CN104768900B - Silicon nitride sinter and use the sliding component of this silicon nitride sinter - Google Patents

Silicon nitride sinter and use the sliding component of this silicon nitride sinter Download PDF

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CN104768900B
CN104768900B CN201380057709.9A CN201380057709A CN104768900B CN 104768900 B CN104768900 B CN 104768900B CN 201380057709 A CN201380057709 A CN 201380057709A CN 104768900 B CN104768900 B CN 104768900B
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silicon nitride
nitride sinter
phase
crystallization
peak value
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CN104768900A (en
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青木克之
小松通泰
船木开
山口晴彦
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Toshiba Corp
Toshiba Materials Co Ltd
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Toshiba Materials Co Ltd
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Abstract

The invention provides a kind of silicon nitride sinter, it is characterized in that: in the time that silicon nitride sinter is carried out to XRD analysis, when being set as I in 29.6 ± 0.3 ° and 31.0 ± 0.3 ° highest peak value intensity of locating to detect corresponding to hexagonal crystal system α-SiAlON crystallization29.6°、I31.0°, on the other hand will be corresponding to β-Si3N433.6 ± 0.3 °, 36.1 ± 0.3 ° highest peak value intensity of locating to detect of crystallization are set as I33.6°、I36.1°Time, each highest peak value intensity meets following relational expression: (I29.6°+I31.0°)/(I33.6°+I36.1°)=0.10～0.30? (1) in the arbitrary cross-section of described silicon nitride sinter, the Area Ratio of the Grain-Boundary Phase of per unit area 100 μ m × 100 μ m is 25～40%, and can process coefficient is 0.100～0.120. According to the present invention, the silicon nitride sinter of the sliding component that is suitable for sliding properties long-term stability can be provided and use the sliding component of this silicon nitride sinter.

Description

Silicon nitride sinter and use the sliding component of this silicon nitride sinter
Technical field
Embodiments of the present invention relate to silicon nitride sinter and use this silicon nitride sinterSliding component.
Background technology
Silicon nitride sinter is widely used as the structural material of the sliding component such as bearing ball, roller. ExampleAs former, as bearing (bearing) member of supporting rotating shaft, particularly roll as bearingThe structural material of pearl, uses the metal materials such as bearing steel conventionally. But, the metal materials such as bearing steelDue to wearability insufficient, thus exist the deviation of bearing life to increase, thus cannot be stablyObtain the problem of the High Rotation Speed driving that reliability is high.
As a kind of means that address the above problem, in recent years, use silicon nitride sinter as axleHold the structural material of ball. Silicon nitride sinter sliding properties in pottery is also good, soUnder a part of use state, wearability is fully, is carrying out high-speed rotary even if can confirmIn situation about turning, within the time limit to a certain degree, also can realize the rotary actuation that reliability is high.
As the sintering composition of former silicon nitride sinter, known have silicon nitride-terres raresOxide-alumina series, silicon nitride-yittrium oxide-aluminium oxide-aluminium nitride-titanium system etc. Above-mentioned sintering compositionIn yittrium oxide (Y2O3) etc. the sintering aids such as rare-earth oxide all the time usually used as sinteringAuxiliary agent uses, thus be in order to improve agglutinating property, make sintered body densified realize high strength andAdd. For example, open in TOHKEMY 2006-36554 communique (patent documentation 1).
In addition, in TOHKEMY 2002-326875 communique (patent documentation 2), disclose in realityExecute in the situation of abrasion test of regulation, demonstrate 400 hours above long-life silicon nitrides and burnKnot body.
On the other hand, for the sliding component such as bearing ball that uses silicon nitride sinter, wantAsk more than 400 hours and then the long-life of about 800 hours. By carrying out the longevity of bearing ballLifeization, can realize non-maintainingization of the sliding parts such as bearing.
The sliding components such as bearing are used in lathe, electronic equipment, automobile, aircraft and also have wind-force to send outThe product in the various fields such as electricity. If realize the long lifetime of sliding component, can realize variousThe long lifetime of product, and then realize non-maintainingization.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-36554 communique
Patent documentation 2: TOHKEMY 2002-326875 communique
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is: provide sliding properties can possess more reliably and with long-termThe silicon nitride sinter of property and use the sliding component of this silicon nitride sinter.
