CN103172384B - Method for forming ceramic fiber - Google Patents
Method for forming ceramic fiber Download PDFInfo
- Publication number
- CN103172384B CN103172384B CN201110449718.5A CN201110449718A CN103172384B CN 103172384 B CN103172384 B CN 103172384B CN 201110449718 A CN201110449718 A CN 201110449718A CN 103172384 B CN103172384 B CN 103172384B
- Authority
- CN
- China
- Prior art keywords
- ceramic fiber
- ceramic
- formation method
- raw embryo
- slurry
- 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
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 140
- 239000000835 fiber Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 25
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004327 boric acid Substances 0.000 claims abstract description 18
- 239000002798 polar solvent Substances 0.000 claims abstract description 4
- 210000001161 mammalian embryo Anatomy 0.000 claims description 92
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 14
- 239000011230 binding agent Substances 0.000 abstract 2
- 239000007787 solid Substances 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 9
- 239000003637 basic solution Substances 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 229920000554 ionomer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000032696 parturition Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention provides a method for forming ceramic fiber, comprising: mixing about 100 parts by weight of a polar solvent with about 10 to 30 parts by weight of an alcohol-based polymer to form a binder; mixing about 70 to 95 parts by weight of a ceramic powder and about 5 to 30 parts by weight of a binder to form a green slurry; extruding the green slurry into an alkaline aqueous solution containing boric acid to form a ceramic fiber green from the green slurry; and sintering the ceramic fiber green body to form the ceramic fiber.
Description
[technical field]
The present invention about ceramic fiber, particularly about super fine ceramic fiber and its formation method.
[background technology]
The manufacture method of several ceramic fibers existing is used in the manufacture of piezoelectric ceramic fibers at present.Wherein have colloidal suspensions spinning processing procedure (Viscoussuspensionspinningprocess, VSSP), such as US Patent No. 6451059 and US5486497, and world patent in early days WO2008125271 is disclosed.
Also have and make piezoelectric ceramic fibers with sol-gel (sol-gel) method.Such as US Patent No. 5945029, US3760049 and US4921328, German patent DE-C4332831, Japanese Patent JP5132320 and Chinese patent CN101190845.
Template is had to make the method for ceramic fiber, such as world patent WO2008056891, Japanese Patent JP9117964 and JP6340475 and Korean Patent KR100806296 in addition.
The present invention proposes the formation method of new ceramic fiber, processing ease and can produce the ceramic fiber of high solids content.
[summary of the invention]
An embodiment of the present invention provides a kind of formation method of ceramic fiber, comprising: the mixing polar solvent of about 100 weight parts forms cakingagent with the alcohol based polymer of about 10 to 30 weight parts; The mixing ceramic powder of about 70 weight part to 95 weight parts and the cakingagent of about 30 weight part to 5 weight parts form raw embryo slurry; Life embryo slurry is squeezed in borated alkaline aqueous solution, makes raw embryo slurry form the raw embryo of ceramic fiber; And the raw embryo of sintered ceramic fiber, form ceramic fiber.
[accompanying drawing explanation]
In Fig. 1 system one embodiment of the invention, the graph of a relation of the ceramic powder content that the viscosity of giving birth to embryo slurry contains with it;
In Fig. 2 system one embodiment of the invention, squeeze pressure and the graph of a relation of giving birth to ceramic powder content in embryo slurry;
In Fig. 3 system one embodiment of the invention, the section microgram of the ceramic fiber of rounded section;
In Fig. 4 system one embodiment of the invention, the section microgram of the ceramic fiber of rounded section;
In Fig. 5 system one embodiment of the invention, the density of ceramic fiber and the graph of a relation of ceramic powder content in raw embryo slurry; And
In Fig. 6 system one embodiment of the invention, the graph of a relation of ceramic powder content in the specific inductivity of the ceramic fiber of piezoelectric and piezo-electric modulus and raw embryo slurry.
