicate starting materials, solid even solidifying agent also is easy to the edge that carries out at low temperatures.And 1 maintenance must be to surpass 10 ℃ curing temperature, preferably carries out 1 maintenance under the curing temperature in 25～80 ℃ of scopes, the condition more than 240 ℃ hours.
By carrying out so 1 maintenance, molding can be brought up to 7kg/cm in the flexural strength of moisture state
2More than and be more than 1.3 times of molding flexural strength before 1 maintenance.
Carry out the molding after above-mentioned 1 maintenance, under habitual hydrothermal reaction condition, carried out hydro-thermal reaction, can make calcium silicate board through habitual operation thereafter.Hydro-thermal reaction can be in pressurized vessel, carry out under 150～200 ℃ of temperature, preferred 170～190 ℃, 5～20 hours, preferred 8～12 hours condition under the saturated vapor.
The loose density that is made by above-mentioned the inventive method is the calcium silicate board that the 7th invention of the present invention below 0.70 relates to, and interlaminar strength (over dry state) demonstrates very good value, is more than 3% of flexural strength (over dry state).Flexural strength is the result who tests with No. 3 test films according to JIS A5418, and the splitting test is the result who carries out with 30 * 30mm.
Below enumerating embodiment and comparative example further specifies the manufacture method of the calcium silicate board of the inventive method.
Embodiment 1 and comparative example 1
Production Example based on the calcium silicate hydrate of amorphousness slurry:
Cooperate slaked lime and silica sand in ratio shown in the table 1, mix with 13 times water and stir, under each condition shown in the table 1, carry out hydro-thermal reaction, obtain calcium silicate hydrate slurry based on amorphousness.Hydro-thermal reaction is used the experiment autoclave.Table 1
| Experiment No. | ||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | |
| Use raw material | The silica sand slaked lime | |||||
| Ca/ (Si+Al) mol ratio temperature (℃) time (hour) water is than stirring velocity (m/ branch) | ????0.4 ????180 ????6 ????13 ????100 | ????0.6 ????180 ????4 ????13 ????100 | ????0.8 ????150 ????4 ????13 ????100 | ????0.2 ????180 ????6 ????13 ????100 | ????1.0 ????150 ????4 ????13 ????100 | ????0.6 ????180 ????10 ????13 ????100 |
| The reactivity (%) of crystalline silicic acid raw material | ????48 | ????57 | ????78 | ????31 | ????95 | ????73 |
| Settling volume (ml/g) | ????6.4 | ????7.1 | ????9.0 | ????5.8 | ????14.5 | ????15.8 |
Cooperate raw material in ratio shown in the table 2, make solid component concentration and be 10% slip after, by the size press forming of 30 * 30 * 0.8mm.The pressure of compacting is 10kg/cm
2Then, depress under 180 ℃, 10 hours condition at saturation steam and carry out hydro-thermal reaction.
