CN103044059B - The manufacture method of molding, cladding, molding and the manufacture method of cutting body - Google Patents

The manufacture method of molding, cladding, molding and the manufacture method of cutting body Download PDF

Info

Publication number
CN103044059B
CN103044059B CN201110308252.7A CN201110308252A CN103044059B CN 103044059 B CN103044059 B CN 103044059B CN 201110308252 A CN201110308252 A CN 201110308252A CN 103044059 B CN103044059 B CN 103044059B
Authority
CN
China
Prior art keywords
molding
quality
silicon
particle
dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201110308252.7A
Other languages
Chinese (zh)
Other versions
CN103044059A (en
Inventor
饭塚千博
新纳英明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Original Assignee
Asahi Kasei Chemicals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Chemicals Corp filed Critical Asahi Kasei Chemicals Corp
Priority to CN201110308252.7A priority Critical patent/CN103044059B/en
Publication of CN103044059A publication Critical patent/CN103044059A/en
Application granted granted Critical
Publication of CN103044059B publication Critical patent/CN103044059B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The present invention relates to molding, cladding, the manufacture method of molding and the manufacture method of cutting body.Problem of the present invention is, provides during compression and avalanche, distortion not easily occur, and carries out while avalanche can not occur cutting off etc. shape processing, and has the molding of heat insulating ability, cladding, the manufacture method of molding and the manufacture method of cutting body.Described molding contains silicon-dioxide and germanium, and the containing ratio of germanium is below more than 10 quality ppm 1000 quality ppm, and the ultimate load under rate of compression 0 ~ 5% is more than 0.7MPa, and the thermal conductivity at 30 DEG C is below 0.05W/mK.