[embodiment]
The invention provides the formation method of ceramic fiber.First, mix the polar solvent (such as water, ethanol, propyl alcohol or acetone) of about 100 weight parts, the alcohol based polymer of about 10 to 30 weight parts forms cakingagent.If the ratio of alcohol based polymer is too high, then cakingagent itself not easily stirs and can produce multiple hole in follow-up sintering process.If the ratio of alcohol based polymer is too low, then cakingagent viscosity can reduce the intensity extruding the raw embryo of fiber not.Alcohol based polymer can be polyvinyl alcohol, Mierocrystalline cellulose (such as methylcellulose gum etc.), and the molecular-weight average of this alcohol based polymer is between 5000 to 100000.In an embodiment of the present invention, alcohol based polymer is the polyvinyl alcohol of weight average molecular weight about between 30000 to 100000.In an alternative embodiment of the invention, alcohol based polymer is the methylcellulose gum of weight average molecular weight between 10000 to 30000.Its weight average molecular weight be suitable for of different alcohol based polymer and concentration range difference.If the weight average molecular weight of alcohol based polymer is too high, then the too high unfavorable uniform stirring of the viscosity of cakingagent.If the molecular-weight average of alcohol based polymer is too low, then cakingagent viscosity is too low, cannot by raw embryo plastotype.In an alternative embodiment of the invention, cakingagent also comprises the boric acid of about 0.1 to 5 weight part, if use the little alcohol based polymer of molecular weight can add boric acid on a small quantity, has the function easily stirred, provides suitable viscosity simultaneously in raw embryo.Then mix the ceramic powder of 70 weight part to 95 weight parts and the above-mentioned cakingagent of 30 to 5 weight parts, form raw embryo slurry.If the ratio of ceramic powder is too high, then cannot extrude the raw embryo of fiber continuously.If the ratio of ceramic powder is too low, then fiber raw embryo follow-up sintering process can produce hole.Ceramic powder can be zirconia titanate lead, barium titanate or titanium oxide etc., and the grain size of this ceramic powder is about between 0.1 μm to 0.6 μm.If the particle diameter of ceramic powder is excessive, then consent can be caused when extruding small-bore die head.In an embodiment of the present invention, its temperature of the mixing step of ceramic powder and cakingagent is about between 25 DEG C to 50 DEG C, and mixing time is about between 3 minutes to 20 minutes.If the overlong time of mixing and/or mixing temperature too high, the viscosity of raw embryo slurry is by too high and increase the pressure of aftermentioned extrusion process.If the time of mixing is too short and/or mixing temperature is too low, raw embryo slurry agitation is irregular and cannot extrusion molding.Through suitable mixing processing procedure, can allow the viscosity of raw embryo slurry about between 10000cps to 38000cps, in order to subsequent extrusion processing procedure.
Then life embryo slurry is squeezed in borated alkaline aqueous solution, makes raw embryo slurry form the raw embryo of ceramic fiber.During the linking agent of general employing boric acid as raw embryo slurry, this linking agent is acidic solution instinctively.But in one embodiment of the invention, adjust the pH value of the boric acid aqueous solution of about 1M to 5M with ammoniacal liquor, make it form pH value and be about greater than 7 and be less than or equal to the basic solution of 12.It is main because aqueous solution mesoboric acid is mainly with unionized B (OH)
3form exists, and only has the OH in minority and water
-in conjunction with formation [B (OH)
4]
-, and [B (OH)
4]
-just can carry out condensation reaction (condensationreaction) with alcohol radical and slough water molecules, make polyvinyl alcohol molecule crosslinked (crosslinking) together.Therefore [B (OH) will be improved
4]
-concentration, suitable proportion add alkali improve [B (OH)
4]
-concentration.If basic solution is not containing boric acid, then the alcohol based polymer molecule in cakingagent only can dewater, and can not produce polymerism.If the borated aqueous solution is for acid and be not adjusted to alkalescence, then boric acid is main still with unionized B (OH)
3form exists, and difficulty is polymerized with the alcohol radical of alcohol based polymer.Boric acid molecule under alkaline aqueous solution forms [B (OH)
4]
-, can react with the alcohol based polymer in raw embryo slurry and form ionomer film layer, and incrementally be polymerized toward the center of the raw embryo of ceramic fiber.In one embodiment, adjustment basic solution uses ammoniacal liquor, and it does not have basic metal race positively charged ion, avoids basic metal race positively charged ion to remain in inside fiber and causes dissipation loss.After above-mentioned polyreaction disengages moisture content, the raw embryo of ceramic fiber can be shunk simultaneously and make its densification.In an embodiment of the present invention, the temperature of the basic solution of this boronic acid containing aqueous solution is about between 25 DEG C to 80 DEG C.If the temperature of the basic solution of the boronic acid containing aqueous solution is too high, then may produce quick partial polymerization.If the temperature of the basic solution of the boronic acid containing aqueous solution is too low, then possibility polyreaction is excessively slow, not easily slurry plastotype.