Loose density shown in the table 2, flexural strength (over dry state) and abrasion index.Table 2
| Example of the present invention | Comparative example | |||||||||
| ????1 | ????2 | ????3 | ????4 | ????1 | ????2 | ????3 | ????4 | ????5 | ||
| Cooperate ︵ weight % ︶ | Lime carbonate hydrate slurry experiment No. cooperates ratio solids component conversion amount | ????1 ????28 | ????2 ????7 | ????3 ????15 | ????1 ????7 | ????2 ????35 | ????4 ????28 | ????5 ????15 | ????6 ????7 | ????2 ????3 |
| Slaked lime silica sand wollastonite halite lime carbonate paper pulp glass fibre | ????32 ????24 ????10 ????- ????- ????5 ????1 | ????28 ????26 ????20 ????5 ????10 ????3 ????1 | ????29 ????28 ????10 ????- ????10 ????7 ????1 | ????34 ????33 ????10 ????- ????10 ????5 ????1 | ????26 ????23 ????10 ????- ????- ????5 ????1 | ????35 ????21 ????10 ????- ????- ????5 ????1 | ????29 ????28 ????10 ????- ????10 ????7 ????1 | ????28 ????26 ????20 ????5 ????10 ????3 ????1 | ????41 ????40 ????10 ????- ????- ????5 ????1 | |
| Loose density flexural strength (kg/cm 2) abrasion index | ????0.55 ????92 ????1.8 | ????0.68 ????115 ????0.43 | ????0.63 ????122 ????1.1 | ????0.78 ????118 ????0.32 | ????0.48 ????88 ????2.3 | ????0.73 ????104 ????0.27 | ????0.61 ????111 ????1.4 | ????0.64 ????118 ????1.2 | ????0.82 ????126 ????0.20 | |
| Productivity | ????○ | ????○ | ????△ | ????○ | ????× | ????○ | ????× | ????× | ????○ | |
In the table 2 about productivity, be to be that 4.2% slip 1 lifting is gone in the Buchner filter that diameter is 16cm with solid component concentration, drainage amount (ml)/filtration time (second) during with the filtering under pressure of 50cm Hg is as filtration velocity (ml/ second), with filtration velocity is that usefulness zero more than 30 is represented, representing below 30 more than 20 with △, the usefulness * expression of less than 20.
Embodiment 2 and comparative example 2
Cooperate slaked lime, silica sand, wollastonite, halite, paper pulp, uncrystalline silicon acid starting material and silicate starting materials with ratio shown in the table 3, mix with 12 times water and stir.
And then, add the former slip that water is made the about 3 weight % of solid component concentration, copying slurry becomes the thick plate of 6mm.
After carrying out 1 maintenance by temperature, the time of record in the table 3 then, in pressurized vessel, under following 180 ℃, 10 hours the condition of saturated vapor, carry out hydro-thermal reaction.
Shown in the table 3 after the hydro-thermal reaction not the plate of slaking have or not peel off, explosion, the flexural strength after 1 maintenance, and loose density and the flexural strength of the calcium silicate board that makes under the over dry state.Table 3
| Example of the present invention | Comparative example | |||||||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ????1 | ????2 | ????3 | ????4 | ????5 | ||
| Cooperate ︵ % ︶ | The white carbon zeolite of calcium hydroxide silica sand halite wollastonite paper pulp diatomite silica flour calcium carbonate montmorillonite allophane attapulgite chlorite | ????40 ????26 ????4 ????10 ????5 ????15 ????- ????- ????- ????- ????- ????- ????- ????- | ????40 ????30 ????6 ????10 ????5 ????- ????9 ????- ????- ????- ????- ????- ????- ????- | ????40 ????33 ????6 ????10 ????5 ????- ????- ????6 ????- ????- ????- ????- ????- ????- | ????40 ????27 ????6 ????10 ????5 ????- ????- ????- ????12 ????- ????- ????- ????- ????- | ????29 ????20 ????6 ????15 ????5 ????- ????- ????- ????- ????15 ????10 ????- ????- ????- | ????38 ????23 ????6 ????10 ????5 ????- ????- ????- ????- ????- ????- ????18 ????- ????