Description

The manufacture method of molding, cladding, molding and the manufacture method of cutting body
Technical field
The present invention relates to molding, cladding, the manufacture method of molding and the manufacture method of cutting body.
Background technology
The mean free path of room temperature in air molecule is about 100nm.Therefore, in the porous plastid in space with below diameter 100nm, by air convection current, conduct the heat transfer that causes and be suppressed, therefore such porous plastid shows excellent heat insulating function.
Follow the principle of this heat insulating function, knownly utilize mini porous structures, the thermal insulation material that thermal conductivity is extremely low can be obtained.Such as, a kind of manufacturing process is disclosed in following non-patent literature 1, wherein, as the material of low thermal conductance degree, select aerosil, coordinate wherein ceramic fiber and for reduce infrared rays through the opaque agent of infrared rays namely there is the thermotolerance metal oxide of special particle diameter and size-grade distribution, emptying aperture is set, is formed by the mode of the sectional area in path to reduce heat.
Prior art document
Non-patent literature
Non-patent literature 1: the work that industry heating Vol.20 No.4 heat-insulation material " Microtherm " Jiangkou is grand
Non-patent literature 2: Tie technology information centre of independent administrative corporation's NEDO (consigner) Co., Ltd., Heisei 19 years investigation entrust achievement Report book about the investigation report (Heisei in March, 20) of material technology of pottery with nanoporous body structure
Summary of the invention
the problem that invention will solve
Mini porous structures contributes to the thermal conduction reducing thermal insulation material really, but the ratio improving emptying aperture can make the intensity of thermal insulation material reduce.On the other hand, when analyzing the application target of thermal insulation material, wish difference according to purposes and be processed into complicated shape, to this, when the intensity of thermal insulation material is insufficient, there is the problem that can not tolerate cut-outs, punching, boring etc. and process.By the research of the present inventor, known, carry out cutting off etc. adding man-hour, bearing capacity when compressing 5% must be comparatively large, and specifically, the ultimate load under rate of compression 0 ~ 5% is necessary for more than 0.7MPa.
But, for the Microtherm (trade(brand)name, Japanese Microtherm Co., Ltd. system) described in non-patent literature 1, for plate and density is 200 ~ 275kg/m 3type in, the load under rate of compression 5% is 2kg/cm 2.In addition, about the thermal insulation material of identical type, the chart (in above-mentioned non-patent literature 1 " resistance against compression of Fig. 4 Microtherm ") of publication shows, at about 4.5kg/cm 2load under, compression set about 10%, the present inventor studies discovery, and the thermal insulation material described in non-patent literature 1 does not have sufficient intensity, for cut off time easy avalanche.
In non-patent literature 2, describing following content: about Microtherm, is the tabular molding of solid state or flexibility, and ultimate compression strength when compressing 5% is according to the 75 ~ 600kN/m that do not coexist of density 2scope in.In addition, Microtherm, for deforming and the indefinite material of breakdown point, therefore, as the method for strength trial, records the relation measuring compressive load and deformation rate.
Describe in non-patent literature 2 and utilize ASTM (American Society for testing and materials; American Society for Testing and Materials) the stdn bioassay standard of ultimate compression strength measure the example (ASTM Test Method C165) of intensity of thermal insulation material.According to the document, describe and measure thermal insulation material with common trier, but owing to not indicating the figure of avalanche under certain stress, therefore, draw load-deflection curve and compare with the load under certain deformation rate.Like this, when there is significantly compression set in thermal insulation material under the effect of load, sometimes occur that heat-insulating property becomes easy reduction, or produce gap because of compression set, produce the intensity at the position in gap and reduce and to become in the practicalities such as easy avalanche preferred problem.
The problem that the present invention has in view of such prior art is carried out, its object is to, there is provided during compression and avalanche, distortion not easily occur, carry out while avalanche can not occur cutting off etc. shape processing, and there is the molding of heat insulating ability, cladding, the manufacture method of molding and the manufacture method of cutting body.
for the scheme of dealing with problems
The present inventor conducts in-depth research repeatedly in order to solve above-mentioned problem, found that, containing silicon-dioxide and germanium and the material showing specific ultimate compression strength also shows high heat insulating ability in the purposes that load is large, thus completes the present invention.That is, the present invention is as follows.
Molding of the present invention contains silicon-dioxide and germanium, and the containing ratio of germanium is below more than 10 quality ppm 1000 quality ppm, and the ultimate load under rate of compression 0 ~ 5% is more than 0.7MPa, and the thermal conductivity at 30 DEG C is below 0.05W/mK.
The molding of the invention described above is preferably below 0.2W/mK containing the thermal conductivity at infrared rays opacification particle and 800 DEG C further.
The preferred median size of infrared rays opacification particle contained in the molding of the invention described above be more than 0.5 μm less than 30 μm and the containing ratio of infrared rays opacification particle with the quality of molding for being below more than 0.1 quality % 39.5 quality % during benchmark.
The molding of the invention described above preferably contains iron (Fe) and the containing ratio of iron (Fe) is below more than 0.005 quality % 6 quality %.
The molding of the invention described above preferably contains inorganic fibre further and the containing ratio of inorganic fibre is below more than 0.1 quality % 50 quality %.
Inorganic fibre contained in the molding of the invention described above preferably has bio-soluble.
Cladding of the present invention possesses above-mentioned molding and is accommodated the outer cover material material of body.
In the cladding of the invention described above, outer cover material material is preferably containing inorganic fibre.
In the cladding of the invention described above, outer cover material material is preferably resin molding.
Manufacture method for obtaining the molding of the invention described above preferably possesses following operation: be the operation of carrying out heat treated at the inorganic mixture of below more than the 10 quality ppm 1000 quality ppm temperature more than 600 DEG C by the containing ratio containing silicon-dioxide and germanium and germanium.
The manufacture method of the molding of the invention described above preferably possesses following operation: be the storage operation that the inorganic mixture of below more than 10 quality ppm 1000 quality ppm is accommodated in shaping dies by the containing ratio containing silicon-dioxide and germanium and germanium; With the forming process that inorganic mixture is shaped,
Forming process has following operation (a) or operation (b),
A () utilizes shaping dies to pressurize to inorganic mixture, be heated to the operation of more than 600 DEG C simultaneously;
B () implements the operation of heat treated after being shaped by described inorganic mixture by pressurization at the temperature more than 600 DEG C.
In above-mentioned forming process, preferably with the volume density of molding for 0.25g/cm 3above 2.0g/cm 3following mode sets compacting pressure.
The manufacture method of the molding of the invention described above preferably possesses following operation further: by the median size D containing silicon-dioxide sfor more than 5nm and the small-particle less than 30nm and the median size D containing germanium and silicon-dioxide lfor the macrobead of more than 40nm less than 50 μm mixes, obtain the operation of inorganic mixture.
The manufacture method of the molding of the invention described above preferably possesses following operation further: by the median size D containing silicon-dioxide sfor more than 5nm and the small-particle less than 30nm and the median size D containing germanium and silicon-dioxide lfor macrobead and the metal oxide sol mixing of more than 40nm less than 50 μm, obtain the operation of inorganic mixture.
Cut a part for the molding of the invention described above and the manufacture method of cutting body that obtains possesses following operation: be the storage operation that the inorganic mixture of below more than 10 quality ppm 1000 quality ppm is accommodated in shaping dies by the containing ratio containing silicon-dioxide and germanium and germanium; With the forming process that inorganic mixture is shaped; With the cutting process cut a part for the molding obtained in forming process,
Forming process has following operation (c) or operation (d),
(c) with the volume density of molding for 0.25g/cm 3above 2.0g/cm 3following mode utilizes described shaping dies to pressurize to described inorganic mixture, carries out the operation heated simultaneously;
D () implements the operation of heat treated after being shaped by inorganic mixture by utilizing shaping dies to carry out pressurizeing at the temperature more than 600 DEG C.
the effect of invention
According to the present invention, can provide during compression and avalanche, distortion not easily occur, carry out while avalanche can not occur cutting off etc. shape processing, and there is the molding of heat-insulating property, cladding, the manufacture method of molding and the manufacture method of cutting body.
Accompanying drawing explanation
Fig. 1 is the diagrammatic cross-section of the cladding of one embodiment of the present invention.
Fig. 2 is the small-particle that contains of the molding of one embodiment of the present invention and oarse-grained diagrammatic cross-section.
description of reference numerals
1... cladding (thermal insulation material)
2... core (molding)
3... outer cover material material
S... small-particle
L... macrobead.
Embodiment
Below, to for implementing mode of the present invention (hreinafter referred to as " present embodiment ".) be described in detail.It should be noted that, the present invention is not limited to following embodiment, can in its main scope, carry out various distortion and implement.
[1] molding
[1-1] silicon-dioxide
The molding of present embodiment contains silicon-dioxide.When the containing ratio of the silicon-dioxide in molding is more than 50 quality %, the heat transfer caused by solid conduction is little, therefore, when thermal insulation material purposes preferably.When the containing ratio of silicon-dioxide is more than the 75 quality % of molding, the sticking power between silica dioxide granule increases, and the dispersing of inorganic mixture as the raw material of molding tails off, therefore more preferably.It should be noted that, in this manual, so-called silicon-dioxide, except referring to by composition formula SiO 2beyond the particle that the composition represented is formed, also refer to containing SiO 2particle, comprise except SiO 2these particles are called silica dioxide granule by particle in addition also containing metal ingredient etc., other mineral compound sometimes.Silica dioxide granule, except pure silicon dioxide, can contain salt, the composite oxides of Si and other element various, can also contain the such hydrous oxide of oxyhydroxide, also can have silanol group.Silicon-dioxide in molding can be crystalline, also can be amorphousness, and can also be their mixture, when thermal insulation material purposes, during for amorphousness, the heat transfer caused by the solid conduction in thermal insulation material be little, and heat-insulating property improves, therefore preferably.
According to the difference of the purposes of molding, molding also can containing the material beyond silica dioxide granule.About the material beyond silica dioxide granule, to describe in detail later, when inorganic mixture contains the material beyond silica dioxide granule, the containing ratio of silica dioxide granule preferably with the total mass of molding for being below more than 50 quality % 99.9 quality % during benchmark.The containing ratio of silica dioxide granule is below more than 50 quality % 97.5 quality % and molding containing inorganic fibre, infrared rays opacification particle shows the effects such as the raising of the heat-insulating property under more excellent high temperature, more preferably.When containing ratio is below more than 60 quality % 97.5 quality %, the volume density of molding is less, therefore more preferably.
[1-2] inorganic fibre
The molding of present embodiment is preferably containing inorganic fibre.During containing inorganic fibre, have the following advantages: in press molding, the situation that particle comes off from molding is few, and productivity is high.In this specification sheets, so-called inorganic fibre, refers to that the mean length of inorganic fibre is the fiber of more than 10 with the ratio (length-to-diameter ratio) of average boldness.Length-to-diameter ratio is preferably more than 10, when being made into body, from the viewpoint of can with little pressure forming, improve the productivity of molding, be more preferably more than 50, from the viewpoint of the flexural strength of molding, more preferably more than 100.The length-to-diameter ratio of inorganic fibre can be obtained by the rugosity of 1000 inorganic fibres utilizing FE-SEM to measure and the mean value of length.Inorganic fibre preferably mixes in molding single dispersing, but the state that also mutually can be wound around with inorganic fibre, multiple inorganic fibre collect the state mixing of bunchy in the same direction.In addition, under monodisperse status, also can for inorganic fibre towards the state collected in same direction, but from the viewpoint of reduction thermal conductivity, inorganic fibre is preferably along perpendicular to the direction orientation in direction of conducting heat.Such as, by pressurizeing on the direction identical with heat transfer direction, easily make the inorganic fibre of heat transfer direction, edge orientation along the direction orientation perpendicular to heat transfer direction.
When illustrating the example of inorganic fibre, can enumerate: long glass fiber (long filament) (SiO 2-Al 2o 3-B 2o 3-CaO), glass fibre, glass wool (SiO 2-Al 2o 3-CaO-Na 2o), alkali resistant glass fibre (SiO 2-ZrO 2-CaO-Na 2o), rock wool (basalt wool) (SiO 2-Al 2o 3-Fe 2o 3-MgO-CaO), slag wool (SiO 2-Al 2o 3-MgO-CaO), ceramic fiber (mullite fiber) (Al 2o 3-SiO 2), silica fiber (SiO 2), sapphire whisker (Al 2o 3-SiO 2), potassium titanate fiber, alumina whisker, silicon carbide whisker, silicon nitride crystal whisker, calcium carbonate crystal whisker, alkali magnesium sulfate crystal whisker, calcium sulfate crystal whiskers (gypsum fiber), ZnOw, Zirconium oxide fibre, carbon fiber, graphite whisker, phosphate fiber, AES (Alkaline Earth Silicate) fiber (SiO 2-CaO-MgO), the wollastonite of natural mineral, sepiolite, attapulgite, brucite.
In inorganic fibre, particularly preferably use the AES fiber (Alkaline Earth Silicate Fiber alkaline earth silicate fibres) of the bio-soluble to human-body safety.As AES fiber, such as, can enumerate: SiO 2the unorganic glass (inorganic polymer) of-CaO-MgO system.
The average boldness of inorganic fibre is preferably more than 1 μm from the viewpoint of preventing from dispersing.From the viewpoint of the heat transfer suppressing to be caused by solid conduction when thermal insulation material, be preferably less than 20 μm.The average boldness of inorganic fibre can utilize FE-SEM to obtain the rugosity of 1000 inorganic fibres, and it is on average obtained.
When adiabatic purposes, the containing ratio of the inorganic fibre in molding departs from from the viewpoint of suppression powder from molding, and relative to the quality of molding entirety, being preferably more than 0.1 quality %, is 10m from making the BET specific surface area of molding 2/ more than g, thermal conductivity at 30 DEG C are that the viewpoint of below 0.05W/mK is considered, are preferably below 50 quality %.
From the viewpoint of the easy degree mixed with silica dioxide granule, infrared rays opacification particle; the containing ratio of inorganic fibre is more preferably below more than 0.2 quality % 40 quality %; diminish from the viewpoint of volume density, more preferably below more than 0.2 quality % 20 quality %.
Inorganic fibre also can contain Ge, in this case, select Ge containing ratio can make the containing ratio of the Ge in molding be below 1000 quality ppm inorganic fibre basis on, also meet the combined amount of the mode determination inorganic fibre of below 1000 quality ppm with the containing ratio of the Ge in molding.In this case, the Ge that certain silica dioxide granule can contain measures the Ge containing ratio of corresponding inorganic fibre and tails off.Therefore, the containing ratio of the Ge in silica dioxide granule, inorganic fibre is preferably measured in advance.When inorganic fibre is not containing Ge, the Ge containing ratio of silica dioxide granule (or mixture of silica dioxide granule and infrared rays opacification particle) meets below more than 10 quality ppm 1000 quality ppm (with the total mass of molding for benchmark).
[1-3] infrared rays opacification particle
When requiring the heat-insulating property under high temperature, the molding of present embodiment is preferably containing infrared rays opacification particle.So-called infrared rays opacification particle, refers to by reflection, scattering or absorbs the particle that ultrared material forms.In thermal insulation material during mixture of red outside line opacification particle, can suppress radiation-induced heat transfer, therefore, the heat-insulating property under the high-temperature area particularly more than 200 DEG C is high.
As the example of infrared rays opacification particle, can enumerate: carbonaceous material, carbon fiber, spinel pigments, aluminum particulate, stainless steel particle, bronze particles, copper/zinc alloy granules, the copper/Chrome metal powder particles such as zirconium white, zirconium silicate, titanium dioxide, iron titanium oxide, ferric oxide, cupric oxide, silicon carbide, gold mine, chromium dioxide, Manganse Dioxide, graphite.Can be used alone above-mentioned metallic particles known as the opaque material of infrared rays so far or non-metallic particle, also two or more kinds may be used described particle.