Be understandable that, the cross-sectional shape of the raw embryo of ceramic fiber, depends on the shape of extruding outlet.Those skilled in the art, from difform extruding can be adopted to export, make the raw embryo of ceramic fiber have different cross-sectional shapes as circle, trilateral, square or other Polygonss, look closely demand and determine.In an embodiment of the present invention, adopt the circular extrusion outlet of diameter about between 40 μm to 500 μm or about between 40 μm to 250 μm, only need about 2kg/cm
2to 50kg/cm
2between pressure can form the raw embryo of ceramic fiber of the rounded section of diameter about between 30 μm to 600 μm or about between 30 μm to 400 μm.Pressure (the > 400kg/cm needed for ceramic fiber is extruded with existing dry type
2) compare, obviously reduce pressure needed for processing procedure, namely reduce processing procedure cost.Significantly, the reason that the pressure of above-mentioned extrusion process is lower is that the viscosity of the raw embryo slurry of the present invention is lower.In addition, winder can be adopted to collect the raw embryo of ceramic fiber, the configuration making the raw embryo of ceramic fiber have specified configuration may to have as the line segment of spring-like, regular length or other filamentary materials.
Then can depending on the circumstances or the needs of the situation, prior to drying of ceramic fiber at low temperature according to appointment 25 DEG C to 100 DEG C.The raw embryo of last sintered ceramic fiber, forms ceramic fiber.In an embodiment of the present invention, sintering condition is the baking oven of under general atmosphere about 1000 DEG C to 1300 DEG C.After above-mentioned sintering step, the cross-linking products of the organism in the raw embryo of ceramic fiber as alcohol based polymer and boric acid will be oxidized also loss in air, makes the diameter of ceramic fiber be less than the raw embryo of ceramic fiber.After above-mentioned steps, for the circular extrusion outlet of aforementioned diameter about between 40 μm to 500 μm or about between 40 μm to 250 μm, the ceramic fiber of the rounded section of diameter about between 30 μm to 600 μm or about between 30 μm to 400 μm can be formed.Microphotograph through tangent plane is known, and ceramic fiber of the present invention is dense structure, does not almost have pore in wherein.
In order to the above and other object of the present invention, feature and advantage can be become apparent, several embodiment cited below particularly coordinates institute's accompanying drawings, is described in detail below:
[embodiment]
Embodiment 1
First zirconia titanate lead (PZT) this piezoelectric is got as ceramic powder, its average particle diameter size 0.1 ~ 0.6 micron.Then the boric acid of the polyvinyl alcohol (weight-average molecular weight 37500) of 22 weight parts, the water of 77.85 weight parts and 0.15 weight part is mixed as cakingagent.
Get the ceramic powder of 80 weight parts and the cakingagent of 20 weight parts respectively, form raw embryo slurry after mixing, its viscosity as shown in Figure 1.
Then with the pH value to 8.2 of the boric acid aqueous solution of ammoniacal liquor adjustment 3M, more above-mentioned raw embryo slurry is squeezed in the alkaline aqueous solution containing boric acid.Extruding outlet is respectively the rounded section tapered tube that diameter is 100 μm and 150 μm.When adjustment slurry extruded velocity is to 2.5cm/sec, the graph of a relation of extrusion pressure and ceramic powder content as shown in Figure 2.The less mouthpiece that squeezes out has higher squeeze pressure, and the slurry with the ceramic powder of high level also needs higher squeeze pressure.
Because raw embryo slurry and borated alkaline aqueous solution system react in the liquid phase, the boron hydroxide anion radical in borated alkaline aqueous solution etc. to form ionomer film layer with the polyvinyl alcohol extruded in slurry, and past fibrillar center is polymerized progressively.Above-mentioned polyreaction, except disengaging moisture, is also shunk the raw embryo of ceramic fiber simultaneously and obtains the raw embryo of finer and close round ceramic fiber.