- | ????38 ????29 ????6 ????10 ????5 ????- ????- ????- ????- ????- ????- ????- ????12 ????- | ????36 ????23 ????6 ????15 ????5 ????- ????- ????- ????- ????- ????- ????- ????- ????15 | ????38 ????35 ????7 ????15 ????5 ????- ????- ????- ????- ????- ????- ????- ????- ????- | ????40 ????26 ????4 ????10 ????5 ????15 ????- ????- ????- ????- ????- ????- ????- ????- | ????45 ????32 ????7 ????10 ????5 ????- ????- ????1 ????- ????- ????- ????- ????- ????- | ????40 ????16 ????4 ????10 ????5 ????25 ????- ????- ????- ????- ????- ????- ????- ????- | ????24 ????15 ????6 ????20 ????5 ????- ????- ????- ????- ????20 ????10 ????- ????- ????- |
| A maintenance | Temperature (℃) time (h) (temperature-15) * hour | ????60 ????8 ????360 | ????40 ????24 ????600 | ????25 ????12 ????120 | ????70 ????10 ????550 | ????60 ????8 ????360 | ????40 ????24 ????600 | ????70 ????10 ????550 | ????60 ????8 ????360 | ????60 ????8 ????360 | ????20 ????10 ????50 | ????25 ????12 ????120 | ????60 ????8 ????360 | ????60 ????8 ????360 |
| Flexural strength (kg/cm 2) | ????12 | ????13 | ????10 | ????21 | ????11 | ????14 | ????17 | ????18 | ????4 | ????4 | ????5 | ????17 | ????10 | |
| Have or not and peel off | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have | Have | Have | Do not have | Do not have | |
| Productivity | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????× | ????○ | |
| Loose density | ????0.73 | ????0.80 | ????0.81 | ????0.84 | ????0.77 | ????0.75 | ????0.84 | ????0.83 | ????0.76 | ????0.73 | ????0.83 | ????0.70 | ????0.75 | |
| Flexural strength (kg/cm 2) | ????111 | ????127 | ????133 | ????132 | ????108 | ????105 | ????128 | ????126 | ????121 | ????117 | ????135 | ????104 | ????91 | |
In the table 3, diatomite is pressed N
2The specific surface area that gas adsorption method obtains is 2.0m
2/ g, the specific surface area of silica flour is 20m
2/ g, the specific surface area of white carbon is 220m
2The specific surface area of/g, zeolite is 6.5m
2/ g.About productivity, zero expression is good, and * expression is bad.
Embodiment 3 and comparative example 3
Cooperate raw material in ratio shown in the table 4, mix, stir it with 12 times water.Gel is with 1: 1 slaked lime of weight ratio and diatomite, by carrying out the material that gelation obtains under the condition of water than 5 times, 90 ℃, 2 hours.Gel use level in the table is shown by solids component conversion scale.
And then, add the former slip that water is made the about 3 weight % of solid component concentration, copy and starch into the plate that thickness is 6mm.
Then, carry out 1 maintenance by temperature, the time of table 4 record after, in pressurized vessel, under following 180 ℃, 10 hours the condition of saturated vapor, carry out hydro-thermal reaction.
Copy at once molding flexural strength, the molding flexural strength after 1 maintenance, loose density, flexural strength and interlaminar strength after the hydro-thermal reaction (all being the over dry state) behind the slurry shown in the table 4.Table 4
| Example of the present invention | Comparative example | |||||||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ????1 | ????2 | ????3 | ????4 | ????5 | ||
