CN100522870C - Composite ceramic and method for producing same - Google Patents
Composite ceramic and method for producing same Download PDFInfo
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- CN100522870C CN100522870C CNB2006800026043A CN200680002604A CN100522870C CN 100522870 C CN100522870 C CN 100522870C CN B2006800026043 A CNB2006800026043 A CN B2006800026043A CN 200680002604 A CN200680002604 A CN 200680002604A CN 100522870 C CN100522870 C CN 100522870C
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Abstract
Disclosed is a composite ceramic which is composed of a bulk alumina crystal phase (A) having an aspect ratio of not more than 3, a bulk zirconia crystal phase (B) having an aspect ratio of not more than 3 and a columnar crystal (C) of a complex oxide containing an alkaline earth metal and aluminum element which has an aspect ratio of more than 3. This composite ceramic has excellent flexural strength, excellent toughness, high hardness, excellent hot water resistance, and high transverse strength after thermal degradation resistance test.
Description
Technical field
The present invention relates to high composite ceramics of high strength, high tenacity and wearability and method for making thereof, particularly be suitable for being used composite ceramics and method for making thereof as various structures or its parts.
Background technology
In recent years, pottery is applied to various structures and its parts from the reason of its excellent mechanical characteristics and erosion resistance etc.For example, the various cutlery classes and the mechanism components of instrument class, bearing etc. are arranged, perhaps the organism of human synovial etc. is with member etc.As being applicable to the as above pottery of purposes, disclosing a kind of zirconium white in patent documentation 1 is composite ceramics, and it contains by CeO
2And Y
2O
3The zirconium white crystallization phases of stabilization and alumina crystal are mutually.This composite ceramics is made of regular crystal based on the zirconium white crystallization phases, excellences such as the mechanical characteristics of its intensity and toughness etc. and heat-resisting water deterioration.
In addition, disclose a kind of aluminum oxide one zirconia composite ceramics of high tenacity in following patent documentation 2, it is a principal constituent with aluminum oxide and zirconium white, contains alkaline-earth metals oxide and silicon oxide for this principal constituent.
Patent documentation 1: special fair 7-64631 communique
Patent documentation 2: No. 2910020 communiques of patent
On the other hand, though patent documentation 2 disclosed aluminum oxide-zirconia composite ceramics toughness height, because the unusual mutually grain growth of alumina crystal, so physical strength is low, particularly hot water resistance is low, exists the folding strength after the hot water deterioration test to reduce such shortcoming greatly.
Summary of the invention
Therefore, the objective of the invention is to, a kind of flexural strength, toughness and hot water resistance (heat-resisting water deterioration) excellence is provided, and high rigidity is arranged, as wearability material useful composite ceramics and method for making thereof.
Can provide a kind of composite ceramics according to the present invention, it is by blocky alumina crystal phase (A), blocky zirconium white crystallization phases (B) and contain alkaline-earth metal and the column crystal of the composite oxides of aluminium element (C) formation.
In composite ceramics of the present invention, be preferably:
(1) column crystal of described composite oxides (C) has than 3 big long-width ratios,
(2) alumina crystal phase (A) and zirconium white crystallization phases (B) exist with 65/35～90/10 mass ratio (A/B),
(3) the average crystallite particle diameter of alumina crystal phase (A) is below the 1.5 μ m, and the average crystallite particle diameter of zirconium white crystallization phases (B) is below the 0.5 μ m,
(4) composite oxides that form described column crystal (C) are at least a kind that selects from following group: Ca
3Ti
8Al
12O
37, SrTi
3Al
8O
19, Ba
3TiAl
10O
20, CaAl
12O
19, SrAl
12O
19And BaAl
12O
19,
(5) Vickers' hardness is more than 1600, destroys toughness value more than 4.5, and the folding strength after the hot water deterioration test is more than the 1050MPa,
When (6) section being carried out electron microscope observation, in the area of 4.5 μ m * 6.0 μ m sizes, described column crystal (C) is 1～20% with respect to the area ratio of the total area of alumina crystal phase (A) and zirconium white crystallization phases (B).