As infrared rays opacification particle, particularly preferably zirconium white, zirconium silicate, titanium dioxide or silicon carbide.The composition of infrared rays opacification particle can be obtained by FE-SEMEDX.
The median size of infrared rays opacification particle, from the viewpoint of heat-insulating property when more than 200 DEG C, is preferably more than 0.5 μm, from the viewpoint of obtain by suppressing solid conduction lower than heat-insulating property when 200 DEG C, preferably less than 30 μm.It should be noted that, the median size of infrared rays opacification particle can utilize the method identical with silica dioxide granule to obtain.Also the size of inorganic fibre, silica dioxide granule is depended on; but when silica dioxide granule is 5nm ~ 50 μm; from the viewpoint of the easy degree mixed with silica dioxide granule, the median size of infrared rays opacification particle is more preferably more than 0.5 μm less than 10 μm.
The containing ratio of the infrared rays opacification particle in molding is preferably below more than 0.1 quality % 39.5 quality %.When the containing ratio of infrared rays opacification particle is greater than 39.5 quality %, the heat transfer caused by solid conduction is large, therefore, exists lower than the low tendency of heat-insulating property when 200 DEG C.Heat-insulating property during in order to improve more than 200 DEG C, the content of infrared rays opacification particle is more preferably below more than 0.5 quality % 35 quality %, more preferably below more than 1 quality % 30 quality %.There is the little tendency of thermal contraction in the molding containing silicon-dioxide and germanium and infrared rays opacification particle, such as, when being exposed to suddenly in overheated environment, has the effect postponing change in shape or molding avalanche.
The containing ratio of infrared rays opacification particle such as can be obtained as follows, that is, utilize FE-SEM EDX to measure the composition of infrared rays opacification particle, utilize fluorescent x-ary analysis to carry out quantitatively, obtaining thus to the element that only infrared rays opacification particle contains.
Infrared rays opacification particle also can contain Ge.When infrared rays opacification particle contains Ge, in the mode that the Ge containing ratio in molding entirety is below more than 10 quality ppm 1000 quality ppm, the Ge amount deducting silica dioxide granule, the Ge containing inorganic fibre sometimes measure and adjust Ge containing ratio, the combined amount of infrared rays opacification particle.Therefore, the containing ratio of the Ge in silica dioxide granule, inorganic fibre is preferably measured in advance.
The containing ratio of [1-4] germanium (Ge)
The molding of present embodiment contains Ge.The containing ratio of Ge with the total mass of molding for during benchmark being more than 10 quality ppm 1000 quality ppm.When the containing ratio of Ge is less than 10 quality ppm, there is the tendency that ultimate compression strength is little, when the containing ratio of Ge is more than 1000 quality ppm, there is the tendency that heat-insulating property is low.Its reason is not yet clear and definite, is presumed as follows.As hereinafter described, in the manufacture of molding, there is the operation of molding being carried out to heat treated.The present inventor infers, in this heating treatment step, by containing Ge in molding, the fusing point as the silicon-dioxide of the main composition composition of molding reduces, and contributes to molding solidification.For the containing ratio of Ge, fully solidifying from the viewpoint of making molding, improving ultimate compression strength, preferably with the total mass of molding for being below more than 20 quality ppm 900 quality ppm during benchmark, be more preferably below more than 20 quality ppm 800 quality ppm, more preferably below more than 20 quality ppm 700 quality ppm.The containing ratio of the Ge in powder can pass through XRF (x-ray fluorescence analysis) and carry out quantitatively.
When molding contains Ge, infer that the fusing point as the silicon-dioxide of the main composition composition of molding when implementing heat treated reduces.Its result, thinks silica dioxide granule each other in granular boundary welding, forms firmly junction.In addition, Si and Ge is congeners in the periodic table of elements, and oxide compound is respectively as SiO 2, GeO 2like this, be 4 valencys, therefore, think and easily mutually enter crystalline texture, form firmly structure.Think, the stabilization of formation to the structure formed by silica dioxide granule of so firmly junction and structure works, result, molding integrally curing, and ultimate compression strength increases.It should be noted that, think, is below 1000 quality ppm by making the containing ratio of germanium, the welding of unnecessary degree can not be carried out at the interface of silica dioxide granule, therefore, in molding, there is not the large heat-transfer path of solid conduction, the thermal conductivity of molding entirety can be made to reduce.
When mixing the inorganic mixture of multiple silica dioxide granule, such as small-particle and macrobead preparation as the raw material of molding, preferably measure the containing ratio of respective Ge in advance, adjust combined amount in the mode that the containing ratio of the Ge of mixed inorganic mixture is below more than 10 quality ppm 1000 quality ppm.Such as, when the containing ratio of mixing Ge is respectively the macrobead of the small-particle of 0 quality ppm and 1700 quality ppm, preferred oarse-grained quality/(short grained quality+oarse-grained quality) is in the scope of 0.006 ~ 0.58.When using inorganic fibre, infrared rays opacification particle, also preferably measure the containing ratio of respective Ge in advance, determine combined amount.Such as, when the containing ratio of Ge be the containing ratio that mixes Ge in the silicon-dioxide of 800 quality ppm is the inorganic fibre of 0 quality ppm, the combined amount of inorganic fibre can be determined arbitrarily.Such as, when the containing ratio of Ge be the containing ratio that mixes Ge in the silicon-dioxide of 800 quality ppm is the infrared rays opacification particle of 30 quality ppm, the combined amount of infrared rays opacification particle can be determined arbitrarily.
[1-5] BET specific surface area
The preferred BET specific surface area of molding is 10m 2/ more than g 350m 2/ below g.There is the little tendency of thermal conductivity in the molding with the BET specific surface area within the scope of this.But the ultimate load under rate of compression 0 ~ 5% is not limited to as more than 0.7MPa.But, there is BET specific surface area in aforementioned range and the containing ratio of Ge is below more than 10 quality ppm 1000 quality ppm time, there is the tendency that the compression set that caused by load is little.Its reason is not yet clear and definite, and as mentioned above, infer that Ge contributes to reducing the fusing point as the silicon-dioxide of the main composition composition of molding, therefore, BET specific surface area is 10m 2/ more than g 350m 2when/below g and the containing ratio of Ge are below more than 10 quality ppm 1000 quality ppm, there is the tendency that ultimate compression strength becomes large, its result, the compression variation caused by load is little, can obtain the molding of heat-insulating property excellence.BET specific surface area is more preferably 10m 2/ more than g 250m 2/ below g, more preferably 10m 2/ more than g 200m 2/ below g.
Mix multiple silica dioxide granule, such as small-particle described later and macrobead, obtain inorganic mixture, and when being prepared into body by the inorganic mixture obtained, preferably measuring respective BET specific surface area, take BET specific surface area as 10m 2/ more than g 350m 2the mode of/below g adjusts combined amount.Such as, mix BET specific surface area and be respectively 200m 2the small-particle of/g and 0.3m 2during/g macrobead, preferred oarse-grained quality/(short grained quality+oarse-grained quality) is in the scope of 0 ~ 0.88.When using inorganic fibre, infrared rays opacification particle, also preferably measure respective BET specific surface area in advance, determine combined amount.Such as, be 200m in BET specific surface area 2mixing BET specific surface area in the silicon-dioxide of/g is 0.15m 2during the inorganic fibre of/g, the combined amount of inorganic fibre is preferably 0.1 quality % ~ 90 quality %.Be such as 200m in BET specific surface area 2mixing BET specific surface area in the silicon-dioxide of/g is 2m 2during the infrared rays opacification particle of/g, the combined amount of infrared rays opacification particle is preferably greater than 0 quality % and be below 95 quality %.As described later, in the manufacture of molding, there is operation molding being implemented to heat treated, but implement the molding of heat treated compared with the molding implemented before heat treated, there is the tendency that BET specific surface area diminishes, therefore, the BET specific surface area of the molding after implementing heat treated also can be measured, the combined amount of adjustment silica dioxide granule, inorganic fibre, infrared rays opacification particle.
[1-6] ultimate compression strength
For the molding of present embodiment, ultimate load when rate of compression is in the scope of 0 ~ 5% is more than 0.7MPa.Be more preferably 0.8MPa, more preferably 0.9MPa.
Rate of compression can be calculated relative to the stroke (press-in distance) of compression direction length by thickness of sample during mensuration ultimate compression strength, sample.Such as, when using the sample determination ultimate compression strength of cubic shaped molding being made 1cm × 1cm × 1cm, be that to be defined as rate of compression be 5% for the state of 0.5mm by stroke.Rate of compression following formula (1) calculates.
The compression direction length (1) of rate of compression=100 × stroke (press-in distance)/sample
Load-rate of compression the graphic representation drawn when measuring ultimate compression strength is not particularly limited.That is, above-mentioned rate of compression is in the scope of 0 ~ 5%, and the molding as sample can avalanche and demonstrate clear and definite breakdown point, also can not avalanche.In the scope that rate of compression is 0 ~ 5%, as sample molding avalanche and when demonstrating breakdown point, the ultimate load of this molding is defined as load during breakdown point.Load during this breakdown point is preferably more than 0.7MPa, is more preferably 0.8MPa, more preferably 0.9MPa.During sample not avalanche, the value of the ultimate load using rate of compression to show in the scope of 0 ~ 5% is evaluated.
Ultimate compression strength can utilize method described later to measure.
[1-7] thermal conductivity
Thermal conductivity at 30 DEG C of molding is below 0.05W/mK.From the viewpoint of heat-insulating property, thermal conductivity is preferably below 0.045W/mK, is more preferably below 0.040W/mK, more preferably below 0.037W/mK.When molding contains infrared rays opacification particle, the thermal conductivity at 800 DEG C is preferably below 0.2W/mK, is more preferably below 0.19W/mK, more preferably below 0.18W/mK.The measuring method of thermal conductivity will describe later.
Mix multiple silica dioxide granule, such as small-particle and macrobead, when preparing inorganic mixture, preferably the containing ratio of Ge is below more than 10 quality ppm 1000 quality ppm, BET specific surface area is 10m making as mentioned above 2/ more than g 350m 2on the basis of/below g, measure thermal conductivity.When thermal conductivity is more than 0.05W/mK, preferably the containing ratio of Ge is below more than 10 quality ppm 1000 quality ppm, BET specific surface area is 10m maintaining 2/ more than g 350m 2combined amount is changed in the scope of/below g.When using inorganic fibre, infrared rays opacification particle, also similarly can determine combined amount.When mixing small-particle and macrobead preparation become the inorganic mixture of the raw material of molding, with inorganic mixture only compared with the situation that macrobead is formed, the tendency that visible thermal conductivity diminishes.Such as, during the macrobead of the mixing small-particle of about 10nm and about 5 μm, oarse-grained quality/(short grained quality+oarse-grained quality) is preferably made to be 0.02 ~ 0.95.When the combined amount of inorganic fibre, infrared rays opacification particle is excessive, heat insulating ability reduces sometimes, and therefore, preferred limit measures and confirms that thermal conductivity limit is appropriately prepared.Such as, mix that fiber diameter is 12 μm in silica, mean length is when being the inorganic fibre of 5mm, the combined amount of inorganic fibre is preferably below 30 quality %.Such as, when mixing median size is the infrared rays opacification particle of 2 μm in silica, the combined amount of infrared rays opacification particle is preferably below 23 quality %.In addition, when the inorganic fibre selecting to be made up of the material that thermal conductivity is little, infrared rays opacification particle use, exist and easily obtain the tendency that thermal conductivity is the molding of below 0.05W/mK.
The containing ratio of [1-8] Fe, other element
The powder of present embodiment disperses from the viewpoint of the powder that has excellent formability, reduces and is preferably Fe during benchmark with the total mass of powder containing ratio is below more than 0.005 quality % 6 quality %, be more preferably below more than 0.005 quality % 3 quality %, more preferably below more than 0.005 quality % 2 quality %, is particularly preferably below more than 0.005 quality % 1 quality %.In addition, powder, except containing except Ge, Fe, can also contain potassium (K), magnesium (Mg), calcium (Ca), phosphorus (P), sulphur (S).For the containing ratio of each element, the containing ratio of preferred K is below more than 0.003 quality % 2 quality %, the containing ratio of Mg is below more than 0.002 quality % 2 quality %, the containing ratio of Ca is below more than 0.002 quality % 0.5 quality %, the containing ratio of P is below more than 0.003 quality % 0.3 quality %, the containing ratio of S is below more than 0.003 quality % 0.3 quality %, and more preferably the containing ratio of K is below more than 0.003 quality % 1.5 quality %, the containing ratio of Mg is below more than 0.002 quality % 1.8 quality %, the containing ratio of Ca is below more than 0.002 quality % 0.4 quality %, the containing ratio of P is below more than 0.003 quality % 0.25 quality %, the containing ratio of S is below more than 0.003 quality % 0.2 quality %, and preferably the containing ratio of K is below more than 0.003 quality % 1.0 quality % further, the containing ratio of Mg is below more than 0.002 quality % 1.6 quality %, the containing ratio of Ca is below more than 0.002 quality % 0.2 quality %, the containing ratio of P is below more than 0.003 quality % 0.2 quality %, the containing ratio of S is below more than 0.003 quality % 0.1 quality %.
[2] manufacture method of molding
The manufacture method of the molding of present embodiment possesses following operation: the operation of the inorganic mixture that is below more than 10 quality ppm 1000 quality ppm of the containing ratio containing silicon-dioxide and germanium and germanium being carried out to heat treated.Above-mentioned manufacture method preferably possesses the storage operation be accommodated in by above-mentioned inorganic mixture in shaping dies and the forming process be shaped by inorganic mixture, forming process has following operation: (a) utilizes shaping dies to pressurize to inorganic mixture, meanwhile, the operation of more than 600 DEG C is heated to; Or inorganic mixture is shaped by pressurization by (b), implements the operation of heat treated at the temperature then more than 600 DEG C.Below, the raw material used in the manufacture of molding and each operation are described.
[2-1] silica dioxide granule
As the concrete example of silica dioxide granule, following substances can be enumerated.Be called as the oxide compound of the silicon of " silicon-dioxide " or " quartz ".The partial oxide of silicon.The composite oxides of the silicon that silica-alumina, zeolite are such.The silicate (glass) of the arbitrary element in Na, Ca, K, Mg, B a, Ce, B, Fe and Al.The mixture of the oxide compound of the oxide compound of the element beyond silicon, partial oxide, salt or composite oxides (aluminum oxide, titanium oxide etc.) and silicon, partial oxide, salt or composite oxides.The oxide compound of S iC, SiN.
During using molding as thermal insulation material, preferably at the temperature used, silica dioxide granule is heat-staple.Specifically, preferably under the maximum operation (service) temperature of thermal insulation material, maintenance 1 is constantly little, and the weight of silica dioxide granule does not reduce more than 10%.In addition, silica dioxide granule maintains the viewpoint of heat-insulating property, the form trait of molding from the viewpoint of when using as thermal insulation material, preferably has water tolerance.Specifically, the meltage of preferred silica dioxide granule in the water 100g of 25 DEG C less than 0.1g, more preferably less than 0.01g.
The proportion of silica dioxide granule is preferably less than more than 2.0 4.0 when using molding as thermal insulation material.When being below more than 2.0 3.0, the volume density of molding is little, therefore more preferably, and more preferably less than more than 2.0 2.5.Here, the proportion of silica dioxide granule refers to the true specific gravity utilizing pycnometric method to obtain.
The molding of present embodiment only can contain a kind of silica dioxide granule, also can contain two or more.Under particularly containing particle diameter different 2 kinds of particles, the small-particle be namely made up of silicon-dioxide and oarse-grained situation; BET specific area, thermal conductivity are different from situation about only existing with small-particle or macrobead; therefore; by mixing 2 kinds of particles in the proper ratio, BET specific area and/or thermal conductivity can be adjusted.Such as, certain median size D lsometimes there is BET specific surface area less than 10m in the macrobead for more than 30nm less than 50 μm 2the situation of/g, mix more than 5nm wherein and small-particle less than 30nm time, easily make BET specific surface area be 10m 2/ more than g.In addition, oarse-grained solid thermal conduction is large, and therefore, thermal conductivity exists the situation more than 0.05W/mK sometimes, by mixing small-particle wherein, there is the tendency easily suppressing solid thermal conduction, make thermal conductivity be below 0.05W/mK.For ultimate compression strength, when being only made up of small-particle, ultimate compression strength is too small sometimes, by adding macrobead relative to small-particle, there is the tendency easily ultimate load under rate of compression 0 ~ 5% being adjusted to more than 0.7MPa.