For solving the means of problem
According to an embodiment of the invention, can obtain a kind of silicon nitride sinter, its featureBe: in the time that silicon nitride sinter is carried out to XRD analysis, when will be corresponding to hexagonal crystal system29.6 ± 0.3 ° and 31.0 ± 0.3 ° highest peak value intensity of locating to detect of α-SiAlON crystallization are set asI29.6°、I31.0°, on the other hand will be corresponding to β-Si3N4Locate for 33.6 ± 0.3 °, 36.1 ± 0.3 ° of crystallizationThe highest peak value intensity detecting is set as I33.6°、I36.1°Time, each highest peak value intensity meets following passBe formula:
(I29.6°+I31.0°)/(I33.6°+I36.1°)＝0.10～0.30(1)
In the arbitrary cross-section of described silicon nitride sinter, the crystalline substance of per unit area 100 μ m × 100 μ mThe Area Ratio of boundary's phase is 25～40%, can process coefficient (machinablecoefficients) and be 0.100～0.120。
In addition, in the time that silicon nitride sinter is carried out to XRD analysis, corresponding to Y4Si2O7N2(JPhase) 39.5 ± 0.3 ° of highest peak value intensity I of locating to detect39.5°Preferably meet following relational expression:
(I39.5°)/(I33.6°+I36.1°)＝0.03～0.10(2)
In addition, in the time that silicon nitride sinter is carried out to XRD analysis, corresponding to Y2Si3O12N(HPhase), YSiO2N (K phase) or Y2Si3O3N4In any above 31.9 ± 0.3 ° locate to detectHighest peak value intensity I31.9°Preferably meet following relational expression:
(I31.9°)/(I33.6°+I36.1°)＝0.05～0.15(3)
In addition, XRD analysis preferably carries out at the arbitrary cross-section of silicon nitride sinter.
In addition, preferably possesses the amorphous that comprises the crystallization of Hf-Y-O based compound and contain Y-Al-OThe Grain-Boundary Phase of matter phase. In addition, preferably possessing average grain diameter is carbide, the oxidation below 2 μ mThe particle such as thing, nitride. In addition, the particle that preferred described particle is molybdenum compound. In addition, excellentThe Al that choosing contains 5～10 quality % in oxide scaled value, contains 1～10 in oxide scaled valueMore than any in the rare earth element of quality %, contain 1～5 quality % in oxide scaled value4A, 5A, 6A element in any more than, and preferably the mol of Al and rare earth element (rubsYou) is than being A1 (mo1) ﹕ rare earth element (mol)=1 ﹕ 1～8 ﹕ 1. In addition, preferably tie upFamily name's hardness (Hv) is more than 1500, Fracture Toughness (K1C) be 6.0MPam1/2Above, andAnd more than preferably 3 bending strengths are preferably 900MPa.
In addition, the sliding component of embodiment is characterised in that the nitrogenize that has used described embodimentSilicon sintered body. In addition, preferably sliding component is bearing ball. In addition, sliding surface is preferably shownSurface roughness (Ra) is the abradant surface below 0.5 μ m.
The effect of invention
Present embodiment can provide a kind of long-term reliability of nitrogen can give to(for) sliding propertiesSiClx sintered body. In addition, can process coefficient owing to having adjusted, so even if carried out surface grindingProcessing, also owing to can reducing threshing, so easily obtain smooth sliding surface. For this reason, evenFor the sliding component that has used this sintered body, also can obtain long-term reliability.
Brief description of the drawings
Fig. 1 represents to use silicon nitride sinter of the present invention and an enforcement of the sliding component that formsThe stereogram of mode.
Detailed description of the invention
Below, describe with regard to embodiment.
(the first embodiment)
The first embodiment relates to a kind of silicon nitride sinter, it is characterized in that: silicon nitride is being burntKnot body is while carrying out XRD analysis, when by 29.6 ± 0.3 ° corresponding to hexagonal crystal system α-SiAlON crystallizationBe set as I with 31.0 ± 0.3 ° of highest peak value intensity of locating to detect29.6°、I31.0°, on the other hand will be rightShould be in β-Si3N433.6 ± 0.3 °, 36.1 ± 0.3 ° highest peak value intensity of locating to detect of crystallization are set asI33.6°、I36.1°Time, each highest peak value intensity meets following relational expression:
(I29.6°+I31.0°)/(I33.6°+I36.1°)＝0.10～0.30(1)
In the arbitrary cross-section of described silicon nitride sinter, the crystalline substance of per unit area 100 μ m × 100 μ mThe Area Ratio of boundary's phase is 25～40%, and can process coefficient is 0.100～0.120.