| Cooperate ︵ % ︶ | Calcium hydroxide silica sand silica flour zeolite montmorillonite allophane attapulgite chlorite halite wollastonite paper pulp glass fibre Portland cement calcium carbonate gel | ????32 ????26 ????6 ????- ????- ????- ????- ????- ????- ????10 ????5 ????1 ????- ????- ????20 | ????30 ????24 ????- ????15 ????- ????- ????- ????- ????5 ????10 ????5 ????1 ????- ????- ????10 | ????17 ????27 ????- ????- ????- ????- ????- ????- ????- ????10 ????5 ????1 ????20 ????- ????20 | ????17 ????27 ????- ????- ????- ????- ????- ????- ????- ????10 ????5 ????1 ????20 ????- ????20 | ????23 ????16 ????- ????- ????10 ????- ????- ????- ????5 ????15 ????5 ????1 ????- ????15 ????10 | ????31 ????15 ????- ????- ????- ????18 ????- ????- ????- ????10 ????5 ????1 ????- ????- ????20 | ????33 ????24 ????- ????- ????- ????- ????12 ????- ????5 ????10 ????5 ????1 ????- ????- ????10 | ????31 ????18 ????- ????- ????- ????- ????- ????15 ????- ????10 ????5 ????1 ????- ????- ????20 | ????32 ????26 ????6 ????- ????- ????- ????- ????- ????- ????10 ????5 ????1 ????- ????- ????20 | ????28 ????24 ????- ????15 ????- ????- ????- ????- ????5 ????10 ????7 ????1 ????- ????- ????10 | ????15 ????24 ????- ????- ????- ????- ????- ????- ????- ????10 ????5 ????1 ????25 ????- ????20 | ????30 ????24 ????- ????15 ????- ????- ????- ????- ????5 ????10 ????5 ????1 ????- ????- ????10 | ????19 ????10 ????- ????- ????10 ????- ????- ????- ????5 ????20 ????5 ????1 ????- ????20 ????10 |
| 1 maintenance | Temperature (℃) time (hour) | ????50 ????12 | ????70 ????3 | ????50 ????8 | ????15 ????24 | ????60 ????8 | ????40 ????24 | ????70 ????10 | ????60 ????8 | Do not have | ????30 ????8 | ????30 ????8 | ????15 ????24 | ????60 ????8 |
| Shaping flexural strength at once is (kg/cm 1. 2) 2. (kg/cm of flexural strength after 1 maintenance 2) ②/① | ????4.8 ????7.1 ????1.48 | ????4.5 ????12.0 ????2.67 | ????4.8 ????8.5 ????1.77 | ????4.9 ????7.2 ????1.47 | ????4.6 ????10.8 ????2.35 | ????4.5 ????7.4 ????1.64 | ????4.8 ????12.4 ????2.58 | ????4.4 ????13.8 ????3.14 | ????4.8 ????5.0 ????1.04 | ????6.4 ????7.1 ????1.11 | ????5.1 ????7.0 ????1.37 | ????4.4 ????5.5 ????1.25 | ????4.6 ????9.9 ????2.15 | |
| Loose density | ????0.63 | ????0.65 | ????0.69 | ????0.69 | ????0.66 | ????0.63 | ????0.65 | ????0.64 | ????0.63 | ????0.65 | ????0.72 | ????0.65 | ????0.66 | |
| Flexural strength is (kg/cm 3. 2) 4. (kg/cm of interlaminar strength 2) ④/③(％) | ????84 ????3.1 ????3.7 | ????83 ????4.9 ????5.9 | ????98 ????7.9 ????8.1 | ????92 ????5.0 ????5.4 | ????90 ????4.8 ????5.3 | ????82 ????3.4 ????4.1 | ????87 ????7.2 ????8.3 | ????86 ????6.8 ????7.9 | ????68 ????0.3 ????0.44 | ????92 ????0.9 ????0.98 | ????103 ????6.7 ????6.5 | ????80 ????0.8 ????1.00 | ????88 ????4.6 ????5.2 | |
| Have or not in the hydro-thermal reaction and peel off | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have | Have | Do not have | Have | Do not have | |
In the table 4, silica flour is pressed N
2The specific surface area that gas adsorption method obtains is 20m
2/ g, the specific surface area of zeolite is 6.5m
2/ g, diatomaceous specific surface area is 2.0m
2/ g.
The 1st manufacture method of inventing the calcium silicate board that relates to according to the present invention. Although bulk density in 0.5～0.8 scope, also can make matrix strength and the high calcium silicate board of wear-resistant degree.
According to the manufacture method of the present invention's the 3rd calcium silicate board that relates to of invention, the plate of the not slaking that can obtain former slip is configured as the regulation shape is given intensity, therefore can prevent in hydro-thermal reaction not the plate of slaking produce peel off, explosion etc.
Manufacture method according to the 4th of the present invention～calcium silicate board that the 6th invention relates to, with copying the slurry method former slip is shaped, can give intensity by 1 maintenance, therefore have can prevent in hydro-thermal reaction formed body produce peel off, explosion, and can to improve the bulk density that makes be the interlaminar strength of the calcium silicate board below 0.70.