When the molding of present embodiment contains two or more silica dioxide granule, with the BET specific surface area of molding for 10m 2/ more than g 350m 2/ below g, thermal conductivity are that the mode of below 0.05W/mK adjusts macrobead and short grained containing ratio, such as, when mixing the macrobead of the small-particle of about 10nm and about 5 μm, preferred oarse-grained quality/(short grained quality+oarse-grained quality) is 0.02 ~ 0.95, is more preferably 0.10 ~ 0.90, is particularly preferably 0.15 ~ 0.85, at this moment, BET specific surface area becomes 250m 2about/g ~ 40m 2about/g, can adjust BET specific surface area.Become the heat conducting bottleneck in space by these granuloplastic spaces, easily suppress the thermal conduction in space.As mentioned above, the known thermal conductivity with the porous plastid in the space of below diameter 100nm is low, is suitable for thermal insulation material.When wishing to get such powder, waiting the shaping of the ultra-fine grain of below particle diameter 100nm by pressurization is fairly simple method.Relative to this, find, even if with the such no small particle of particle diameter of the such as micron order being considered to be not suitable for use in thermal insulation material raw material in the past for raw material, by mixing with ultra-fine grain (small-particle) with appropriate amount, excellent heat-insulating property also can be shown.This discovery is utilized to be one of preferred configuration of the present invention.By heat treated, there is the large tendency of change in the ultimate compression strength of molding, thermal conductivity, BET specific surface area exists the tendency diminished, and therefore, when implementing heat treated to molding, after enforcement heat treated, measures ultimate compression strength, thermal conductivity and BET specific surface area.
The BET specific surface area of grain diameter influence's molding of silica dioxide granule, when molding is only made up of silicon-dioxide, the BET specific surface area of silica dioxide granule is preferably 10m 2/ more than g 350m 2/ below g, when inorganic mixture contains the composition beyond silica dioxide granule, preferably according to the particle diameter of the BET specific surface area setting silicon-dioxide of its composition.Specifically, when inorganic mixture contains inorganic fibre, the BET specific surface area of general inorganic fibre is less than the BET specific surface area of silicon-dioxide, and therefore, the BET specific surface area of silicon-dioxide is preferably set to 50m 2about/g ~ 400m 2about/g, the particle diameter of silica dioxide granule is preferably set to about 7nm ~ about 50nm.When inorganic mixture contains infrared rays opacification particle, the BET specific surface area of general infrared rays opacification particle is less than the BET specific surface area of silicon-dioxide, and therefore, the BET specific surface area of silicon-dioxide is preferably set to 70m 2about/g ~ 450m 2about/g, the particle diameter of silica dioxide granule is preferably set to about 5nm ~ about 40nm.The particle diameter of silica dioxide granule can by carrying out observing with field emission type scanning electron microscope (FE-SEM) and measuring.Short grained median size D s, oarse-grained median size D lby observing each 1000 small-particles, macrobeads with FE-SEM, its homalographic equivalent circle diameter can be obtained, calculate several mean value, thus confirming.From the viewpoint of the solid conduction of silica dioxide granule, the median size of silica dioxide granule is preferably more than 10nm and less than 80 μm, is more preferably more than 10nm and less than 50 μm, more preferably more than 10nm and less than 30 μm.
Macrobead and short grained molding is contained, short grained median size D in raw material sbe preferably more than 5nm and less than 30nm.D sduring for more than 5nm, with D ssituation outside above-mentioned numerical range is compared, and there is the tendency of small-particle chemical stabilization, there is the tendency that heat-insulating property is easily stable.D sduring less than 30nm, with D ssituation outside above-mentioned numerical range is compared, have that contact area between small-particle is little, the heat transfer caused by solid conduction of molding less, tendency that thermal conductivity is little.
From the viewpoint of reduction thermal conductivity, more preferably D sfor more than 5nm below 25nm, more preferably more than 5nm below 15nm.
Oarse-grained median size D lpreferably meet D s< D l, and be more than 40nm less than 50 μm.D lcan utilize and aforementioned D sidentical method is obtained.D lduring for more than 40nm, there is the tendency that the resilience of molding is little.Here, so-called resilience, refers to after the thermal insulation material precursor press molding using ultra-fine grain as principal constituent, during relief pressure, and the phenomenon that molding significantly expands.D lwhen being below 50 μm, there is the tendency that thermal conductivity is little.
Oarse-grained median size D lduring for more than 40nm less than 10 μm, when molding contains inorganic fibre, infrared rays opacification particle, when preparing the inorganic mixture as the raw material of molding, easy and their Homogeneous phase mixing, therefore more preferably.D lduring for more than 40nm less than 5 μm, the sticking power of particle is large, and the situation that particle comes off from the inorganic mixture of the raw material as molding is few, therefore further preferably.
D lfor D smore than 2 times time, the resilience of molding diminishes, therefore preferably.D lfor D smore than 3 times time, the bulk density of the molding be made up of small-particle and macrobead is large, if molding volume is little, then workability is high, therefore more preferably.D lfor D smore than 4 times time, the difference of small-particle and oarse-grained particle diameter is large, and when mix with macrobead by small-particle, the relative short grained dispersion of macrobead is easy, therefore preferred further.Molding when thermal insulation material purposes, from the viewpoint of the solid heat transfer that the cohesion of particle causes, preferred each Granular composite.
When suppression water immerses molding, cause operability reduction, molding distortion, be full of cracks etc., molding is preferably containing water-resisting agent.As water-resisting agent, such as, can enumerate: the wax system water-resisting agents such as paraffin, polyethylene wax, acrylic acid ethylene co-polymer wax; The silicon system water-resisting agents such as silicone resin, polydimethylsiloxane, alkylalkoxy silane; The fluorine system water-resisting agents such as perfluoroalkyl carboxylate, perfluoralkyl phosphate, perfluoroalkyl leptodactyline; The silane coupling agents such as the organoalkoxysilane containing alkyl or full-fluorine group; The silylating agents etc. such as trimethylchlorosilane and 1,1,1,3,3,3-hexamethyldisilazane.These water-resisting agents can use one kind or two or more.These water-resisting agents can directly use, and also can use with the form of solution or emulsion.In addition, also can by water-resisting agent directly or to be coated on the form of solution or emulsion on molding that inorganic mixture press molding is obtained thus to use.The method of coating is not particularly limited, such as, can enumerate: brushing, roller coat, spraying, spraying, Airless spraying, roller coating machine, impregnating.Use water-resisting agent added to as in the powder of the raw material of molding, the powder that implements WATER REPELLENT be made into body time, also can obtain waterproof effect.The method of adding water-resisting agent in powder is not particularly limited, such as, can enumerate: the method that then powder carries out drying is stirred on the solution limit that limit interpolation water or alcohol equal solvent dilute these water-resisting agent gained; Powder is dispersed in water or alcohol equal solvent and makes slurry, add after water-resisting agent carries out stirring and filter in slurry, carry out dry method; And the vapour cure utilizing trimethylchlorosilane etc. to carry out.In present embodiment, preferably use wax system water-resisting agent, silicon system water-resisting agent.For the containing ratio of the water-resisting agent in inorganic mixture, from the viewpoint of the sufficient waterproof effect of imparting, the mass ratio of the quality/water-resisting agent of inorganic mixture entirety is preferably 100/30 ~ 100/0.1, is more preferably 100/20 ~ 100/0.5, and more preferably 100/10 ~ 100/1.
As silica dioxide granule, can in order to the particle with silica composition manufactured by existing manufacture method being raw material, the particle carrying out adjusting gained to the containing ratio of germanium, thermal conductivity.Such as, silica dioxide granule can for utilizing the damp process under acidity or alkaline condition to make silicate ion condensation and the particle manufactured.Inorganic compound particle containing silicon-dioxide can for utilizing damp process to make organoalkoxysilane hydrolytic condensation and the particle manufactured.Silica dioxide granule also can for the particle manufactured utilizing the silica composition of damp process manufacture to burn till.Inorganic compound particle containing silicon-dioxide can also for burning the compound of the silicon such as muriate and the particle manufactured in the gas phase.Silica dioxide granule can for by silicon metal, the silicon gaseous oxidation burning that obtains containing the heating raw materials of silicon and the particle that manufactures.Silica dioxide granule also can for the particle making the meltings such as silica manufacture.
As the composition beyond silica composition contained in silica dioxide granule, the composition be present in as impurity in above-mentioned manufacture method in raw material can be utilized.Also the composition beyond silica composition can be added in the manufacturing process of silicon-dioxide.
For the manufacture method of known silicon-dioxide, there is following methods.
utilize the silicon-dioxide that damp process synthesizes
Take water glass as the gel silica that raw material manufactures in acid condition.
Take water glass as the precipitated silica that raw material manufactures in the basic conditions.
The silicon-dioxide synthesized by the hydrolytic condensation of organoalkoxysilane.
utilize the silicon-dioxide that drying process is synthesized
The muriate of burning silicon and the aerosil that manufactures.
Burning silicon metal gas and the silicon-dioxide that manufactures.
The fine silica powder that by-product is raw when manufacturing ferrosilicon etc.
Utilize the silicon-dioxide that arc process or plasma method manufacture.
Make silica melting and the fused silica etc. manufactured.
When the mixing of two or more silica dioxide granule, such as small-particle and macrobead is prepared into the raw material of body, in above-mentioned silicon-dioxide, as small-particle, more preferably use aerosil.As macrobead, more preferably use aerosil, burning silicon metal gas and the silicon-dioxide, fine silica powder, the fused silica that manufacture.
As silica dioxide granule, natural silicate minerals can be used.As natural mineral, such as, can enumerate: peridotites class, pistacite class, quartz, feldspar, zeolites etc.By implementing the process such as pulverizing to natural silicate minerals, adjustment BET specific surface area, can use as silica dioxide granule.The containing ratio of Ge insufficient or excessive time, can utilize method described later implement Ge interpolation or removing process, the containing ratio of Ge is adjusted to arbitrary value, as form inorganic mixture silica dioxide granule use.
[2-2]Ge
When silica dioxide granule contains small-particle and macrobead, small-particle or oarse-grained at least one can contain Ge.In addition, the compound containing Ge can also be added in the small-particle not containing Ge, macrobead or small-particle and macrobead.In addition, the mode that small-particle or macrobead are preferably below more than 10 quality ppm 1000 quality ppm with the containing ratio of the Ge in powder contains Ge.According to the difference in source, also have the silicon-dioxide of the Ge containing 10 ~ 1000 quality ppm, but Ge concentration, less than 10 quality ppm, therefore, is preferably adjusted in the mode in above-mentioned scope by the Ge concentration of silicon-dioxide usually.In the manufacturing process of the manufacturing process of silicon-dioxide, powder, by taking the concentration of Ge as the compound that the mode of 10 ~ 1000 quality ppm adds containing Ge, the silica dioxide granule containing Ge can be obtained.As the compound containing Ge, be not particularly limited, such as, can enumerate: the inorganic Ge compound such as oxide compound, composite oxides, nitride, carbide of Ge, as the tetraethoxy germanium [Ge (C of the alkoxide of germanium 2h 5o) 4], four n-butoxy germanium [Ge (C 4h 9o) 4], tetraisopropoxide germanium [Ge (C 3h 7o) 4] etc., carboxyethyl germanium sesquioxide [(GeCH 2cH 2cOOH) 2o 3], tetraethyl-germanium [Ge (C 2h 5) 4], tetrabutyl germanium [Ge (C 4h 9) 4], tributyl germanium [Ge (C 4h 9) 3] etc. organic germanium compounds.These compounds can add separately, also can add their mixture.As long as concentration is 10 ~ 1000 quality ppm, then from the viewpoint of productivity, cost, workability, using containing Ge as impurity containing the inorganic compound particle of silicon-dioxide on the basis that have adjusted thermal conductivity etc. as the raw material of powder be preferred mode.
The method of adding the compound containing Ge is not particularly limited.Such as, can be added in the above-mentioned silicon-dioxide utilizing damp process or drying process to obtain, also can add in above-mentioned each manufacturing process of silicon-dioxide.Compound containing Ge can be water-soluble, also can be water insoluble.Can add with the form of the aqueous solution of the compound containing Ge and/or slurry, and carry out drying as required, also the compound containing Ge can be added with the state of solid matter or fluent meterial.Compound containing Ge can be crushed to the particle diameter of regulation in advance, or, also can carry out coarse reduction in advance.
When silica dioxide granule contains excessive Ge, preferably some process is implemented to silica dioxide granule, the containing ratio of Ge is adjusted to 10 ~ 1000 quality ppm.The method that excessive Ge adjusts to 10 ~ 1000 quality ppm is not particularly limited.Such as, can enumerate and utilize acidic substance or alkaline matter or other element to carry out the method etc. of replacing, extracting, removing, can after the inorganic compound particle chloroazotic acid containing silicon-dioxide, the sodium peroxide aqueous solution etc. be processed, carry out drying, the raw material as powder uses.The minimizing of excessive Ge can be carried out after the inorganic compound particle containing silicon-dioxide is crushed to desired particle diameter in advance, also after Ge is adjusted to specialized range, can pulverize silica dioxide granule again.
[2-3] Fe, other element
In the manufacturing process of the manufacturing process of silicon-dioxide, powder, Fe or K, Mg, Ca, P, S can be added respectively with the form of the compound containing Fe or K, Mg, Ca, P, S, also can use in advance containing F e or K of q.s, the silica dioxide granule of Mg, Ca, P, S.As the compound containing Fe or K, Mg, Ca, P, S, be not particularly limited, such as, can enumerate: the oxide compound of Fe or K, Mg, Ca, P, S, composite oxides, oxyhydroxide, nitride, carbide, carbonate, acetate, nitrate, indissoluble salt and alkoxide etc.These compounds can add separately, also can add their mixture.Using containing as the inorganic compound particle containing silicon-dioxide of Fe or K of impurity, Mg, Ca, P, S as the raw material of powder from the viewpoint of productivity, cost, workability be preferred mode.The inorganic compound particle containing silicon-dioxide so such as can with the particle from silica dioxide gel utilizing the precipitator method to obtain, manufacture ferrosilicon time etc. the form of the raw fine silica powder of by-product obtain.
The method of adding the compound respectively containing Fe or K, Mg, Ca, P, S in silica dioxide granule is not particularly limited.Such as, can be added on not containing in the silica dioxide granule of these metals, also can add these metals in the manufacturing process of silicon-dioxide.Compound respectively containing Fe or K, Mg, Ca, P, S can be water-soluble, also can be water insoluble.Can add with the form of the aqueous solution of the compound respectively containing Fe or K, Mg, Ca, P, S, and carry out drying as required, also the compound respectively containing Fe or K, Mg, Ca, P, S can be added with the state of solid matter or fluent meterial.Compound respectively containing Fe or K, Mg, Ca, P, S can be crushed to the particle diameter of regulation in advance, or, also can carry out coarse reduction in advance.
When silica dioxide granule contains excessive Fe or K, Mg, Ca, P, S, some process can be implemented in the manufacturing process of the manufacturing process of silicon-dioxide, powder, the containing ratio of aforementioned elements is adjusted in specialized range.The method excessive Fe or K, Mg, Ca, P, S being adjusted to specialized range is not particularly limited.Such as, as the inflation method of the containing ratio of Fe, can enumerate and utilize acidic substance or other element to carry out the method etc. of replacing, extracting, removing, can after the inorganic compound particle chloroazotic acid containing silicon-dioxide etc. be processed, carry out drying, the raw material as powder uses.Excessive Fe or K, the adjustment of Mg, Ca, P, S are carried out after the inorganic compound particle containing silicon-dioxide can being crushed to preferable particle size in advance, also Fe or K, Mg, Ca, P, S can be pulverized silica dioxide granule after being adjusted to preferred scope again.
[2-4] blending means