First, describe with regard to the condition of implementing XRD analysis. Measurement face is any table of sintered bodyFace or arbitrary cross-section, be set as surface roughness Ra and be milled to the abradant surface below 1 μ m. XRDAnalysis is set as in Cu target (Cu-K α), tube voltage 40kV, tube current 40mA, sweep speedUnder 10 °～60 ° of 2.0 °/min, slit (RS) 0.15mm, sweep limits (2 θ), carry out. In addition,Sweep limits (2 θ), if comprise 10 °～60 °, also can be regarded as and carry out broad scope. SpecialThe not preferably section of sintered body. If analyze with section, also can be used as and obtain crystalline substanceThe face of the Area Ratio of boundary's phase.
The first embodiment is in the time carrying out XRD analysis, when will be corresponding to hexagonal crystal system α-SiAlON29.6 ± 0.3 ° and 31.0 ± 0.3 ° highest peak value intensity of locating to detect of crystallization are set as I29.6°、I31.0°、On the other hand will be corresponding to β-Si3N433.6 ± 0.3 °, 36.1 ± 0.3 ° locate to detect the strongest of crystallizationPeak strength is set as I33.6°、I36.1°Time, each highest peak value intensity meets following relational expression: (I29.6°+I31.0°)/(I33.6°+I36.1°)=0.10～0.30. Carry out the peak position of XRD analysis by tying separatelyBrilliant lattice paprmeter determines.
If there is hexagonal crystal system α-SiAlON crystallization, locate inspection at 29.6 ± 0.3 ° and 31.0 ± 0.3 °Measure peak value. In other words, if locate to detect peak value at 29.6 ± 0.3 ° and 31.0 ± 0.3 °, just meaningTaste and is had hexagonal crystal system α-SiAlON crystallization. In addition, use I29.6°And I31.0°Two peak strengthsReason is the impact in order to relax the variation that peak strength causes by crystalline orientation.
In addition, if there is β-Si3N4Crystallization, locates to detect peak at 33.6 ± 0.3 ° and 36.1 ± 0.3 °Value. In other words,, if locate to detect peak value at 33.6 ± 0.3 ° and 36.1 ± 0.3 °, just mean and depositAt β-Si3N4Crystallization. In addition, use I33.6°And I36.1°The reason of two peak strengths is in order to relaxThe impact of the variation that peak strength is caused by crystalline orientation.
In the first embodiment, meet (I29.6°+I31.0°)/(I33.6°+I36.1°)＝0.10～0.30。The size basis of the peak strength separately amount of crystallization decides. So-called (hexagonal crystal α-SiAlONCrystallization/β-Si3N4Crystallization) peak strength than i.e. (I29.6°+I31.0°)/(I33.6°+I36.1°) be 0.10～0.30, refer to respect to β-Si3N4, there is hexagonal crystal system α-SiAlON crystallization of ormal weight in crystallization.
In addition, if there is hexagonal crystal α-SiAlON crystallization, near 34.4 °, 35.1 °, also detectGo out peak value. In addition, if there is β-Si3N4Crystallization also detects peak near 23.4 °, 27.1 °Value. Near having or not of the peak value detecting this, also can be for holding hexagonal crystal α-SiAlON crystallizationAnd β-Si3N4Having or not of the existence of crystallization. In addition, overlapping and difficult with other crystallization peak value described laterWhen distinguishing, also can with various qualitative analyses combinations.
By existing hexagonal crystal system α-SiAlON crystallization to become hexagonal crystal system α-SiAlON crystallizationAnd β-Si3N4The tissue that crystallized mixed exists, can reduce the deviation that exists of Grain-Boundary Phase, thereby canStrengthening Grain-Boundary Phase. For this reason, be improved as hardness, the toughness etc. of sintered body, thereby also canImprove wearability. Hexagonal crystal system α-SiAlON crystallization also can have spherical shape or columnar shape this twoPerson.
Especially, hexagonal crystal α-SiAlON crystallization preferably asperratio be below 2. β-Si3N4It is more than 2 long column shape shapes that crystallization is asperratio. The nitrogenize of patent documentation 1 and patent documentation 2Silicon sintered body is by making β-Si3N4The intricate ground of crystallization be wound around mutually and form hardness and toughness highSilicon nitride sinter. On the other hand, due to β-Si3N4Crystallization is long column shape shape, so β-Si3N4The deviation of crystallization grain boundary size is each other larger, thereby forms partly the position that Grain-Boundary Phase is manyThe position few with Grain-Boundary Phase. For this reason, can see the reduction of the long term life of sliding properties.
In the first embodiment, due to the β-Si of long column shape shape3N4Crystallization and spherical or columnHexagonal crystal α-SiAlON crystallized mixed exists, thereby becomes hexagonal crystal α-SiAlON crystallization and enterβ-Si3N4The structure in crystallization gap each other, thus can make the ratio that exists of Grain-Boundary Phase stablize.