Claims (4)
1. the manufacture method of light weight calcium silicate board, the former slip that will contain calcareous raw material 17～50 weight %, silicic acid raw material 15～45 weight %, cellulose raw material 2-8 weight % and inanimate matter packing material 5～40 weight % as solid is in accordance with regulations behind the shape die forming, the gained molding is carried out hydro-thermal reaction and makes the light weight calcium silicate board in pressurized vessel, it is characterized in that, as the part of silicic acid raw material, use specific surface area to be 1m by 2～20 weight %
2Uncrystalline silicon acid starting material or more than a kind or 2 kinds of silicate starting materials that/g is above, and before molding is carried out hydro-thermal reaction are with molding 1 maintenance in universe ground under the condition more than (curing temperature-15) * curing time=120 ℃ hour.
2. loose density is the manufacture method of the calcium silicate board below 0.70, to contain calcareous raw material 5～35 weight % as solid, silicic acid raw material 5-40 weight %, cellulose raw material 2-8 weight %, inanimate matter packing material 5～40 weight % and the former slip of using the gel of silicic acid raw material 3～25 weight % acquisition by gelation with calcareous raw material 2～20 weight % and gelation, after copying slurry method laminating molding, the gained molding is placed on carries out hydro-thermal reaction in the pressurized vessel and make calcium silicate board, it is characterized in that, as the part of silicic acid raw material, use specific surface area to be 1m by 2～20 weight %
2Uncrystalline silicon acid starting material or more than a kind or 2 kinds of silicate starting materials that/g is above, and before molding was carried out hydro-thermal reaction, molding is carried out 1 maintenance under the condition more than (curing temperature-15) * curing time=120 ℃ hour to make the flexural strength of this molding under wetting regime be 7kg/cm
2More than and be more than 1.3 times of flexural strength before 1 maintenance.
3. loose density is the manufacture method of the calcium silicate board below 0.70, to contain calcareous raw material 5～35 weight % as solid, silicic acid raw material 5～40 weight %, cellulose raw material 2-8 gives birth to amount %, inanimate matter packing material 5～40 weight and the former slip of using the gel of silicic acid raw material 3-25 weight % acquisition by gelation calcareous raw material 2-20 weight % and gelation, after copying slurry method laminating molding, the gained molding is placed on carries out hydro-thermal reaction in the pressurized vessel and make calcium silicate board, it is characterized in that, as the part of silicic acid raw material, press 2-20 weight % and use specific surface area to be 1m
2Uncrystalline silicon acid starting material or more than a kind or 2 kinds of silicate starting materials that/g is above, and then, former slip contains the solidifying agent that is selected from portland cement, alundum cement and blast furnace granulated slag with the amount below the 20 weight %, and before making molding carry out hydro-thermal reaction, molding is carried out 1 maintenance under the condition more than (curing temperature-10) * curing time=120 ℃ hour to make the flexural strength of this molding under wetting regime be 7kg/cm
2More than and be more than 1.3 times of flexural strength before 1 maintenance.