Raw for above-mentioned ceramic fiber embryo is cut into suitable length and puts into baking oven cryodrying, carry out high temperature sintering (place excess pbo in the raw embryo surrounding of fiber and carry out high temperature sintering together, as compensation atmosphere) afterwards.The raw embryo of ceramic fiber of the rounded section of diameter about 120 μm (extruding outlet is 150 μm) and 45 μm (extruding outlet is 100 μm) is after 1250 DEG C/2hr sinters, and the section SEM microstructure of the ceramic fiber of formation is as shown in the 3rd and 4 figure.Maintained the proper circle of the raw embryo of original ceramic fiber by the 3rd and 4 figure known ceramic fiber outward appearance, after sintering, diameter is contracted to about 90 μm and 39 μm from 120 μm and 45 μm, shrinking percentage 16 ~ 21% respectively.The shrinking percentage (18 ~ 20%) sintered with traditional briquetting bulk is close, the fiber that display manufactures in this approach raw embryo solid content density further can be increased to the degree close to the raw embryo of traditional ceramics bulk, is conducive to the electrical specification after keeping ultra-fine fibre sintering.
As shown in Figure 5, the density of ceramic fiber becomes positive correlation with the solid content of raw embryo slurry.When the solid content of raw embryo slurry is 80%, the density of ceramic fiber is about 7.2g/cm
3, be slightly less than the density (7.7g/cm of briquetting sintering
3).
Ceramic powder due to this embodiment is piezoelectric, therefore can measure the piezoelectric property of ceramic fiber further.Solid content is the raw embryo of piezoelectric ceramic fibers of 80wt%, the piezoelectric property of the ceramic fiber after sintered as specific inductivity (Dk) and piezo-electric modulus (D33) as shown in Figure 6.
Embodiment 2
Get the ceramic powder described in 85 parts by weight of example 1 and the cakingagent described in 15 parts by weight of example 1 respectively, form raw embryo slurry after mixing, its viscosity as shown in Figure 1.
Then with the pH value to 8.2 of the boric acid aqueous solution of ammoniacal liquor adjustment 3M, more above-mentioned raw embryo slurry is squeezed in the alkaline aqueous solution containing boric acid.Extruding outlet is respectively the rounded section tapered tube that diameter is 100 μm and 150 μm.When adjustment slurry extruded velocity is to 2.5cm/sec, the graph of a relation of extrusion pressure and ceramic powder content as shown in Figure 2.
Because raw embryo slurry and borated alkaline aqueous solution system react in the liquid phase, the boron hydroxide anion radical in borated alkaline aqueous solution etc. to form ionomer film layer with the polyvinyl alcohol extruded in slurry, and past fibrillar center is polymerized progressively.Above-mentioned polyreaction, except disengaging moisture, is also shunk the raw embryo of ceramic fiber simultaneously and obtains the raw embryo of finer and close round ceramic fiber.
Similar to Example 1, raw for above-mentioned ceramic fiber embryo is cut into suitable length and puts into baking oven cryodrying, carry out high temperature sintering (place excess pbo in the raw embryo surrounding of fiber and carry out high temperature sintering together, as compensation atmosphere) afterwards.The raw embryo of ceramic fiber of the rounded section of diameter about 135 μm (extruding outlet is 150 μm) and 47 μm (extruding outlet is 100 μm) is after 1250 DEG C/2hr sinters, the ceramic fiber outward appearance formed maintains the proper circle of the raw embryo of original ceramic fiber, after sintering, diameter is contracted to about 107 μm and 39 μm from 135 μm and 47 μm, shrinking percentage 20.7 ~ 17% respectively.The shrinking percentage (18 ~ 20%) sintered with traditional briquetting bulk is close, the fiber that display manufactures in this approach raw embryo solid content density further can be increased to the degree close to the raw embryo of traditional ceramics bulk, is conducive to the electrical specification after keeping ultra-fine fibre sintering.