At (hexagonal crystal α-SiAlON crystallization/β-Si3N4Crystallization) peak strength than lower than 0.10 o'clock,Hexagonal crystal α-SiAlON crystallization is very few, thereby the deviation that has ratio of Grain-Boundary Phase increases. The opposing partyFace, at (hexagonal crystal α-SiAlON crystallization/β-Si3N4Crystallization) peak strength larger and exceed 0.30Time, β-Si3N4The ratio of crystallization reduces, β-Si3N4The tissue that the intricate ground of crystallization is wound around mutually subtractsFew, thus sliding properties reduces.
In addition, by the crystalline substance of the per unit area of the arbitrary cross-section of silicon nitride sinter 100 μ m × 100 μ mThe Area Ratio of boundary's phase is set as 25～40%, easily controls thus the deviation that exists of Grain-Boundary Phase. FirstIn embodiment, to remove β-Si3N4Beyond crystallization and hexagonal crystal α-SiAlON crystallization is Grain-Boundary Phase mutually.Even if the silicon nitride sinter of the first embodiment is to arbitrary cross-section, namely whichever section entersRow is measured, and the Area Ratio of the Grain-Boundary Phase of per unit area 100 μ m × 100 μ m is also at 25～40% modelIn enclosing. Owing at unit are 100 μ m × 100 these tiny areas of μ m, the ratio of Grain-Boundary Phase being carried outControl, so not only the hardness of sintered body and fracture toughness are improved, and can be slidedThe long-term reliability of characteristic.
In addition, the measuring method of the Area Ratio of Grain-Boundary Phase is as described below. First, obtaining silicon nitride burnsThe arbitrary cross-section of knot body. This section is implemented to attrition process, to make its surface roughness Ra be 1 μ m withUnder. For clear and definite β-Si3N4The region of crystallization and hexagonal crystal α-SiAlON crystallization and Grain-Boundary Phase, to obtainingAbradant surface carry out plasma etch process.
If enforcement plasma etch process, due to β-Si3N4Crystallization and hexagonal crystal α-SiAlONCrystallization is different from the etch-rate of Grain-Boundary Phase, so that one party can be pruned is more. For example, usingCF4Plasma etching in, β-Si3N4Crystallization and hexagonal crystal α-SiAlON crystallization are due to etch-rateLarge (easily etched), so β-Si3N4Crystallization and hexagonal crystal α-SiAlON crystallization become recess,And Grain-Boundary Phase becomes protuberance.
In addition, etch processes can be also the chemical etching that uses bronsted lowry acids and bases bronsted lowry. To after etch processesMinute surface carries out SEM image taking (1000 times of above multiplication factors). In SEM photo, canDistinguish β-Si with the difference by contrast3N4Crystallization and hexagonal crystal α-SiAlON crystallization and Grain-Boundary Phase. LogicalOften, Grain-Boundary Phase seems to be white in color. By carrying out etch processes, can make the difference of contrast moreClear.
By SEM photo is carried out to graphical analysis, can measure the face of the Grain-Boundary Phase of per unit areaLong-pending ratio. In addition, in graphical analysis, chromoscan Grain-Boundary Phase part and the side that carries out graphical analysisMethod is effective. In addition, a visual field less than unit are 100 μ m × 100 μ m in the situation that,Also can repeatedly take, make it add up to unit are 100 μ m × 100 μ m.
In addition, the coefficient processed of the silicon nitride sinter of the first embodiment is 0.100-0.120.
The above-mentioned coefficient Mc that processes is the value calculating from following formula (4).
Mc＝Fn9/8/(K1c 1/2·Hv5/8)(4)
In formula (4), Fn is loading of pressing in, in this case 20kgf. The loading of pressing in Fn of 20kgf existsHardness and the toughness aspect of measuring silicon nitride sinter are suitable numerical value. Vickers hardness (Hv) rootMeasure according to JIS-R-1610. Fracture Toughness (K1C) according to the indentation method (IF of JIS-R-1607Method, IndentationFracturemethod) measure. In the time of the calculating of Fracture Toughness, makeWith new former formula. About bearing ball described later, use its section to measure.
Can process coefficient Mc is to represent to have used loading of pressing in (Fn), Vickers hardness (Hv) and disconnectedSplit toughness value (K1C) the coefficient of processability. This is the relational expression of transversal crack fracture model, McRepresent the amount of being removed by 1 abrasive particle. Mean that can to process coefficient Mc larger, once can processAmount larger.