4. loose density is the manufacture method of the calcium silicate board below 0.70, to contain calcareous raw material 5～35 weight % silicic acid raw materials 5～40 weight % as solid, cellulose raw material 2-8 weight %, inanimate matter packing material 5～40 weight % and the former slip of using the gel of silicic acid raw material 3-25 weight acquisition by gelation with calcareous raw material 2～20 weight % and gelation, after copying slurry method laminating molding, the gained molding is placed on carries out hydro-thermal reaction in the pressurized vessel and make calcium silicate board, it is characterized in that, former slip contains with the amount below the 20 weight % and is selected from portland cement, the solidifying agent of aluminum oxide ripples and blast furnace granulated slag, and before making molding carry out hydro-thermal reaction, molding is carried out 1 maintenance under the condition more than (curing temperature-10) * curing time=120 ℃ hour to make the flexural strength of this molding under wetting regime be 7kg/cm
2More than and be more than 1.3 times of flexural strength before 1 maintenance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011255498A CN1166581C (en) | 1996-06-25 | 1996-06-25 | Calcium silicate board and making method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011255498A CN1166581C (en) | 1996-06-25 | 1996-06-25 | Calcium silicate board and making method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96190738A Division CN1080708C (en) | 1996-06-25 | 1996-06-25 | Calcium silicate plate and process for producing the plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1358687A true CN1358687A (en) | 2002-07-17 |
| CN1166581C CN1166581C (en) | 2004-09-15 |
Family
ID=4665990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011255498A Expired - Lifetime CN1166581C (en) | 1996-06-25 | 1996-06-25 | Calcium silicate board and making method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN1166581C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366571C (en) * | 2002-10-11 | 2008-02-06 | 莱州祥云防火隔热材料有限公司 | Process for producing high temperature resistant, high strength and high density calcium silicate plate |
| CN1863750B (en) * | 2003-10-02 | 2010-10-27 | 圣戈班建筑材料股份有限公司 | Cement sheet product and production method thereof |
| CN103291028A (en) * | 2013-05-10 | 2013-09-11 | 苏州工业园区方圆金属制品有限公司 | Calcium silicate board |
| CN104016628A (en) * | 2014-06-24 | 2014-09-03 | 洛斐尔建材（沈阳）集团有限公司 | Environmental-friendly calcium silicate board and production process thereof |
| CN105130362A (en) * | 2015-07-21 | 2015-12-09 | 汪涛涛 | Humidity-regulating light-weight calcium silicate board and production method thereof |
| CN105198342A (en) * | 2015-07-15 | 2015-12-30 | 常州市武进金阳光电子有限公司 | Composite nano oil-resistant high-temperature-resistant calcium silicate board and preparation method thereof |
| CN114988840A (en) * | 2022-06-20 | 2022-09-02 | 广东新元素板业有限公司 | Preparation method of anti-cracking asbestos-fiber-free calcium silicate board |
| CN116375442A (en) * | 2023-03-02 | 2023-07-04 | 武汉理工大学 | High-strength calcium silicate board containing white calcium zeolite and preparation method thereof |
| CN115429099B (en) * | 2022-09-28 | 2024-04-26 | 武汉苏泊尔炊具有限公司 | Corrosion-resistant cooker and method for manufacturing same |
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1996
- 1996-06-25 CN CNB011255498A patent/CN1166581C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366571C (en) * | 2002-10-11 | 2008-02-06 | 莱州祥云防火隔热材料有限公司 | Process for producing high temperature resistant, high strength and high density calcium silicate plate |
| CN1863750B (en) * | 2003-10-02 | 2010-10-27 | 圣戈班建筑材料股份有限公司 | Cement sheet product and production method thereof |
| CN103291028A (en) * | 2013-05-10 | 2013-09-11 | 苏州工业园区方圆金属制品有限公司 | Calcium silicate board |
| CN104016628A (en) * | 2014-06-24 | 2014-09-03 | 洛斐尔建材（沈阳）集团有限公司 | Environmental-friendly calcium silicate board and production process thereof |
| CN105198342A (en) * | 2015-07-15 | 2015-12-30 | 常州市武进金阳光电子有限公司 | Composite nano oil-resistant high-temperature-resistant calcium silicate board and preparation method thereof |
| CN105130362A (en) * | 2015-07-21 | 2015-12-09 | 汪涛涛 | Humidity-regulating light-weight calcium silicate board and production method thereof |
| CN114988840A (en) * | 2022-06-20 | 2022-09-02 | 广东新元素板业有限公司 | Preparation method of anti-cracking asbestos-fiber-free calcium silicate board |
| CN115429099B (en) * | 2022-09-28 | 2024-04-26 | 武汉苏泊尔炊具有限公司 | Corrosion-resistant cooker and method for manufacturing same |
| CN116375442A (en) * | 2023-03-02 | 2023-07-04 | 武汉理工大学 | High-strength calcium silicate board containing white calcium zeolite and preparation method thereof |
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| Publication number | Publication date |
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| CN1166581C (en) | 2004-09-15 |
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