According to the present invention, a kind of method for making of composite ceramics also is provided, comprising:
With median size is that alumina powder below the 2 μ m and the powder that contains the alkaline-earth metal element carry out the blended operation;
Described mixed powder is carried out the operation that pre-burning reaches alumina powder and contains the powder-stuck degree of alkaline-earth metal element;
Mixing median size in the powder of pre-burning is the operation that the Zirconium oxide powder below the 0.5 μ m is modulated the usefulness powder that is shaped; And
After described shaping powder forming is the regulation shape, in the oxidizing atmosphere below 1600 ℃, carry out the incinerating operation.
In method for making of the present invention, be preferably:
(1) as containing the powder of described alkaline-earth metal element, use at least a in strontium carbonate powder, calcium carbonate powders, the barium carbonate powder,
(2) powder and the titanium dioxide powder that will contain described alkaline-earth metal element is blended in the alumina powder,
(3) measure 100 mass parts with respect to the total of blended Zirconium oxide powder after alumina powder and the pre-burning, the amount of using described titanium dioxide powder is more than 0.2 mass parts, and using the amount of the powder that contains described alkaline-earth metal element is more than 0.2 mass parts,
(4) behind described calcination process, carry out the hot hydrostaticpressure calcining below 1500 ℃ again.
According to the present invention, also provide a kind of sliding component organism of using described composite ceramics and being shaped to use member.
Also have, in the present invention, so-called blocky crystallization phases be meant for example calculate by electron micrograph, be crystalline particle below 3 as the long-width ratio of the ratio of crystalline major diameter and minor axis, the shape of crystallization phases does not have directive property.The long-width ratio of this crystallization phases is the major diameter of the crystalline particle that occurs in the section and is major diameter/minor axis ratio that minor axis is tried to achieve with its vertical direction.
Composite ceramics of the present invention, because alumina crystal phase and zirconium white crystallization phases all are block, institute thinks high strength, high rigidity and excellent in wear resistance.In addition, between blocky alumina crystal phase and zirconium white crystallization phases, be formed with the column crystallization of the composite oxides that contain alkaline-earth metal and aluminium element, therefore be high tenacity, hot water resistance is also high, and for example the reduction of the folding strength after the hot water deterioration test is suppressed effectively.
Composite ceramics of the present invention with such characteristic, can be used as various structures and parts thereof, for example various cutlery classes and instrument class, the perhaps mechanism components of bearing etc., the organism of human synovial etc. is used member, in particular as the sliding component of spot contact bearing (ball bearing) and human synovial etc.
Description of drawings
Fig. 1 is the sketch chart of the structure of expression composite ceramics of the present invention.
Embodiment
Below explain the present invention based on concrete example shown in the drawings.
(structure of composite ceramics)
With Fig. 1 is reference, composite ceramics of the present invention, have as crystallization phases and be blocky alumina crystal mutually 1 and zirconium white crystallization phases 3, have column crystal 5 between these crystallization phasess, this column crystal 5 is made of the composite oxides that contain alkaline-earth metal and aluminium element.
Promptly, composite ceramics of the present invention, the alumina crystal phase 1 and the zirconium white crystallization phases 3 that are formed on the main body that becomes crystallization phases in the sintered compact are the blocky tissue that does not have directive property, between so blocky crystallization phases, be formed with the column crystal 5 that constitutes by the composite oxides of stipulating, so the grain of alumina crystal phase and zirconium white crystallization phases is grown up and is suppressed, thereby can avoid an intensity of the sintered compact that growth brings to reduce, realize high strength, the mechanical characteristics of toughness, folding strength, hardness etc. is improved, hot water resistance is improved.