So-called transversal crack fracture model, the material while referring to as grinding is removed mechanism, byThe model that EvansShi and MarshallShi propose. In this model, 1 grinding abrasive particle passes through materialThe amount of substance (Δ V) being removed in the power that abrasive particle is pressed into along the vertical direction of material when on material the surfaceFn, Vickers hardness (Hv) and Fracture Toughness (K1C) be related to aspect, be represented as and [Fn9/8/(K1c 1/2·Hv5/8)] value be directly proportional. At this, Δ V is replaced into and can processes coefficient Mc.
Processing is roughly distinguished, and can be divided into brittle mode and ductility pattern. Brittle mode is equivalent to what is calledRoughing, ductility pattern is equivalent to so-called fine finishining. So-called abrasion, it is generally acknowledged and be equivalent toDuctility pattern, think and the performance that requires that meets wearability member importantly do not reduce ductility mouldThe processability of formula and improve the processability of brittle mode. In addition, as one of abrasion model, generalThe mechanism of thinking is: produce small pre-crackle (precrack) at crystal boundary, because of its propagation untilMaterial surface destroys, thereby produces abrasion.
Represent abrasion model Mechanical Contact harsh degree parameter S c.m according to coefficientoffrictionμ,Crystallization particle diameter d, the Fracture Toughness K of dahe sesame stress Pmax, material1cRepresent with following formula.
Sc.m＝[(1+10·μ)·Pmax·(d1/2)]/K1c
This means when parameter S c.m is larger, abrasion are just large, and parameter S c.m hour, wears away just little.Hence one can see that: by reducing the crystallization particle diameter d of material or strengthening Fracture Toughness K1c, can suppress millConsumption.
Considering these aspects in the situation that, can process coefficient Mc preferably at 0.100～0.120 modelEnclose. Can process coefficient Mc lower than 0.100 in the situation that, the attrition process amount being caused by abrasive particle is less,So the attrition process time of silicon nitride sinter increases. Exceed 0.120 if can process coefficient Mc,The attrition process quantitative change that silicon nitride sinter is caused by abrasive particle is too much. If attrition process amountGreatly, processability is improved, but reduces as the durability of sliding component.
Can process the silicon nitride sinter of coefficient Mc in 0.100～0.120 scope as sintered bodyMake, on basis that hardness and fracture toughness be improved, can also improve sliding properties. In addition, byThreshing vestige in the time can reducing sliding surface to carry out attrition process, so it is thick easily to obtain surfaceRugosity Ra is below 0.5 μ m and then is the tabular surface below 0.1 μ m. If consideration processability,Can process coefficient Mc preferably in 0.110～0.120 scope.
In addition, in the time that silicon nitride sinter is carried out to XRD analysis, corresponding to Y4Si2O7N2(JPhase) 39.5 ± 0.3 ° of highest peak value intensity I of locating to detect39.5°Preferably meet relational expression: (I39.5°)/(I33.6°+I36.1°)＝0.03～0.10。
Y4Si2O7N2(J phase) is for being present in the crystalline phase of Grain-Boundary Phase. What is called is located inspection at 39.5 ± 0.3 °Measure peak value, refer to and have Y4Si2O7N2(J phase). By by Y4Si2O7N2The peak value of (J phase)Strength ratio (I39.5°)/(I33.6°+I36.1°) be set in 0.03～0.10 scope, can strengthen crystal boundaryPhase. By strengthening Grain-Boundary Phase, can further improve the long-term reliability of sliding properties.
In addition, if there is Y4Si2O7N2(J phase), 31.0 °, 34.4 °, 36.1 °, 39.5 °,Near 44.5 °, (± 0.3 °) locates also can detect peak value. Why select I39.5°, be because rightShould in the peak value of J phase, represent that the possibility of highest peak value is higher.
In addition, in the time that silicon nitride sinter is carried out to XRD analysis, corresponding to Y2Si3O12N(HPhase), YSiO2N (K phase) or Y2Si3O3N4In any above 31.9 ± 0.3 ° locate to detectHighest peak value intensity I31.9°Preferably meet (I31.9°)/(I33.6°+I36.1°)＝0.05～0.15。
Y2Si3O12N (H phase), YSiO2N (K phase) or Y2Si3O3N4In any for existIn the crystalline phase of Grain-Boundary Phase. What is called locates to detect peak value at 31.9 ± 0.3 °, refers to and has Y2Si3O12N(H phase), YSiO2N (K phase) or Y2Si3O3N4In any above crystalline phase.