Silica dioxide granule, infrared rays opacification particle and inorganic fibre can use the mixing machine recorded in known powder mixer, such as revision six editions chemical engineering handbooks (ball is apt to) to mix.At this moment, also can mix two or more silica dioxide granule or mix the compound or its aqueous solution that contain Na, K, Mg, Ca, Fe, P, S respectively.As known powder mixer, can enumerate: as container rotating type (container self rotates, vibration, shake) horizontal circle cartridge type, V-type (can with agitating vane), bicone, cubic type and shake rotary-type; As single shaft banding pattern, multiaxis slurry type, rotation rake, dual shaft planetary stirring-type, circular cone screw type, high-speed stirring type, rotary disk type, band roller rotary container type, band stirring rotary container type, the high speed elliptic rotor type of mechanical stirring (container is fixed, and stirs with blade etc.); As flowing stirring-type (utilize air, gas stir) airflow stirring type, utilize gravity to carry out without stirring-type.Also can combine these mixing machines to use.
The mixing of silica dioxide granule, infrared rays opacification particle and inorganic fibre can limit use known pulverizer, such as revise pulverizer pulverized particles or the severing inorganic fibre recorded in six editions chemical engineering handbooks (ball is apt to) or improve particle, the dispersed limit of inorganic fibre carries out.At this moment, the inorganic compound particle that two or more also can be made to contain silicon-dioxide is pulverized, dispersion, or makes the compound respectively containing Na, K, Mg, Ca, Fe, P, S or its aqueous solution pulverize, disperse.As known pulverizer, can enumerate: roller mill (high pressure compressed roller mill, roller rotary grinder), stamp mill, crushing mill (multi-mull mixer, Chile's formula wheel roller), cut off and shear shredder (knife mill etc.), rod mill, autogenous mill (aerofall mill, cascade mill etc.), vertical roll grinder (ring roller mill, roller finishing machine, ball shredder), high-speed rotary is gone round and round a millstone (hammer mill, squirrel cage mill, pulverizer (Disintegrator), screen mill, dials formula grinding machine), grading machine internally-arranged type high-speed rotary is gone round and round a millstone (to be fixed and impacts template shredder, Scroll-type shredder, centrifugal classification type shredder, circular-gap sand mill), container driving medium shredder (rotary mill (mill,pot, tuber grinder, conical bell mill), (circular vibration grinds vibromill, rotational vibration is ground, centrifugal mill), planetary mills, centrifugal flowization is ground), media-agitation type mill (tower mill, stir slot type shredder, horizontal circulation slot type shredder, vertical circulation slot type shredder, circular-gap sand mill), jet mill (air-flow induction type, type is passed through in nozzle, conflict type, fluidised bed sprays blowing-type), (high speed centrifugation roller grinds compacting cutting mill, interior abrasive disc (Inner piece) formula), mortar, grinding stone etc.Also can combine these pulverizers to use.
In these mixing machines and pulverizer, the dispersiveness that powder mixer, the high-speed rotary with agitating vane are gone round and round a millstone, grading machine internally-arranged type high-speed rotary is gone round and round a millstone, container driving medium shredder, compacting cutting mill improve particle, inorganic fibre, therefore preferably.In order to improve the dispersiveness of particle, inorganic fibre, the circumferential speed preferably making the top of agitating vane, swivel plate, hammer plate, blade, pin etc. is more than 100km/h, is more preferably more than 200km/h, more preferably more than 300km/h.
When mixing multiple silica dioxide granule, preferably with the order that bulk density is ascending, silica dioxide granule is dropped in stirrer or pulverizer.During containing inorganic fibre, infrared rays opacification particle, after mixed silica particle, preferably add infrared rays opacification particle mix, then mix adding inorganic fibre thereafter.
In silica dioxide granule, metal oxide sol can be added on the basis of inorganic fibre, infrared rays opacification particle, inorganic fibre, infrared rays opacification particle also can be replaced to add metal oxide sol.Metal oxide sol becomes inorganic adhesive, can easily obtain the molding with high compressive strength.When mixing multiple silica dioxide granule, from the viewpoint of making metal oxide sol be highly dispersed in molding entirety, preference, as utilized aforesaid method to mix in advance small-particle and macrobead, then adds metal oxide sol and mixes.During mixed metal oxide colloidal sol, also same with mixing small-particle and oarse-grained situation, preferred limit use known possess agitating vane pulverizer pulverized particles or severing inorganic fibre or improve the dispersiveness of particle, inorganic fibre, while make the circumferential speed on agitating vane top be that 100km/h mixes.In order to improve the dispersiveness of metal oxide sol, preferred use has the powder mixer of agitating vane, the circumferential speed on agitating vane top is made to be more than 100km/h, from the viewpoint of the contact reduced further between macrobead, be more preferably more than 200km/h, more preferably more than 300km/h.
As the example of metal oxide sol, can enumerate: silicon dioxide gel, alumina sol, zirconia sol, cerium oxide sol, titanium oxide sol.From the viewpoint of the viewpoint and the thermotolerance that reduce thermal conductivity, preferred silicon dioxide gel, alumina sol.The particle diameter of metal oxide sol is preferably 2nm ~ 450nm from the viewpoint of reduction thermal conductivity, is more preferably 4nm ~ 300nm, more preferably 4nm ~ 200nm.
From the viewpoint of mixture when suppressing to mix with silicon-dioxide, inorganic fibre, infrared rays opacification particle be attached to steel basin inwall, stir and become uneven; for the addition of metal oxide sol; relative to the total mass of molding; the containing ratio of the solids component of metal oxide sol is preferably 0.5 quality % ~ 30 quality %; be more preferably 1 quality % ~ 25 quality %, more preferably 2 quality % ~ 25 quality %.
[2-5] manufacturing process
Inorganic mixture press molding as raw material can obtain by the molding of present embodiment, and forming process and heating process described later can be carried out for (a) simultaneously, also can carry out heating process for (b) after forming process.Namely, the method that mould (shaping dies) limit of mineral compound can be had to pressurize for (a) limit heating filling (storage), also can for (b) by pressurizeing after mineral compound shaping to mould under the state being filled with mineral compound, the method heated under the molding obtained being taken out post-heating from mould or being in the state mould at the molding obtained.In two kinds of modes, pressure and the Heating temperature of preferred pressurization are roughly the same.
As pressing/molding method, the current known ceramic press molding methods such as mould press forming method (plunger tpe press molding method), rubber rolling process (hydrostaticpressure moulding method), extrusion molding method can be utilized to form.From the viewpoint of productivity, preferred mold press forming method.
In mould press forming method, rubber rolling process, when inorganic mixture is filled in a mold, make the inorganic mixture vibration of the raw material as molding etc. and fill uniformly, due to the thickness of molding can be made to become evenly, therefore preferably.While when inorganic mixture being filled in mould to degassed limit of reducing pressure in mould, can fill at short notice, therefore, be preferred from the viewpoint of productivity.
When being target sizes to set the condition of press molding from the viewpoint of the ultimate load made under rate of compression 0 ~ 5% and/or thermal conductivity, preferably with the volume density of the molding obtained for 0.25g/cm 3above 2.0g/cm 3following mode sets.During for controlling molding condition with moulding pressure, according to the difference of the inlet of the air between the particle of the sliding of used powder, powder and in pore etc., with the passage of the time kept under pressurised conditions, force value changes, therefore, there is the tendency that production management becomes difficult.Consider in contrast, never need the period can easily make the load of the molding obtained become in target value this point, the method controlling volume density is preferred.The volume density of molding, from the viewpoint of burden when alleviating carrying, is more preferably 0.25g/cm 3above 1.7g/cm 3below, more preferably 0.25g/cm 3above 1.5g/cm 3below.It should be noted that, the volume density as molding is 0.25g/cm 3above 2.0g/cm 3following compacting pressure, be such as the pressure of more than 0.01MPa below 50MPa, the volume density as molding is 0.25g/cm 3above 1.7g/cm 3following compacting pressure, be such as the pressure of more than 0.01MPa below 40MPa, the volume density as molding is 0.25g/cm 3above 1.5g/cm 3following compacting pressure is such as the pressure of more than 0.01MPa 30MPa.
When the example mode being prescribed level with the volume density of the molding obtained being manufactured to the method for body is described, first, the weight of required inorganic mixture is obtained by the volume of molding and volume density.Then, the inorganic mixture of weighing is filled in shaping dies, carries out press molding in the mode becoming specific thickness.Specifically, factory length 30cm, width 30cm, thickness 20mm and volume density is 0.5g/cm 3molding time, by the volume making target volume density be multiplied by the molding of manufacture, the weight of the powder needed for manufacture of molding can be obtained.That is, in the example of above-mentioned molding, be 0.5 [g/cm 3] × 30 [cm] × 30 [cm] × 2 [cm]=900 [g], required powder is 900g.
Generalization, manufacturing volume is α (cm 3), volume density is β (g/cm 3) molding of (wherein, β is greater than the volume density of powder) time, preferably weigh α β (g) powder, by powder compression to volume α, thus form.
[2-6] heating treatment method
When supplying practical application after the molding in press molding or after press molding being carried out in the condition and range of the sufficient temperature and time of the thermotolerance of molding the planar water of heat drying, removing molding, thermal conductivity step-down, therefore preferably.And then, can also heat treated be implemented.
The manufacture method of the molding of present embodiment preferably has following operation: to containing silicon-dioxide and germanium and according to the operation that behaviour in service is added with infrared rays opacification particle, inorganic fibre and the molding formed carry out heat treated.From the viewpoint of dimensional stability, heat treatment temperature is preferably the temperature also higher than the maximum operation (service) temperature of this molding.Described heat treatment temperature is of all kinds according to the difference of the purposes of molding, specifically, is preferably 600 ~ 1200 DEG C, is more preferably 700 ~ 1200 DEG C, more preferably 800 ~ 1200 DEG C.
In order to make the ultimate load under rate of compression 0 ~ 5% be more than 0.7MPa, molding can comprise metal oxide sol as mentioned above.When molding comprises metal oxide sol, there is the tendency that molding easily solidifies under lower heat treatment temperature, therefore, specifically, heat treatment temperature is preferably 200 ~ 1200 DEG C, is more preferably 300 ~ 1200 DEG C, more preferably 400 ~ 1200 DEG C.
The atmosphere of heat treated can be enumerated in air in (or in air), oxidizing atmosphere in (oxygen, ozone, oxynitride, carbonic acid gas, hydrogen peroxide, hypochlorous acid, inorganic organo-peroxide etc.) and non-active gas atmosphere (helium, argon, nitrogen etc.).Heating treatment time is suitably selected according to the amount of heat treatment temperature and molding.
Heat treated can be implemented after the inorganic mixture of the raw material as molding is filled in field of employment, also can implement by the molding of inorganic mixture press molding gained.
The manufacture method of [2-7] cutting body
The molding of present embodiment can obtain cutting body by cutting its part.As the manufacture method of cutting body, such as, comprise following operation: the inorganic mixture storage storage operation in a mold by the containing ratio containing silicon-dioxide and germanium and germanium being below more than 10 quality ppm 1000 quality ppm; With the forming process that inorganic mixture is shaped; With the cutting process cut a part for the molding obtained in forming process.As the topping machanism of molding, be not particularly limited, the milling machines etc. such as lathe, General Milling Cutter, vertical NC machine tools with automatic tool changer, horizontal NC machine tools with automatic tool changer, 5 axis processing machines such as cutter, disc saw, scroll saw, scroll saw sawing machine, drill bit, grinding machine, band saw, side cutter milling cutter, universal lathe, bench lathe and NC lathe can be used, particularly preferably band saw, lathe, milling machine.
Here, in the forming process in the manufacture method of above-mentioned cutting body, from the viewpoint of not easily avalanche during machining, preferably possess (c) with the volume density of molding for 0.25g/cm 3above 2.0g/cm 3following mode is pressurizeed to shaping dies, carries out the operation heated simultaneously, also preferably possessing (d) by pressurizeing after inorganic mixture shaping to shaping dies, implementing the operation of heat treated at the temperature more than 600 DEG C.
[3] cladding
Cladding has molding and is accommodated the outer cover material material of body.Cladding has easy process, also easy such advantage of constructing compared with molding.Fig. 1 is an example of the diagrammatic cross-section of the cladding of present embodiment.In addition, Fig. 2 is the small-particle of present embodiment and an example of oarse-grained diagrammatic cross-section.As shown in Figures 1 and 2, the cladding 1 of present embodiment is made up of the molding 2 containing the large multiple macrobead L of multiple small-particle S and particle diameter ratio small-particle S and the outer cover material material 3 that is accommodated body 2.In molding 2, small-particle S and macrobead L mixes existence, there is small-particle S around macrobead L.It should be noted that, sometimes molding is called core.
[3-1] outer cover material material
As long as the molding that outer cover material material can be received as core is just not particularly limited, as an example, can enumerate: woven fiber glass, alumina fibre cloth, the inorganic fibre fabrics such as titanium dioxide silicon cloth, inorganic fibre compiles thing, polyester film, polyethylene film, polypropylene screen, nylon membrane, polyethylene terephthalate film, the resin moldings such as fluorine resin film, plastic-metal film, aluminium foil, stainless steel foil, the tinsels such as Copper Foil, ceramic paper, inorganic fiber nonwoven fabrics, organic fibre non-woven fabrics, glass fiber paper, carbon fiber paper, rock wool paper, inorganic fill paper, organic fibre paper, ceramic coating, fluor resin coating, the resin coatings etc. such as silicone resin coating.During using cladding as thermal insulation material, from the viewpoint of the thermal capacitance reducing outer cover material material, the preferably thinner thickness of outer cover material material, suitably can select according to behaviour in service, desirable strength etc.Outer cover material material by use core temperature under stable material form time, during use, also for cover the inorganic mixture of material storage as core or the state of molding outward.At high temperature when spendable cladding, be easy to viewpoint from using the process of rear core consider, the outer cover material material that preferred thermotolerance is high, in this specification sheets, " outer cover material material ", except receiving the material of core when comprising and use core, is also included in the material receiving core in the carrying of core, working procedure.That is, outer cover material material comprise only when carrying, construction time protection core and the material of melting and/or volatilization in use, therefore, outer cover material material himself, organic composition contained in outer cover material material can melting under the use temperature of core, disappearance.
Outer cover material material is easy to viewpoint from coated operation and considers, the sheet that the tinsels such as resin molding, plastic-metal film, aluminium foil, stainless steel foil, Copper Foil such as the inorganic fibre fabrics such as preferred glass cloth, alumina fibre cloth, titanium dioxide silicon cloth, inorganic fibre volume thing, polyester film, polyethylene film, polypropylene screen, nylon membrane, polyethylene terephthalate film, fluorine resin film, ceramic paper, inorganic fiber nonwoven fabrics, organic fibre non-woven fabrics, glass fiber paper, carbon fiber paper, rock wool paper, inorganic fill paper, organic fibre paper are such.
When at high temperature using cladding, from the viewpoint of thermostability, outer cover material material is more preferably the inorganic fibre fabrics such as woven fiber glass, alumina fibre cloth, titanium dioxide silicon cloth, inorganic fibre compiles thing, ceramic paper, inorganic fiber nonwoven fabrics.From the viewpoint of intensity, outer cover material material more preferably inorganic fibre fabric.
[3-2] is by the coated method of outer cover material material
For the molding of present embodiment, can to add macrobead, infrared rays opacification particle, inorganic fibre and the inorganic mixture that formed for raw material containing silica dioxide granule according to behaviour in service, by this inorganic mixture press molding, as core, then coated with outer cover material material.During using molding as core, can as described later, using the inorganic mixture of the raw material as molding and outer cover material material press molding simultaneously, also can be coated with outer cover material material after by inorganic mixture press molding.
The core method that outer cover material material is coated is not particularly limited, can implement simultaneously the preparation of core and shaping and utilize outer cover material material to carry out coated, also can be coated with outer cover material material after preparing core or making it be shaped.
When outer cover material material is the lamellar morphologies such as inorganic fibre fabric, resin molding, plastic-metal film, tinsel, ceramic paper, inorganic fiber nonwoven fabrics, organic fibre non-woven fabrics, glass fiber paper, carbon fiber paper, rock wool paper, inorganic fill paper, organic fibre paper, can by the stitching that such as utilizes inorganic fibre yarn or resin fibre yarn etc. to carry out, being adhesively fixed of outer cover material material, sew up and bonding the two carry out coated.