As understanding according to Fig. 1, composite ceramics of the present invention is preferably rich aluminum oxide on substantially, for example, alumina crystal mutually 1 and the mass ratio of zirconium white crystallization phases 3 preferably be in following scope:
Alumina crystal phase/zirconium white crystallization phases=65/35～90/10
Particularly 75/25～85/15
So becoming rich aluminum oxide by making, is favourable realizing high rigidityization, making in the wearability raising.
In addition, alumina crystal phase 1 so its average crystallite particle diameter particularly is in the scope of 0.6～1.3 μ m usually, can be reached high strength and high tenacityization because its growth is suppressed thus below 1.5 μ m.
On the other hand, the average crystallite particle diameter of average crystallite particle diameter ratio aluminum oxide that is preferably zirconium white crystallization phases 3 is little, particularly below 0.5 μ m, preferably is in the scope of 0.1～0.4 μ m.That is, in the present invention, not only in alumina crystal phase 1,, therefore, can realize high strength and high tenacityization by micronize or densification even in zirconium white crystallization phases 3, also have the weave construction that grain is grown up and effectively suppressed.
In addition, in composite ceramics of the present invention, median size ratio aluminum oxide crystallization phases 1 as above-mentioned preferred rich aluminum oxide and zirconium white crystallization phases 3 is little, but in such form, constitute with alumina crystal phase 1 as mother metal, zirconium white crystallization phases 3 is dispersed in such aluminum oxide mother metal, the stabilization by the stress under compression of coming the self-alumina mother metal.Promptly, even contained stablizer is a small amount of in the zirconium white crystallization phases 3, but zirconium white crystallization phases 3 is as regular crystal and stabilization, so oblique crystal and separating out of cube crystalline substance are suppressed, consequently intensity (for example folding strength) and toughness improve, and hardness also improves in addition.For example, if stablizer exists in a large number, then stress-induced phase transformation will be difficult to take place, and folding strength, toughness reduce, but in the present invention, can avoid the reduction of the mechanical characteristics that such stablizer causes.
Also have, as zirconic stablizer, normally used Y
2O
3Be the oxide compound of 3 valencys, if at zirconium white (ZrO as 4 valency oxide compounds
2) middle solid solution, then form the oxygen room, because water is had an effect to this oxygen room, zirconic combination can be cut off, and causes the hot water deterioration.That is, if use Y
2O
3As the stablizer of zirconium white crystallization phases 3 and make the Zirconia-stabilized regular crystal that turns to, then hot water resistance significantly reduces, and for example the folding strength after the hot water deterioration test reduces greatly.Yet, in composite ceramics of the present invention, do not use Y
2O
3Such stablizer also can make zirconium white crystallization phases 3 stabilizations, therefore can avoid by Y effectively
2O
3The reduction of the hot water resistance that causes.
As understanding, in composite ceramics of the present invention, also be extremely micro-even preferably do not add stablizer or add according to above-mentioned explanation.That is, the consistent dose of above-mentioned zirconium white crystallization phases 3, preferred unit zirconium white (ZrO
2) in have below the 2mol%.Also have, stability for the tetragonal phase that increases the zirconium white crystallization phases 3 behind the sintering, also can add a spot of other stablizers (for example oxide compound of Sc, Ce, Yb etc.), in addition, other such stablizers also can add with the form (salt, alkoxide (alkoxide) etc.) that finally becomes oxide compound.
In the present invention, extremely important is at the above-mentioned alumina crystal phase 1 and the crystal boundary of zirconium white crystallization phases 3, has the column crystal 5 of the composite oxides that contain alkaline-earth metal and aluminium element.That is, when calcining alkaline-earth metal react with aluminum oxide, it is column crystal 5 more than 3 that the composite oxides that contain alkaline-earth metal and aluminum oxide thus are generated as long-width ratio.Generation by such column crystal 5, the grain of alumina crystal phase 1 and zirconium white crystallization phases 3 is grown up and is suppressed, and consequently, these crystallization phasess 1,3 form long-width ratio in the bulk below 3, the intensity reduction that the grain growth causes is suppressed, thereby can realize high strength.