By by peak strength than (I31.9°)/(I33.6°+I36.1°) be set in 0.05～0.15 scope,Can strengthen Grain-Boundary Phase. By strengthening Grain-Boundary Phase, can further improve for a long time can of sliding propertiesLean on property. In addition, about selecting I31.9°Reason, be because it be corresponding to Y2Si3O12N (H phase),YSiO2N (K phase) or Y2Si3O3N4In any above peak value in one of highest peak.
In addition, preferably possesses the amorphous that comprises the crystallization of Hf-Y-O based compound and contain Y-Al-OThe Grain-Boundary Phase of matter phase. The crystallization of Hf-Y-O based compound is the compound crystallization that contains hafnium, yttrium and oxygen.In addition, the amorphous phase that contains Y-Al-O is the amorphous phase that at least contains yttrium, aluminium and oxygen.
Hafnium is active component, reacts and form the crystallization of Hf-Y-O based compound with yttrium and oxygen, promotes Si3N4Growth response. At this moment, it is generally acknowledged and also contribute to Y4Si2O7N2(J phase), Y2Si3O12N(HPhase), YSiO2N (K phase) or Y2Si3O3N4In a kind of above formation.
In addition, by being set as mutually amorphous phase (glassy phase) by what contain Y-Al-O, becomeEasily control the homogeneous distribution of Grain-Boundary Phase. In addition Hf-Y-O based compound crystallization and contain Y-Al-O,Having or not of existence of amorphous phase can confirm by tem analysis.
In addition, preferably possessing average grain diameter is the grains such as carbide below 2 μ m, oxide, nitrideSon. As above-mentioned particle, be preferably selected from silicon (Si), 5A family vanadium (V), niobium (Nb),On at least a kind among the chromium (Cr) of tantalum (Ta), 6A family, molybdenum (Mo), tungsten (W)Particle.
Above-mentioned particle, by being present in Grain-Boundary Phase, contributes to the strengthening of Grain-Boundary Phase. In addition, for realityThe strengthening of existing Grain-Boundary Phase, preferably average grain diameter is below 2 μ m, more preferably below 1.5 μ m.If average grain diameter is compared with exceeding 2 μ m greatly, the continuous distributed that hinders crystal boundary, likely becomes knotThe cause of structure defect.
In addition, above-mentioned particle is preferably molybdenum compound particle. Molybdenum compound particle is lubricated owing to havingProperty, so by being present in sliding surface (surface of silicon nitride sinter), can improve sliding surfaceSliding properties. In addition, in molybdenum compound particle, molybdenum carbide (Mo2C) lubricity of particleGood.
In addition, at β-Si3N4In crystallization, preferably major axis is more than 2 μ m, maximum asperratioBe below 7. In addition, in hexagonal crystal α-SiAlON crystallization, no matter be spherical shape or column shapeShape, its average grain diameter is all preferably below 2 μ m. In addition spherical shape, columnar shape (chi in length and breadth,Very little ratio is below 2) average grain diameter will use the diameter of a circle of equal value of major axis to be set as particle diameter, and byThe mean value of 100 is obtained.
In addition, the Al that preferably contains 5～10 quality (wt) % in oxide scaled value, to be oxidizedMore than any in the rare earth element that thing scaled value meter contains 1～10 quality %, change with oxideMore than any in 4A, 5A, 6A element that calculation value meter contains 1～5 quality %, and preferred AlCompare for Al (mol) ﹕ rare earth element (mo1)=1 ﹕ 1～8 ﹕ 1 with the mol of rare earth element.
A1 (aluminium) is for improving the composition of agglutinating property, and be form hexagonal crystal α-SiAlON crystallization andThe necessary composition of Y-Al-O based compound amorphous phase. In addition, as sintering aid addIn situation, preferably A12O3(aluminium oxide), A1N (aluminium nitride). If Al is with oxideConvert meter lower than 5 quality %, likely make the ratio of Grain-Boundary Phase reduce, and likely make variousThe formation deficiency of crystallised component and noncrystalline composition. On the other hand, if exceed 10 quality %, haveMay make Grain-Boundary Phase too increase.
Rare earth element preferably Y (yttrium), La (lanthanum), Ce (cerium), Pr (praseodymium),Nd (neodymium), Pm (promethium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium),Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium), Lu (lutetium) itIn more than at least a kind. In addition, in the situation that adding as sintering aid, preferably as rare earthType oxide and adding. In addition, any in rare earth element is above in oxide scaled valueIf lower than 1 quality %, exceed 10 quality %, the ratio of Grain-Boundary Phase is likely in embodimentScope outside, and become difficulty with the adjustment of the mol ratio of Al element.