When the outer cover material material of sheet is resin molding, plastic-metal film, tinsel etc., from the viewpoint of the easy degree of coated operation, preferably vacuum packed, shrink packaging.
When outer cover material material is ceramic coating, resin coating etc., can be coated with outer cover material material by core by being coated on hairbrush or sprayer on core.
The indenture of wire also can be set on the molding be made up of core and the outer cover material material of press molding gained, be given to body with flexibility.The form of line can select linearity, curve-like, dotted line shape etc. according to the behaviour in service of molding, also can combine wherein two or more.The rugosity of line, the degree of depth of indenture decide according to the thickness of molding, intensity, behaviour in service.
Outer cover material material can the whole surface of coated core, also can the part of coated core.
[4] purposes
The molding containing silica dioxide granule and Ge of present embodiment and cladding, except may be used for thermal insulation material, can also be preferred for the carrier, reodorant, deodorant, humidity adjusting material, weighting agent, pigment etc. of the chemical reagent such as sound absorbent material, soundproof material, sound-proof material, anti-noise-reflecting material, quieter material, abrasive, support of the catalyst, sorbent material, absorption perfume compound and sterilant.
[5] mensuration of parameter
The mensuration of the containing ratio of the Ge of inorganic mixture, BET specific surface area mensuration, the mensuration of ultimate compression strength, the mensuration of thermal conductivity utilize following method to implement.
the mensuration of the containing ratio of Ge
Molding agate mortar is pulverized, is filled in in vinylchlorid ring, carry out press molding with XRF tablet former, make tablet, as working sample.With Co., Ltd. Neo-Confucianism fluorescent x-ray analyzer RIX-3000, it is measured.
ultimate compression strength
Molding is processed into length 2cm, width 2cm, thickness 2cm, uses Shimadzu Scisakusho Ltd's system accurate universal testing machine Autograph AG-100KN, measured ultimate compression strength with press-in speed 0.5mm/ minute.
the mensuration of thermal conductivity
Using make length 30cm, width 30cm, thickness 20mm the molding of shape as working sample, use heat flowmeter HFM 436Lambda (trade(brand)name, NETZSCH Inc.) to measure thermal conductivity at 30 DEG C.Correct according to JISA1412-2, use density 163.12kg/m 3, thickness 25.32mm NIST SRM 1450c correction on-gauge plate, under the temperature head of high temperature side and low temperature side is the condition of 20 DEG C, implement at 15,20,24,30,40,50,60,65 DEG C in advance.Thermal conductivity at 800 DEG C measures based on the method for JIS A 1421-1.2 are made into diameter 30cm, thickness 20mm discoideus molding as working sample, use protection hot plate method measuring thermal conductivity device (Eko Instruments Trading's system) as determinator.
Embodiment
Below, utilize embodiment to illustrate in greater detail the present invention, but the present invention is not limited to these embodiments.Those skilled in the art can carry out various change to the content comprising embodiment shown below and implement, and described change is also contained in the scope of Patent right requirement of the present invention.It should be noted that, the mensuration of the mensuration of the containing ratio of the Ge of the inorganic mixture in embodiment and comparative example, the mensuration of thermal conductivity, ultimate compression strength is as described above respectively carries out.
embodiment 1
Be that the silicon-dioxide powdery of 0 quality ppm adds in the ethanolic soln of isopropoxy germanium (IV) by Ge containing ratio, be stirred to complete drying.After 24 hours heat treated are implemented at 100 DEG C to the powder obtained, then heat 24 hours at 700 DEG C.To obtain length 30cm, width 30cm, thickness 20mm, volume density for 0.25g/cm 3the mode of molding, be length 30cm in interior dimensions, fill silicon-dioxide powdery 450g in the mould of width 30cm, carry out press molding, result, obtaining volume density is 0.25g/cm 3molding.At 1000 DEG C, 24 hours heat treated are implemented to this molding, makes the molding of embodiment 1.The containing ratio of the Ge of the molding of embodiment 1 is 21 quality ppm, and the thermal conductivity at 30 DEG C is 0.0201W/mK.Vertically cut off by molding, make the cutting body of 25 length 6cm, width 6cm, thickness 20mm, any one in these 25 cutting bodies does not all occur cracked, damaged.And then cut off by the cutting body of this length 6cm, width 6cm, thickness 20mm, be processed as length 2cm, width 2cm, thickness 2cm, measure ultimate compression strength, result, when rate of compression=3.9%, there is breakdown point in sample avalanche, and load is now 0.7MPa.
embodiment 2
Obtaining using hammer mill to be silicon-dioxide powdery (small-particle) the 50 quality % of 0 quality ppm and Ge containing ratio by Ge containing ratio is the mixed uniformly silicon-dioxide powdery of silicon-dioxide powdery (macrobead) 50 quality % of 571 quality ppm.Use this silicon-dioxide powdery 594g, carry out press molding similarly to Example 1, obtain length 30cm, width 30cm, thickness 20mm, volume density be 0.33g/cm 3molding after, at 1000 DEG C implement 5 hours heat treated, obtain the molding of embodiment 2.The containing ratio of the Ge of the molding of embodiment 2 is 286 quality ppm, and the thermal conductivity at 30 DEG C is 0.0198W/mK.Cut off similarly to Example 1 by the molding of embodiment 2, make 25 cutting bodies, any one in these 25 cutting bodies does not all occur cracked, damaged.And then operate similarly to Example 1, measure ultimate compression strength, result, the ultimate load under rate of compression=5.0% is 0.8MPa.
In addition, use above-mentioned silicon-dioxide powdery, in the mode of length 30cm, width 30cm, thickness 20mm, use thermocompressor to implement 5 hours stress and heating at 1000 DEG C.The thermal conductivity of the molding obtained at 30 DEG C is 0.0199W/mK.Cut off similarly to Example 1, make 25 cutting bodies, any one in these 25 cutting bodies does not all occur cracked, damaged.And then operate similarly to Example 1, measure ultimate compression strength, result, the ultimate load under rate of compression=5.0% is 0.9MPa.It should be noted that, short grained median size D sfor 7.5nm, oarse-grained median size D lfor 80nm.
embodiment 3
Obtaining using hammer mill to be silicon-dioxide powdery (small-particle) the 25 quality % of 0 quality ppm and Ge containing ratio by Ge containing ratio is the mixed uniformly silicon-dioxide powdery of silicon-dioxide powdery (macrobead) 75 quality % of 0 quality ppm.This silicon-dioxide powdery is added in the ethanolic soln of isopropoxy germanium (IV), be stirred to complete drying.After 24 hours heat treated are implemented at 100 DEG C to the powder obtained, then heat 24 hours at 700 DEG C.Use this powder 1260g, carry out press molding similarly to Example 1, obtain length 30cm, width 30cm, thickness 20mm, volume density be 0.70g/cm 3molding after, at 1000 DEG C implement 5 hours heat treated, obtain the molding of embodiment 3.The containing ratio of the Ge of the molding of embodiment 3 is 897 quality ppm, and the thermal conductivity at 30 DEG C is 0.0314W/mK.Cut off similarly to Example 1 by the molding of embodiment 3, make 25 cutting bodies, any one in these 25 cutting bodies does not all occur cracked, damaged.And then operate similarly to Example 1, measure ultimate compression strength, result, when rate of compression=2.8%, there is breakdown point in sample avalanche, and load is now 1.6MPa.It should be noted that, short grained median size D sfor 14nm, oarse-grained median size D lit is 10 μm.
embodiment 4
Using hammer mill to be silicon-dioxide powdery (small-particle) the 22.5 quality % of 0 quality ppm and Ge containing ratio by Ge containing ratio is after silicon-dioxide powdery (macrobead) the 67.5 quality % Homogeneous phase mixing of 571 quality ppm, add the glass fibre 10 quality % that fiber diameter is 11 μm, average fiber length is 6.4mm, heat resisting temperature is 1050 DEG C, Homogeneous phase mixing in high shear mixers, obtains silicon-dioxide powdery.Use this powder 864g, carry out press molding similarly to Example 1, obtain length 30cm, width 30cm, thickness 20mm, volume density be 0.48g/cm 3molding after, at 1000 DEG C implement 24 hours heat treated, obtain the molding of embodiment 4.The containing ratio of the Ge of the molding of embodiment 4 is 385 quality ppm, and the thermal conductivity at 30 DEG C is 0.0263W/mK.Cut off similarly to Example 1 by the molding of embodiment 4, make 25 cutting bodies, any one in these 25 cutting bodies does not all occur cracked, damaged.And then operate similarly to Example 1, measure ultimate compression strength, result, when rate of compression=3.0%, there is breakdown point in sample avalanche, and load is now 1.7MPa.It should be noted that, short grained median size D sfor 7.5nm, oarse-grained median size D lfor 80nm.
embodiment 5
Using hammer mill to be silicon-dioxide powdery (small-particle) the 19 quality % of 0 quality ppm and Ge containing ratio by Ge containing ratio is after silicon-dioxide powdery (macrobead) the 57 quality % Homogeneous phase mixing of 571 quality ppm, the glass fibre 10 quality % that to add median size be the zirconium silicate 14 quality % as infrared rays opacification particle, the fiber diameter of 1 μm is 11 μm, average fiber length is 6.4mm, heat resisting temperature is 1050 DEG C, Homogeneous phase mixing in high shear mixers, obtains silicon-dioxide powdery.Use this powder 972g, carry out press molding similarly to Example 1, obtain length 30cm, width 30cm, thickness 20mm, volume density be 0.54g/cm 3molding after, at 1000 DEG C implement 24 hours heat treated, obtain the molding of embodiment 5.The containing ratio of the Ge of the molding of embodiment 5 is 325 quality ppm, and the thermal conductivity at 30 DEG C is 0.0273W/mK.Cut off similarly to Example 1 by the molding of embodiment 5, make 25 cutting bodies, any one in these 25 cutting bodies does not all occur cracked, damaged.And then operate similarly to Example 1, measure ultimate compression strength, result, when rate of compression=3.4%, there is breakdown point in sample avalanche, and load is now 1.9MPa.It should be noted that, short grained median size D sfor 7.5nm, oarse-grained median size D lfor 80nm.
embodiment 6
Use Ge containing ratio to be 571 quality ppm and the median size silicon-dioxide powdery 1170g that is 80nm, carry out press molding similarly to Example 1, obtain length 30cm, width 30cm, thickness 20mm, volume density be 0.65g/cm 3molding after, at 1000 DEG C implement 5 hours heat treated, obtain the molding of embodiment 6.The containing ratio of the Ge of the molding of embodiment 6 is 571 quality ppm, and the thermal conductivity at 30 DEG C is 0.0387W/mK.Cut off similarly to Example 1 by the molding of embodiment 6, make 25 cutting bodies, any one in these 25 cutting bodies does not all occur cracked, damaged.And then operate similarly to Example 1, measure ultimate compression strength, result, when rate of compression=2.8%, there is breakdown point in sample avalanche, and load is now 1.3MPa.
embodiment 7
The carboxyethyl germanium sesquioxide aqueous solution of 0.5% is slowly added drop-wise to silicon dioxide gel solution (Nissan Chemical Inc., trade(brand)name " Snowtex 40 ", the SiO of the colloidal particle size 10 ~ 20nm of the whipped state remained at 15 DEG C 2containing ratio: 40 quality %) in, obtain the mixed slurry of silicon dioxide gel, carboxyethyl germanium sesquioxide.Thereafter, be set as that the spray drying unit of 130 DEG C carries out spraying dry to mixed slurry by temperature out, obtain solid matter.Then, by the solid matter that obtains in electric furnace with 2 hours after room temperature to 300 DEG C, keep 3 hours at 300 DEG C.After being warming up to 550 DEG C with 2 hours again, after at 550 DEG C, maintenance is burnt till for 3 hours, Slow cooling, obtains the silicon-dioxide powdery of embodiment 7.Use this powder 990g, carry out press molding similarly to Example 1, obtain length 30cm, width 30cm, thickness 20mm, volume density be 0.55g/cm 3molding after, at 1000 DEG C implement 24 hours heat treated, obtain the molding of embodiment 7.The containing ratio of the Ge of the molding of embodiment 7 is 53 quality ppm, and the thermal conductivity at 30 DEG C is 0.0341W/mK.Cut off similarly to Example 1 by the molding of embodiment 7, make 25 cutting bodies, any one in these 25 cutting bodies does not all occur cracked, damaged.And then operate similarly to Example 1, measure ultimate compression strength, result, when rate of compression=2.6%, there is breakdown point in sample avalanche, and load is now 0.8MPa.
embodiment 8
In the flame formed by oxygen gas-supplying in the burner and hydrogen, supply silicon tetrachloride and germanium tetrachloride, the glass fine particle of Porous is deposited in target bar.Take this glass fine particle, the content obtaining Ge is 357 quality ppm, BET specific surface area is 117m 2the silicon-dioxide powdery of/g.Use this powder 450g, carry out press molding similarly to Example 1, obtain length 30cm, width 30cm, thickness 20mm, volume density be 0.25g/cm 3molding after, at 1000 DEG C implement 5 hours heat treated, obtain the molding of embodiment 8.The containing ratio of the Ge of the molding of embodiment 8 is 473 quality ppm, and the thermal conductivity at 30 DEG C is 0.0215W/mK.Cut off similarly to Example 1 by the molding of embodiment 8, make 25 cutting bodies, any one in these 25 cutting bodies does not all occur cracked, damaged.And then operate similarly to Example 1, measure ultimate compression strength, result, when rate of compression=3.1%, there is breakdown point in sample avalanche, and load is now 1.0MPa.
embodiment 9
Using hammer mill to be silicon-dioxide powdery (small-particle) the 21 quality % of 0 quality % and Ge containing ratio by Ge containing ratio is after silicon-dioxide powdery (macrobead) the 64 quality % Homogeneous phase mixing of 571 quality ppm, add the zirconium silicate 15 quality % as infrared rays opacification particle that median size is 1 μm, proceed Homogeneous phase mixing, obtain the silicon-dioxide powdery of embodiment 9.Use this powder 918g, carry out press molding similarly to Example 1, obtain length 30cm, width 30cm, thickness 20mm, volume density be 0.51g/cm 3molding after, at 1000 DEG C implement 5 hours heat treated, obtain the molding of embodiment 9.The containing ratio of the Ge of the molding of embodiment 9 is 365 quality ppm, and the thermal conductivity at 30 DEG C is 0.0273W/mK.In addition, each this silicon-dioxide powdery of use 721g, uses the round tube type mould that internal diameter is diameter 30cm, carries out press molding, obtain the discoideus molding of 2 diameter 30cm, thickness 20mm.Use this 2 moldinies, the thermal conductivity at measuring 800 DEG C is 0.0633W/mK.Cut off similarly to Example 1 by the molding of embodiment 9, make 25 cutting bodies, any one in these 25 cutting bodies does not all occur cracked, damaged.And then operate similarly to Example 1, measure ultimate compression strength, result, when rate of compression=4.4%, there is breakdown point in sample avalanche, and load is now 0.8MPa.It should be noted that, short grained median size D sfor 14nm, oarse-grained median size D lfor 80nm.
embodiment 10
Using hammer mill to be silicon-dioxide powdery (small-particle) the 21 quality % of 0 quality ppm and Ge containing ratio by Ge containing ratio is after silicon-dioxide powdery (macrobead) the 63 quality % Homogeneous phase mixing of 571 quality ppm, the glass fibre 1 quality % that to add median size be the zirconium silicate 15 quality % as infrared rays opacification particle, the fiber diameter of 1 μm is 11 μm, average fiber length is 6.4mm, heat resisting temperature is 1050 DEG C, Homogeneous phase mixing in high shear mixers, obtains silicon-dioxide powdery.Use this powder 864g, carry out press molding similarly to Example 1, obtain length 30cm, width 30cm, thickness 20mm, volume density be 0.48g/cm 3molding after, at 1000 DEG C implement 5 hours heat treated, obtain the molding of embodiment 10.The containing ratio of the Ge of the molding of embodiment 10 is 357 quality ppm, and the thermal conductivity at 30 DEG C is 0.0246W/mK.Cut off similarly to Example 1 by the molding of embodiment 10, make 25 cutting bodies, any one in these 25 cutting bodies does not all occur cracked, damaged.And then operate similarly to Example 1, measure ultimate compression strength, result, the ultimate load under rate of compression=5.0% is 0.9MPa.It should be noted that, short grained median size D sfor 14nm, oarse-grained median size D lfor 80nm.
comparative example 1
Except not adding except Ge, operating similarly to Example 1, obtaining the molding of comparative example 1.For being cut off similarly to Example 1 by the molding of comparative example 1, make 25 cutting bodies, but cracked, badly broken, the cutting body of length 6cm, width 6cm, thickness 20mm can not be obtained.And then operate similarly to Example 1, measure ultimate compression strength, result, in the scope of rate of compression=0 ~ 5%, with compression, sample deforms, and does not occur clear and definite breakdown point, and the load under rate of compression=5% is 0.1MPa.
comparative example 2
Except unreal applying thermal treatment, operate similarly to Example 6, obtain the molding of comparative example 2.For being cut off similarly to Example 1 by the molding of comparative example 2, make 25 cutting bodies, but cracked, badly broken, the cutting body of length 6cm, width 6cm, thickness 20mm can not be obtained.And then operate similarly to Example 1, measure ultimate compression strength, result, in the scope of rate of compression=0 ~ 5%, with compression, sample deforms, and does not occur clear and definite breakdown point, and the load under rate of compression=5% is 0.3MPa.
comparative example 3
Be that the silicon-dioxide powdery of 571 quality ppm adds in the ethanolic soln of isopropoxy germanium (IV) by Ge containing ratio, be stirred to complete drying.After 24 hours heat treated are implemented at 100 DEG C to the powder obtained, then heat 24 hours at 700 DEG C.Use this powder 1170g, carry out press molding similarly to Example 1, obtain length 30cm, width 30cm, thickness 20mm, volume density be 0.65g/cm 3molding after, at 1000 DEG C implement 5 hours heat treated, result, molding breaks, and can not measure thermal conductivity.It should be noted that, the containing ratio of the Ge of the molding of comparative example 3 is 1107 quality ppm, time-and-motion study ultimate compression strength similarly to Example 1, result, and when rate of compression=1.9%, breakdown point, appears in sample avalanche, and load is now 2.1MPa.