In addition in the present invention, because the formation of column crystal 5 also can improve toughness.For example, when above-mentioned such column crystal 5 did not exist, the deflection of crackle was difficult to take place, because that the propagation of crackle becomes is linear, therefore destroyed toughness and reduced.In addition, the grain of alumina crystal phase is grown up and is taken place easily, although toughness is kept, folding strength and wearability reduce, and particularly hot water resistance reduces, and the folding strength after the hot water deterioration test reduces greatly.
In the present invention, the employed alkaline-earth metal of formation as the composite oxides that are used to constitute this column crystal 5 is not particularly limited, for example Ca, Sr, Ba etc. can, but preferred especially Sr.When adopting Sr to form the column crystal 5 of composite oxides, the use of Sr by less amount, the effect that not only has physical strength to improve, and also have the generation of the liquid phase under the low temperature to be suppressed, grow up thereby can suppress grain effectively, and the also low such advantage of the toxicity of composition.
Also have, though before only carried out setting forth simply, the column crystal 5 that is made of composite oxides is from the alkali earth metallic compound that uses as auxiliary agent, for example with alkali earth metallic compound and the titanium compound that adds as required mix with aluminum oxide and zirconium white and calcine, the part of alkaline-earth metal and aluminum oxide reaction thus, the column crystal 5 that contains the composite oxides of alkaline-earth metal and Al is separated out.The composite oxides that constitute such column crystal 5 are expressed from the next as representative:
Ca
3Ti
8Al
12O
37、
SrTi
3Al
8O
19、
Ba
3TiAl
10O
20、
CaAl
12O
19、
SrAl
12O
19, or
BaAl
12O
19。
In composite ceramics of the present invention, the column crystal 5 that is made of such composite oxides is in order to satisfy above-mentioned area ratio, per 100 quality % of the total amount of preferred alumina crystal phase and zirconium white crystallization phases, containing alkaline-earth metal (Ca, Sr, Ba) is at least more than the 0.24 quality % with the oxide compound conversion, especially preferably with titanium (Ti) and alkaline-earth metal (Ca, Sr, Ba), the scope that is aggregated in 0.4 quality %～3 quality % as oxide compound contains.
Other compositions
Also have, composite ceramics of the present invention except above-mentioned each composition, also can contain composition from the sintering aid beyond the alkali earth metallic compound (SiO for example
2, MgO etc.), this oxide components generally is present in the crystal boundary of each crystallization phases, but its part also can be solid-solubilized in the crystallization phases.
As above-mentioned, composite ceramics of the present invention, avoided effectively because the intensity that the increment of aluminum oxide causes reduces, intensity and tenacity excellent, for example demonstrate the Vickers' hardness more than 1600,4.5 above destruction toughness value is even and still demonstrate folding strength more than the 1050MPa after the hot water deterioration test.
Composite ceramics of the present invention with characteristic like this extremely is suitable for use as various structure parts, for example various cutlery classes and instrument class, and perhaps the bearing components of spot contact bearing etc. and artificial joint etc. are the slip of the representative purposes with member.
(manufacturing of composite ceramics)
Composite ceramics of the present invention can be made according to following method: satisfying the mode of above-mentioned composition, prepare to become the various raw material powders in column crystal source of the composite oxides of alumina crystal source, zirconium white crystallization source, alkaline-earth metal element and aluminum oxide.Modulate shaping than mixing this raw material powder with the amount of regulation and use mixed powder, then form and calcine.
Raw material powder
As the alumina crystal source, use alumina powder, but the median size of this alumina powder below 1 μ m, most preferably is below the 0.6 μ m especially below 2 μ m.This is because if use the big thick powder of average crystallite particle diameter, then sintering temperature uprises, and the average crystallite particle diameter of alumina crystal phase 1 is big, intensity takes place reduce.In addition, also the purity of preferred this alumina powder is more than the 99.9 quality %.