As shown in Figure 5, the density of ceramic fiber becomes positive correlation with the solid content of raw embryo slurry.When the solid content of raw embryo slurry is 85wt%, the density of ceramic fiber is about 7.6g/cm
3, be slightly less than the density (7.7g/cm of briquetting sintering
3).
Ceramic powder due to this embodiment is piezoelectric, therefore can measure the piezoelectric property of ceramic fiber further.Solid content is the raw embryo of piezoelectric ceramic fibers of 85wt%, the piezoelectric property of the ceramic fiber after sintered as specific inductivity (Dk) and piezo-electric modulus (D33) as shown in Figure 6.
Embodiment 3
Get cakingagent described in ceramic powder described in 90 parts by weight of example 1 and 10 parts by weight of example 1 respectively, form raw embryo slurry after mixing, its viscosity as shown in Figure 1.As shown in Figure 1, slurry viscosity increases with ceramic powder content and increases, and when ceramic content is up to 90wt%, slurry viscosity is about 25000cps.
Then with the pH value to 8.2 of the boric acid aqueous solution of ammoniacal liquor adjustment 3M, more above-mentioned raw embryo slurry is squeezed in the alkaline aqueous solution containing boric acid.Extruding outlet is respectively the rounded section tapered tube that diameter is 100 μm and 150 μm.When adjustment slurry extruded velocity is to 2.5cm/sec, the graph of a relation of extrusion pressure and ceramic powder content as shown in Figure 2.The less mouthpiece that squeezes out has higher squeeze pressure, and the slurry with the ceramic powder of high level also needs higher squeeze pressure.In any case even if the diameter of extruding outlet is little of 100 μm, and the ceramic powder content in slurry is up to 90wt%, and squeeze pressure also only has 22kg/cm
2, much smaller than pressure 400 ~ 1500kg/cm that mould pressure injection is conventional
2.From the above, the colloid of the present invention's use is cross-linked ceramic powder significantly can improve ceramic powder content in raw embryo, and the raw embryo of the continuous extruded ceramic fiber of pressure that can be extremely low.
Because raw embryo slurry and borated alkaline aqueous solution system react in the liquid phase, the boron hydroxide anion radical in borated alkaline aqueous solution etc. to form ionomer film layer with the polyvinyl alcohol extruded in slurry, and past fibrillar center is polymerized progressively.Above-mentioned polyreaction, except disengaging moisture, is also shunk the raw embryo of ceramic fiber simultaneously and obtains the raw embryo of finer and close round ceramic fiber.
Similar to Example 1, raw for above-mentioned ceramic fiber embryo is cut into suitable length and puts into baking oven cryodrying, carry out high temperature sintering (place excess pbo in the raw embryo surrounding of fiber and carry out high temperature sintering together, as compensation atmosphere) afterwards.The raw embryo of ceramic fiber of the rounded section of diameter about 150 μm (extruding outlet is 150 μm) and 83 μm (extruding outlet is 100 μm) is after 1250 DEG C/2hr sinters, the ceramic fiber outward appearance formed maintains the proper circle of the raw embryo of original ceramic fiber, after sintering, diameter is contracted to about 122 μm and 70 μm from 150 μm and 83 μm, shrinking percentage 18.7 ~ 18.6% respectively.The shrinking percentage (18 ~ 20%) sintered with traditional briquetting bulk is close, the fiber that display manufactures in this approach raw embryo solid content density further can be increased to the degree close to the raw embryo of traditional ceramics bulk, is conducive to the electrical specification after keeping ultra-fine fibre sintering.
As shown in Figure 5, when the ceramic powder content of the raw embryo of ceramic fiber reaches 90wt%, the density after its sintering is 7.65g/cm
3, with the density (7.7g/cm of briquetting sintering
3) compare without obvious gap.Therefore not only can make ultra-fine wire diameter ceramic fiber with aforesaid method, and significantly can improve the ceramic powder content in the raw embryo of ceramic fiber, the ceramic fiber density formed after simultaneously improving sintering.