Claims (17)

1. a molding, it contains silicon-dioxide and germanium, and the containing ratio of described germanium is below more than 21 quality ppm 897 quality ppm, and the ultimate load under rate of compression 0 ~ 5% is more than 0.7MPa, and the thermal conductivity at 30 DEG C is below 0.05W/mK,
Described molding is by by containing silicon-dioxide and germanium and the inorganic mixture that the containing ratio of described germanium is below more than 10 quality ppm 1000 quality ppm is accommodated in the storage operation in shaping dies; Obtain with the forming process that described inorganic mixture is shaped,
Described forming process has following operation (a) or operation (b),
A () utilizes described shaping dies to pressurize to described inorganic mixture, be heated to the operation of more than 600 DEG C simultaneously,
B () implements the operation of heat treated after being shaped by described inorganic mixture by pressurization at the temperature more than 600 DEG C.
2. molding according to claim 1, wherein, further containing infrared rays opacification particle, the thermal conductivity at 800 DEG C is below 0.2W/mK.
3. molding according to claim 2, wherein, the median size of described infrared rays opacification particle is more than 0.5 μm less than 30 μm, and the containing ratio of infrared rays opacification particle with the quality of molding for being below more than 0.1 quality % 39.5 quality % during benchmark.
4. the molding according to any one of claims 1 to 3, wherein, containing iron, the containing ratio of described iron is below more than 0.005 quality % 6 quality %.
5. the molding according to any one of claims 1 to 3, wherein, further containing inorganic fibre, the containing ratio of described inorganic fibre is below more than 0.1 quality % 50 quality %.
6. molding according to claim 4, wherein, further containing inorganic fibre, the containing ratio of described inorganic fibre is below more than 0.1 quality % 50 quality %.
7. molding according to claim 5, wherein, described inorganic fibre has bio-soluble.
8. molding according to claim 6, wherein, described inorganic fibre has bio-soluble.
9. a cladding, it outer cover material material possessing the molding according to any one of claim 1 ~ 8 and receive described molding.
10. cladding according to claim 9, wherein, described outer cover material material contains inorganic fibre.
11. claddings according to claim 9, wherein, described outer cover material material is resin molding.
The manufacture method of 12. 1 kinds of moldinies, the manufacture method of its molding according to any one of claim 1 ~ 8, wherein, following operation is possessed: by containing silicon-dioxide and germanium and the containing ratio of described germanium is the operation of carrying out heat treated at the inorganic mixture of below more than the 21 quality ppm 897 quality ppm temperature more than 600 DEG C.
The manufacture method of 13. 1 kinds of moldinies, it possesses following operation: by containing silicon-dioxide and germanium and the inorganic mixture that the containing ratio of described germanium is below more than 21 quality ppm 897 quality ppm is accommodated in the storage operation in shaping dies; With the forming process that described inorganic mixture is shaped,
Described forming process has following operation (a) or operation (b),
A () utilizes described shaping dies to pressurize to described inorganic mixture, be heated to the operation of more than 600 DEG C simultaneously,
B () implements the operation of heat treated after being shaped by described inorganic mixture by pressurization at the temperature more than 600 DEG C.
The manufacture method of 14. moldinies according to claim 13, wherein, in described forming process, with the volume density of described molding for 0.25g/cm 3above 2.0g/cm 3following mode sets compacting pressure.
The manufacture method of 15. moldinies according to claim 13, wherein, possesses following operation: further by the median size D containing silicon-dioxide sfor more than 5nm and the small-particle less than 30nm and the median size D containing germanium and silicon-dioxide lfor the macrobead of more than 40nm less than 50 μm mixes, obtain the operation of described inorganic mixture.
The manufacture method of 16. moldinies according to claim 13, wherein, possesses following operation: further by the median size D containing silicon-dioxide sfor more than 5nm and the small-particle less than 30nm and the median size D containing germanium and silicon-dioxide lfor macrobead and the metal oxide sol mixing of more than 40nm less than 50 μm, obtain the operation of described inorganic mixture.
The manufacture method of 17. 1 kinds of cutting bodies, it possesses following operation: by containing silicon-dioxide and germanium and the inorganic mixture that the containing ratio of described germanium is below more than 21 quality ppm 897 quality ppm is accommodated in the storage operation in shaping dies; With the forming process that described inorganic mixture is shaped; With the cutting process cut a part for the molding obtained in described forming process,
Described forming process has following operation (c) or operation (d),
(c) with the volume density of molding for 0.25g/cm 3above 2.0g/cm 3following mode utilizes described shaping dies to pressurize to described inorganic mixture, carries out the operation heated simultaneously,
D () implements the operation of heat treated after being shaped by described inorganic mixture by utilizing described shaping dies to carry out pressurizeing at the temperature more than 600 DEG C.
CN201110308252.7A 2011-10-11 2011-10-11 The manufacture method of molding, cladding, molding and the manufacture method of cutting body Active CN103044059B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110308252.7A CN103044059B (en) 2011-10-11 2011-10-11 The manufacture method of molding, cladding, molding and the manufacture method of cutting body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110308252.7A CN103044059B (en) 2011-10-11 2011-10-11 The manufacture method of molding, cladding, molding and the manufacture method of cutting body