As zirconium white crystallization source, use the Zirconium oxide powder of market sale.This zirconium white does not preferably contain stablizer, but contains yet can using of stablizer.As stablizer, preferred Y
2O
3, but this stablizer sets forth as preceding choosing, is the zirconium white (ZrO of unit
2) in have 2 moles below the %, this in the reduction of avoiding hot water resistance for preferred.
In addition, the median size of this Zirconium oxide powder can be preferably below the 0.4 μ m for below the 0.5 μ m.If use the big powder of median size, then the average crystallite particle diameter of zirconium white crystallization phases 3 becomes big, promotes from the regular crystal zirconium white to the monoclinic zirconia phase transformation, might be insufficient by the high tenacityization that zirconic interpolation brings.Such Zirconium oxide powder also has, though can contain hafnium oxide (HfO
2) etc. unavoidable impurities, but usually preferred its pure be more than the 99.9 quality %.
In the present invention, above-mentioned alumina powder and Zirconium oxide powder, so that alumina crystal phase 1 and zirconium white crystallization phases 3 become the mode of the mass ratio of aforementioned range, according to 65/35～90/10, particularly 75/25～85/15 mass ratio uses.
In addition, as the powder that becomes the column crystallization source that uses with above-mentioned alumina powder and Zirconium oxide powder, use the powder of alkali earth metallic compound.Such alkali earth metallic compound for example can use the compound of oxide compound form in addition, but preferably use carbonate if can become then being not particularly limited of oxide compound by calcining, most preferably uses Strontium carbonate powder (SrCO
3).This is because Strontium carbonate powder has agent of low hygroscopicity as carbonate compound, also stable aspect environment, when pre-burning and calcining, be easy to decompose, and the effect that the physical strength raising is just arranged by the interpolation of less amount, in addition if use strontium, then the generation of the liquid phase under the low temperature is suppressed, and can suppress grain and grow up, and also has the low such advantage of toxicity of composition in addition.In addition, separate out apace, most preferably with titanium oxide (TiO in order to make column crystal
2) powder and above-mentioned alkali earth metallic compound powder and use.
In order with homogeneous dispersive state fine column crystal 5 to be separated out, preferred its median size of above-mentioned alkali earth metallic compound powder and titanium dioxide powder is below the 1 μ m, below 0.5 μ m.In addition, the usage quantity of these powder should become the amount that makes the column crystal 5 of separating out satisfy the area ratio of regulation.Promptly, as previous elaboration, unit 100 mass parts of the total amount of alumina powder and Zirconium oxide powder, using the amount of alkali earth metallic compound powder by the oxide compound conversion is more than 0.24 mass parts, and titanium dioxide powder is the amount use of the scope of 0.4～3 mass parts according to the total amount of titanium dioxide powder and alkali earth metallic compound powder.
In this is bright,, can also use the oxide powder of Si, Zn, Nb, Ta etc. as required as sintering aid in order to improve coking property.In addition, for the painted oxide powder of Cr, Mn, Fe, Co, Ni etc. that can add as tinting material.Certainly, the such sintering aid and the powder of tinting material are not limited to oxide compound, also can be to form the form of the compound of oxide compound by calcining, and for example oxyhydroxide, carbonate, composite oxides, alkoxide add.The median size of the powder of these sintering aids and tinting material is general preferred below 1 μ m, below 0.5 μ m.Also have, the advantage of the coking property that can improve porcelain is arranged as Mn, Fe, Co, the Ni composition of additive.These sintering aid powder and tinting material powder, its total amount is for to have below 3 mass parts in Zirconium oxide powder and alumina powder total amount unit 100 mass parts, below 2 mass parts.
Be shaped with the modulation of powder
In order to make composite ceramics of the present invention, at first, within above-mentioned raw material powder, according to the amount that satisfies aforesaid amount ratio, mixed oxidization aluminium powder form, aforesaid alkali earth metallic compound powder reach as required and silicon oxide powder and the sintering aid powder and the tinting material powder of use this powder of pre-burning.By this pre-burning, make alkali earth metallic compound and silicon oxide powder and alumina powder bonding.The temperature of this pre-burning is preferably 700～1000 ℃ temperature range usually, and the pre-burning time was generally about 0.5～5 hour.