In addition, in rare earth element, yttrium is preferred. If yttrium contains as formationY4Si2O7N2(J phase), Y2Si3O12N (H phase), YSiO2N (K phase), Y2Si3O3N4、The composition of the amorphous phase of the crystallization of Hf-Y-O based compound, Y-Al-O and playing a role. In addition, alsoPromote the generation of α-SiAlON crystallization.
In addition, in the 4A, the 5A that preferably contain 1～5 quality % in oxide scaled value, 6A elementAny more than. 4A family element is Ti (titanium), Zr (zirconium), Hf (hafnium). In addition, 5AFamily's element is V (vanadium), Nb (niobium), Ta (tantalum). In addition, 6A family element be Cr (chromium),Mo (molybdenum), W (tungsten). It is to use TiO that the oxide of 4A family element converts2、ZrO2、HfO2Convert. In addition, the conversion of the oxide of 5A family element is to use V2O5、Nb2O5、Ta2O5Carry outConvert. In addition, the conversion of the oxide of 6A family element is to use Cr2O3、MoO3、WO3Convert.
In addition, in the situation that adding as sintering aid, preferably with oxide, carbide, nitrogenAny in compound adds above. In addition, 4A family element preferably adds with the form of oxide,5A family element and 6A family element preferably add with the form of carbide. In addition, 4A family element is preferablyHf, 6A family element is preferably Mo. Hf as previously mentioned, as forming the crystallization of Hf-Y-O based compoundComposition and play a role. In addition, preferably by Mo with molybdenum carbide (Mo2C) form of particle is added.As previously mentioned, molybdenum compound particle becomes Grain-Boundary Phase strengthening composition, the sliding surface of conduct raising simultaneouslyThe composition of lubricity and playing a role. The particle of 5A family element and 6A family element has lubricity, stillWherein molybdenum compound has the best lubricity.
In addition, as the composition beyond above-mentioned, can list the carborundum as carbide particle(SiC). In the situation that adding carborundum, preferably in the scope of 1～5wt%.
In addition, the mol of Al and rare earth element ratio is preferably Al (mol) ﹕ rare earth element (mol)=1 ﹕ 1～8 ﹕ 1. By Al amount is existed with 1～8 times of rare earth element amount, hexagonal crystalα-SiAlON crystallization becomes easy formation. In addition, preferably at Al (mol) ﹕ rare earth element (mol)In the scope of=1.4 ﹕ 1～7.0 ﹕ 1.
In addition, in the case of adding above-mentioned each composition as sintering aid, when by silicon nitrideWhen amount of powder is set as 100 mass parts, the total oxygen amount of sintering aid is preferably in 1.20～2.50 qualityThe scope of part. As the interpolation form of various sintering aids, by allocating with nitride or carbideForm add ratio, just the amount of adding as oxide can be set as to above-mentioned scope. ExampleAs, can list with AlN interpolation Al composition, use Mo2C etc. add the method for Mo composition. Pass throughReduce the total oxygen amount of sintering aid, increase nitride, also easily form hexagonal crystal α-SiAlON knotBrilliant. In addition, oxidesintering auxiliary agent contributes to the noncrystalline that contains Y-Al-O to equate the shape of Grain-Boundary PhaseBecome. For this reason, by making the total oxygen amount of sintering aid in above-mentioned scope, also can control Grain-Boundary PhaseArea Ratio.
In addition, above-mentioned silicon nitride sinter if, can demonstrate good characteristic, itsVickers hardness (Hv) is more than 1500, Fracture Toughness (K1c) be 6.0MPam1/2Above, 3Point bending strength is more than 900MPa.
In addition, Vickers hardness (Hv) is measured according to JIS-R-1610. Fracture Toughness (K1C)Measure according to the indentation method of JIS-R-1607 (IF method). In addition, in the calculating of Fracture ToughnessIn, use new former formula. In addition, 3 bending intensity are measured according to JIS-R-1601.
(the second embodiment)
The second embodiment is the sliding component that has used the silicon nitride sinter of the first embodiment.As sliding component, can list bearing ball, roller, check ball, wear-resistant pad, plunger,Roller etc. These sliding components slide with the counter-element being made up of hardware and pottery etc.In order to improve the durability of sliding surface, be preferably designed for surface roughness (Ra) attrition process and become 0.5 μ mBelow and then be that 0.1 μ m is following, the abradant surface below 0.05 μ m more preferably. By making sliding surfaceBecome smooth, can improve the durability of silicon nitride sinter, reduce for counter-element simultaneouslyAggressive. By reducing the aggressiveness for counter-element, owing to can reducing disappearing of counter-elementConsumption, so can improve the durability of the device that enrolls sliding component.