Ceramic powder due to this embodiment is piezoelectric, therefore can measure the piezoelectric property of ceramic fiber further.Solid content is the raw embryo of piezoelectric ceramic fibers of 90%, the piezoelectric property of the ceramic fiber after sintered as specific inductivity (Dk) and piezo-electric modulus (D33) as shown in Figure 6.Under 1KHz resonant frequency, when PZT ceramic powder content is higher, its specific inductivity and piezo-electric modulus are also higher.When in raw embryo slurry, ceramic powder content is 90wt%, the specific inductivity after sintering and piezo-electric modulus are respectively up to 4500 and 600 (pC/N).In the raw embryo slurry of display, PZT ceramic powder content is higher, and entity is after sintering finer and close, and therefore piezoelectric property is better.
Although the present invention discloses as above with several preferred embodiment; so itself and be not used to limit the present invention, anyly have the knack of this those skilled in the art, without departing from the spirit and scope of the invention; when doing any change and retouching, the protection domain of therefore the present invention is when being as the criterion depending on those as defined in claim.
Claims (14)
1. a formation method for ceramic fiber, comprising:
The alcohol based polymer of the polar solvent and 10 to 30 weight parts that mix 100 weight parts forms cakingagent;
The cakingagent of the ceramic powder and 5 to 15 weight parts that mix 85 weight part to 95 weight parts forms raw embryo slurry;
This life embryo slurry is squeezed in borated alkaline aqueous solution, makes this life embryo slurry form the raw embryo of ceramic fiber; And
Sinter the raw embryo of this ceramic fiber, form ceramic of compact fiber.
2. the formation method of ceramic fiber as claimed in claim 1, wherein this alcohol based polymer comprises polyvinyl alcohol or Mierocrystalline cellulose, and the weight average molecular weight of this alcohol based polymer is between 5000 to 100000.
3. the formation method of ceramic fiber as claimed in claim 1, wherein this ceramic powder comprises zirconia titanate lead, barium titanate or titanium oxide.
4. the formation method of ceramic fiber as claimed in claim 1, wherein the grain size of this ceramic powder is between 0.1 μm to 0.6 μm.
5. the formation method of ceramic fiber as claimed in claim 1, wherein the viscosity of this raw embryo slurry is between 10000cps to 38000cps.
6. the formation method of ceramic fiber as claimed in claim 1, wherein the pH value of this borated alkaline aqueous solution is greater than 7 and is less than or equal to 12, and its boric acid concentration is between 1M to 5M.
7. the formation method of ceramic fiber as claimed in claim 1, wherein this life embryo slurry is squeezed to the extruding outlet of the step employing in borated alkaline aqueous solution for circular, and diameter is between 40 μm to 500 μm.
8. the formation method of ceramic fiber as claimed in claim 6, is wherein squeezed to the squeeze pressure of the step employing in the alkaline aqueous solution of boronic acid containing between 2kg/cm by this life embryo slurry
2to 50kg/cm
2between.
9. the formation method of ceramic fiber as claimed in claim 6, wherein the cross section of the raw embryo of this ceramic fiber is the circle of diameter between 30 μm to 600 μm.
10. the formation method of ceramic fiber as claimed in claim 6, wherein the cross section of this ceramic fiber is the circle of diameter between 30 μm to 600 μm.
The formation method of 11. ceramic fibers as claimed in claim 1, wherein the temperature of this borated alkaline aqueous solution is between 25 DEG C to 80 DEG C.
The formation method of 12. ceramic fibers as claimed in claim 1, wherein sinters the temperature of the raw embryo of this ceramic fiber between 1000 DEG C to 1300 DEG C.
The formation method of 13. ceramic fibers as claimed in claim 1, before being also included in the step of the raw embryo of this ceramic fiber of sintering, with the raw embryo of this ceramic fiber of cryodrying between 25 DEG C to 100 DEG C.