In the preburning powder that obtains by above-mentioned such pre-burning, mix the Zirconium oxide powder of aforementioned specified amount, obtain being shaped and use powder.That is, the shaping that will obtain through this pre-burning is paid with powder in the shaping and calcination process of the following stated, can access the composite ceramics as target thus.For example, do not carry out above-mentioned such pre-burning, and when the mixed powder of each raw material powder directly formed and calcines, then can not the inhibited oxidation crystalline aluminophosphate mutually 1 and the grain of zirconium white crystallization phases 3 grow up, the column crystal 5 of wishing size is separated out, thereby can not improve mechanical characteristics and hot water resistance.
Also have, aforesaid sintering aid powder and tinting material powder also can according to circumstances be mixed together in the preburning powder with Zirconium oxide powder.
Be shaped and calcining
Adopt above-mentioned shaping to carry out according to following method: to follow prescriptive procedure with the shaping of powder, as required, solvent, the organic binder bond of water and organic solvent etc. are waited modulate glutinous slurry or paste (perhaps dry glutinous slurry of modulation or paste and the powder that obtains), using such glutinous slurry, paste or powder forming is to stipulate shape.As manufacturing process, can adopt known method always such as extrusion molding, casting, calm hydraulic forming or the processing of cooling hydrostaticpressure.
Then, with the calcining of the molding that obtains, this calcining below 1600 ℃, is carried out with 1300～1550 ℃ temperature in the oxidizing atmosphere of air atmosphere etc. especially.If under the high temperature more than the needs, calcine, then zirconium white crystallization phases 3 and alumina crystal 1 growth mutually, folding strength and hardness reduce, and in addition, if calcining temperature was low temperature, then are difficult to obtain the sintered compact of densification.In addition, if calcine in reducing atmosphere, then zirconium white is reduced, and becomes zirconium and nitride etc.
In addition, the relative density based on Archimedes's method that described calcining proceeds to sintered compact usually becomes more than 95%, the degree more than 98% particularly, normally about 1～10 hour.
In the present invention, after above-mentioned calcining, with the temperature below 1500 ℃, the particularly temperature below 1400 ℃, most preferably be 1200～1350 ℃ temperature, usually, preferably in argon gas atmosphere or oxidizing atmosphere, (for example contain in the Ar gas of 20% oxygen) and carry out hot hydrostaticpressure calcining about 1～2 hour.Can either suppress to constitute the zirconium white crystallization phases and alumina crystal grain growth mutually of composite ceramics thus, can further realize densification again, the relative density of sintered compact is brought up to more than 99%.
Also have, if in argon gas, carry out hot hydrostaticpressure extruding, then since under the high temperature at ZrO
2In can produce oxygen defect and the situation of turning black, therefore in order to prevent the generation of oxygen defect, and after hot hydrostaticpressure extruding, in atmosphere, heat-treat, or in containing the atmosphere of aerobic, carry out hot hydrostaticpressure and push, can access does not thus have painted sintered compact.
As more than, can access the composite ceramics of alumina zirconia of the present invention with aforesaid composition and characteristic.
(embodiment)
The effect of excellence of the present invention is described by following experimental example.
(experimental example 1)
At first, the alumina powder of average crystallite particle diameter 0.3 μ m, purity 99.9 quality % and the various additives shown in the table 1 are mixed, carry out pre-burning with 800 ℃, 1 hour condition.Secondly, in this preburning powder, press the mixed average crystallite particle diameter 0.3 μ m shown in the table 1, the Zirconium oxide powder of purity 99.9 quality %, being modulated into is shaped uses powder.