Publications (2)

Publication Number Publication Date
CN103044059A CN103044059A (en) 2013-04-17
CN103044059B true CN103044059B (en) 2015-10-21

Family

ID=48056947

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110308252.7A Active CN103044059B (en) 2011-10-11 2011-10-11 The manufacture method of molding, cladding, molding and the manufacture method of cutting body

Country Status (1)

Country Link
CN (1) CN103044059B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116169275B (en) * 2023-04-25 2023-07-07 北京科技大学 Germanium-coated silica composite material and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101193835A (en) * 2005-05-31 2008-06-04 先进玻璃陶瓷公司 Heat insulating composite and methods of manufacturing thereof
CN102040367A (en) * 2009-10-16 2011-05-04 霓佳斯株式会社 Thermal insulation material and method of producing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101193835A (en) * 2005-05-31 2008-06-04 先进玻璃陶瓷公司 Heat insulating composite and methods of manufacturing thereof
CN102040367A (en) * 2009-10-16 2011-05-04 霓佳斯株式会社 Thermal insulation material and method of producing the same

Also Published As

Publication number Publication date
CN103044059A (en) 2013-04-17

Similar Documents

Publication Publication Date Title
CN103043996B (en) Thermal insulation material and manufacture method thereof
KR101506413B1 (en) Heat insulation material and production method for same
US9884982B2 (en) Abrasive grain based on melted spherical corundum
JP5824298B2 (en) Molded body, encapsulated body, method for manufacturing molded body, and heat insulation method
CN102725102A (en) Method and apparatus for roll grinding
CN103043998B (en) Thermal insulation material and manufacture method thereof
CN103189331A (en) Method for producing alumina sintered body, alumina sintered body, abrasive grains, and grindstone
CN107129261B (en) Powder, its formed body and covering body
CN103044059B (en) The manufacture method of molding, cladding, molding and the manufacture method of cutting body
JP5683989B2 (en) Insulating material and manufacturing method thereof
CN103044061B (en) Formed body, coated body, manufacturing method of formed body and heat insulation method
CN103043667B (en) The manufacture method of powder, its molding, cladding and powder
CN103044062B (en) The manufacture method of formed body, cladding, formed body and the manufacture method of cutting body
JP5824272B2 (en) Powder, molded body, enveloping body, and method for producing powder
EP3305729A1 (en) Alkali-metal titanate and friction material
CN103044060B (en) Formed body, coated body and manufacturing method of formed body
CN103043997B (en) The manufacture method of powder, molding, cladding and powder
CN103043931B (en) The manufacture method of powder, molding, cladding and powder
JP5854642B2 (en) Powder manufacturing method
CN103043666B (en) The manufacture method of powder, molding, cladding and powder
JP2012218961A (en) Powder, molding, covered body, and method for producing the powder
JP5824228B2 (en) Powder, molded body, enveloping body, and method for producing powder
JP5700548B2 (en) Molded body, encapsulated body, and method for producing molded body
JP5675507B2 (en) Powder, molded body, enveloping body, and method for producing powder
EP3814053A1 (en) Abrasive articles and methods for forming same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20160504

Address after: Tokyo, Japan, Japan

Patentee after: Asahi Kasei Kogyo K. K.

Address before: Tokyo, Japan, Japan

Patentee before: Asahi Kasei Chemical K. K.