The formation method of 14. ceramic fibers as claimed in claim 1, wherein this cakingagent also comprises the boric acid of 0.1 to 5 weight part.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100147693A TWI491581B (en) | 2011-12-21 | 2011-12-21 | Methods of forming ceramic fibers |
| TW100147693 | 2011-12-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103172384A CN103172384A (en) | 2013-06-26 |
| CN103172384B true CN103172384B (en) | 2016-03-02 |
Family
ID=48632660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110449718.5A Active CN103172384B (en) | 2011-12-21 | 2011-12-29 | Method for forming ceramic fiber |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103172384B (en) |
| TW (1) | TWI491581B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279642B (en) * | 2020-10-22 | 2022-08-05 | 江西欧迈斯微电子有限公司 | Piezoelectric fiber and method for producing same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229772A (en) * | 1998-03-20 | 1999-09-29 | 陶瓷技术公司 | Multi-channel porous ceramic fiber |
| CN102066247A (en) * | 2008-06-18 | 2011-05-18 | 高级金属陶瓷有限公司 | Boron carbide ceramic fibers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI379820B (en) * | 2009-03-25 | 2012-12-21 | Ind Tech Res Inst | Piezoelectric ceramic fibers and fabrication method thereof |
| CN101817681B (en) * | 2010-03-24 | 2013-04-17 | 江苏工业学院 | Method for preparing bending-free piezoelectric ceramic fiber with low cost |
-
2011
- 2011-12-21 TW TW100147693A patent/TWI491581B/en active
- 2011-12-29 CN CN201110449718.5A patent/CN103172384B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229772A (en) * | 1998-03-20 | 1999-09-29 | 陶瓷技术公司 | Multi-channel porous ceramic fiber |
| CN102066247A (en) * | 2008-06-18 | 2011-05-18 | 高级金属陶瓷有限公司 | Boron carbide ceramic fibers |
Non-Patent Citations (1)
| Title |
|---|
| 交联剂对聚乙烯醇溶液粘度的影响;蔡夫柳等;《北京服装学院学报》;19941031;第14卷(第2期);1-6 * |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI491581B (en) | 2015-07-11 |
| TW201326086A (en) | 2013-07-01 |
| CN103172384A (en) | 2013-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20070116640A1 (en) | Titanium dioxide nanorod and preparation method thereof | |
| US3117944A (en) | Coagula of colloidal fibrous boehmite and acrylamide polymers and processes for making same | |
| CN104496469A (en) | Method for preparing dense micro/nano ceramic fiber by virtue of coaxial electrospinning technology | |
| CN106495671B (en) | Cellulose nanocrystal modified ceramic green body and preparation method thereof | |
| CN104893187A (en) | High energy storage density and efficiency polymer composite film and preparation method thereof | |
| CN102181962A (en) | Method for preparing thin-diameter zirconium oxide fibers and fiber board thereof | |
| CN112521161B (en) | Gel injection molding method of aluminum oxide-zirconium dioxide complex phase ceramic | |
| CN108017861A (en) | A kind of polymer-based dielectric composite material of coated with silica CaCu 3 Ti 4 O nanofiber and preparation method thereof | |
| CN101708435A (en) | Method for preparing asymmetric structure ceramic hollow fiber and tubular ultra-filtration membrane | |
| CN109851328A (en) | A kind of preparation process of high-performance ceramic flat membrane support | |
| CN103172384B (en) | Method for forming ceramic fiber | |
| CN111622016A (en) | Pressure-resistant heat-insulating paper containing hollow porous silica microspheres and preparation method thereof | |
| JPH04139079A (en) | Production of porous ceramics | |
| CN108172419A (en) | A kind of enhanced super electrolytic capacitor diaphragm paper and preparation method thereof | |
| CN101871138A (en) | Method for manufacturing nylon6/nanometer SiO2 composite fiber material | |
| CN101358388B (en) | PZT piezoelectric fabric and preparation method thereof | |
| CN1235567A (en) | Consolidated material of coated pulverized bodies and method of manufacturing the same | |
| CN106007779B (en) | The preparation method of high purity aluminium oxide flat ceramic film support | |
| CN102786307A (en) | Method for manufacturing piezoelectric ceramic fiber | |
| CN109852030A (en) | Complex media substrate and preparation method thereof | |
| CN109629032A (en) | A kind of preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique | |
| CN105970326B (en) | A kind of preparation method of continuous hollow cellulose aerogels fiber | |
| CN104098337A (en) | Method for molding integrated coaxial medium filter | |
| CN110707270A (en) | Fiber alumina-based lithium ion battery ceramic diaphragm and preparation method thereof | |
| US20130285510A1 (en) | Method for fabricating piezoelectric composite material and piezoelectric power generating device |
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 |