Also have, the mixing of alumina powder and various additives, and the mixing of Zirconium oxide powder and preburning powder, all use wear-resistant alumina balls of high purity and polythene container, utilizing with Virahol (IPA) be that the wet-type ball mill mixing (mixing time 100 hours) of solvent is carried out.
Shaping to above-mentioned acquisition is carried out drying with powder, and then extrusion molding in atmosphere, with 1400～1550 ℃ of calcinings of carrying out 2 hours, is made bar-shaped sintered compact test portion.
Then, carry out hot hydrostaticpressure calcining (HIP) 1 hour, obtain the dense sintering body (test portion No.1～16) of relative density more than 99.5% by the condition shown in the table 1 (atmosphere and temperature).
Also have, in order to compare, in test portion No.1, do not use various additives fully, in test portion No.6, do not carry out the calcining after heat hydrostaticpressure calcining (HIP) in the atmosphere, in test portion No.14, do not carry out pre-burning, be mixed together alumina powder, Zirconium oxide powder and various additive powder, be modulated into the shaping powder.
Grind and cut processing by above-mentioned each sintered compact that obtains, make the test portion of 4 * 3 * 35mm, measure its folding strength, and carrying out crystal structure with scanning electron microscope and transmission electron microscope observes, carry out the compositional analysis result and the various characteristics evaluation of column crystal, its result is presented in the table 2.
In crystal structure is observed,, try to achieve zirconium white crystallization phases and alumina crystal average crystallite particle diameter and long-width ratio mutually for the crystallization phases that on the diagonal lines of electron micrograph, exists.At this moment be the major diameter of crystallization phases and the mean value of minor axis.In addition, long-width ratio is tried to achieve with the ratio (major diameter/minor axis) of minor axis as major diameter.In addition, long-width ratio is than the area ratio of 3 big column crystals to the total area of zirconium white crystallization phases and alumina crystal phase, be at 10 places arbitrarily in the cut surface, in the scope of 4.5 μ m * 6.0 μ m sizes, utilize the scanning electron microscope observation and try to achieve (multiplying power: 20,000 times), be shown as its mean value.
In addition, each characteristic, based on the folding strength under the room temperature of JIS-R1601, and the folding strength that (carries out handling in 300 hours the back under 120 ℃, 100%RH) after the hot water deterioration test, based on the destruction toughness value of JIS-R1607 according to the SEPB method, also have based on the carrying out according to Vickers' hardness of JIS-R1610, the evaluation of crystallization phases is carried out according to XRD.
[table 1]
* represent the data outside the scope of the present invention
* is together: whole raw material powders are mixed together calcining.
2 stages: be pre-mixed sintering aid and alumina powder, carry out pre-burning, it is mixed with Zirconium oxide powder.
[table 2]
* represent the data that the present invention is outer.
*Crystallization phases CTA:Ca
3Ti
8Al
13O
37, STA:SrTi
8Al
8O
19, BTA:Ba
3TiAl
10O
20
CA：CaAl
12O
19、SA：SrAl
12O
19、Ba：BaAl
12O
19
As indicated in table 1,2 the result, there is being long-width ratio to generate than 3 big column crystals, the long-width ratio of alumina crystal phase becomes in blocky test portion No.2～12,15,16 (example of the present invention) below 3, destroying toughness value is more than the 4.5GPa, Vickers' hardness is more than 1610, folding strength is more than the 1050MPa, and the folding strength after the hot water deterioration test is also more than 700MPa, particularly more than 1010MPa.With respect to this, in extraneous test portion of the present invention, among the folding strength after destruction toughness, Vickers' hardness, folding strength and the hot water deterioration test, have at least a certain characteristic low.
Claims (13)
1. a composite ceramics is characterized in that, by blocky alumina crystal phase A, blocky zirconium white crystallization phases B and contain alkaline-earth metal and the column crystal C of the composite oxides of aluminium element constitutes,
Wherein, contain from Ca as the described composite oxides that form column crystal
3Ti
8Al
12O
37, SrTi
3Al
8O
19, Ba
3TiAl
10O
20In select at least a.
2. composite ceramics according to claim 1, wherein, the column crystal C of described composite oxides has than 3 big long-width ratios.
3. composite ceramics according to claim 1, wherein, alumina crystal phase A and zirconium white crystallization phases B exist with 65/35～90/10 mass ratio A/B.
4. composite ceramics according to claim 1, wherein, the average crystallite particle diameter of alumina crystal phase A is below the 1.5 μ m, the average crystallite particle diameter of zirconium white crystallization phases B is below the 0.5 μ m.
5. composite ceramics according to claim 1 wherein, also contains from CaAl as the described composite oxides that form column crystal C
12O
19, SrAl
12O
19And BaAl
12O
19In select at least a.
6. composite ceramics according to claim 1, wherein, Vickers' hardness is more than 1600, destroying toughness value is more than 4.5, and the folding strength after the hot water deterioration test is more than the 1050MPa.
7. composite ceramics according to claim 1, wherein, when section was carried out electron microscope observation, on the face of 4.5 μ m * 6.0 μ m sizes, described column crystal C was 1～20% with respect to the area ratio of the total area of alumina crystal phase A and zirconium white crystallization phases B.
8. the method for making of a composite ceramics is characterized in that, comprising:
With median size is that alumina powder below the 2 μ m and the powder that contains the alkaline-earth metal element carry out the blended operation;
Described mixed powder is carried out the operation that pre-burning reaches the alumina powder and the degree of the powder-stuck that contains the alkaline-earth metal element;
The mixing median size is the Zirconium oxide powder below the 0.5 μ m in the powder of pre-burning, and modulation is shaped with the operation of powder; And
After described shaping powder forming is the regulation shape, in the oxidizing atmosphere below 1600 ℃, carry out the incinerating operation.
9. the method for making of composite ceramics according to claim 8 wherein, as the described powder that contains the alkaline-earth metal element, is used at least a in strontium carbonate powder, calcium carbonate powders, the barium carbonate powder.
10. the method for making of composite ceramics according to claim 8 wherein, is blended in described powder and the titanium dioxide powder that contains the alkaline-earth metal element in the alumina powder.
11. the method for making of composite ceramics according to claim 10, wherein, total with respect to blended Zirconium oxide powder after alumina powder and the pre-burning is measured 100 mass parts, the amount of using described titanium dioxide powder is more than 0.2 mass parts, and using the described amount that contains the powder of alkaline-earth metal element is more than 0.2 mass parts.
12. the method for making of composite ceramics according to claim 8 wherein, behind described calcination process, is carried out the hot hydrostaticpressure calcining below 1500 ℃ again.
13. a sliding component is characterized in that, is made of the described composite ceramics of claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005019708 | 2005-01-27 | ||
| JP019708/2005 | 2005-01-27 | ||
| JP186497/2005 | 2005-06-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101107205A CN101107205A (en) | 2008-01-16 |
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| US8927446B2 (en) | 2009-06-30 | 2015-01-06 | Aktiebolaget Skf | Zirconia-alumina ceramic materials |
| JP2014141985A (en) * | 2013-01-22 | 2014-08-07 | Nsk Ltd | Rolling bearing |
| WO2015141099A1 (en) * | 2014-03-19 | 2015-09-24 | 日本碍子株式会社 | Ceramic body and method for producing same |
| US11527388B2 (en) * | 2017-07-28 | 2022-12-13 | Kyocera Corporation | Member for plasma processing devices |
| CN108753290B (en) * | 2018-06-05 | 2021-01-15 | 湘南学院 | Bismuth and europium ion co-activated titanium aluminate fluorescent powder and preparation and application thereof |
| CN112739661A (en) * | 2018-07-27 | 2021-04-30 | 京瓷株式会社 | Alumina ceramic and ceramic heater |
| CN114988899B (en) * | 2022-06-11 | 2023-04-25 | 广东欧文莱陶瓷有限公司 | Ceramic sheet capable of releasing anions |
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