As the device that enrolls sliding component, can list lathe, electronic equipment, automobile, flyMachine also has the product in the various fields such as wind-power electricity generation.
Fig. 1 shows bearing ball as an example of sliding component and revolving member. In Fig. 1,Symbol 1 is bearing ball. Bearing ball 1 is the spheroid of proper sphere shape. In general, configure multiple axlesHold ball and form bearing. Bearing ball makes whole surface become sliding surface. In addition, forming axleWhile holding, owing to using multiple bearing balls, so also require the uniformity of shape. The first enforcement sideThe silicon nitride sinter of formula is due to the Area Ratio of Grain-Boundary Phase is adjusted into 25～40%, and can process systemNumber Mc are adjusted into 0.100～0.120, so even to have implemented surface roughness (Ra) be 0.5 μ m withUnder attrition process, its threshing is also few, thus threshing vestige is also little. For this reason, usingIn the situation of the attrition process of diamond abrasive grain, can obtain few and clean smooth of threshing vestigeFace.
In addition, by controlling Area Ratio, the crystallization of Grain-Boundary Phase of per unit area 100 μ m × 100 μ mCompositions etc., can make sliding properties stabilisation chronically. For example, the feelings of former bearing ballUnder condition, in the time of continuous operation, there is the durability of 400～500 hours, and the present invention can obtain 700Durability more than hour and then more than 800 hours. Therefore, not only can maintain sliding componentLong-term reliability, and can obtain the device that enrolls bearing ball of the present invention long-term reliability orNon-maintainingization texts.
(manufacture method of the silicon nitride sinter of the first embodiment)
Describe with regard to manufacture method below. As long as the silicon nitride sinter of the first embodiment hasAbove-mentioned formation, just there is no particular limitation for manufacture method, but effectively obtain this nitrogenize as being used forThe method of silicon sintered body, can list following method.
First, prepare alpha-silicon nitride powders. Alpha-silicon nitride powders is preferably: oxygen content is 1.7 quality %Below, contain α facies pattern silicon nitride (α-Si more than 85 quality %3N4), average grain diameter is 1.0 μ mBelow, and then be below 0.8 μ m. By make α-Si in sintering circuit3N4Powder grain is grown toβ-Si3N4Crystallization, can obtain the good silicon nitride sinter of sliding properties.
Secondly, prepare sintering aid powder. As sintering aid, with Al composition and rare earth elementComposition is neccessary composition. In addition, as required, add and be selected from 4A family elemental composition, 5A family elementAt least a kind of above and carborundum among composition and 6A family elemental composition.
In addition, as previously mentioned, preferably add, to make the mol ratio of Al and rare earth element beAl (mol) ﹕ rare earth element (mol)=1 ﹕ 1～8 ﹕ 1. In addition, adding sintering aidTime, in the time that alpha-silicon nitride powders amount is set as to 100 mass parts, preferably the total oxygen amount of sintering aid isThe scope of 1.20～2.50 mass parts. In order to control the oxygen amount of the composition adding as sintering aid, excellentChoosing is added Al composition with the form of AlN, by 5A family elemental composition and 6A family elemental composition with carbonizationThe form of thing is added. Especially, AlN is together with rare earth element and α-Si3N4React and form sixPrismatic crystal α-SiAlON crystallization aspect is effective sintering aid.
Then, mix above-mentioned alpha-silicon nitride powders and sintering aid powder. Mixed processes uses ball milling mixedClose machine etc. and mix, thereby becoming even admixture. Especially, by making α-Si3N4The dispersity of powder and AlN powder and rare-earth compounds becomes even mixing, hexagonal crystalα-SiAlON crystallization is just easily formed uniformly. In addition, for even mixing, preferably will use ballThe mixed processes of mill mixer etc. is implemented more than 50 hours. In addition, be set as mixing in solutionThe wet mixed method of closing operation is also effective to even mixing.
In addition, allocating in wet type mode in the operation of raw mixture, preferably in advance by Al systemizationCompound and rare-earth compounds are deployed into the slip of favorable dispersibility, are then mixed in as mainly formerIn the slip of the alpha-silicon nitride powders of material. At this moment dispersed index optimization uses following thixotropic index(TI value) manages. If improve continuously shear rate a, b in rotation viscometer,Having in coherent fluid, viscosity can reduce conventionally. Now, under shear rate a and the bThe ratio of viscosity number η becomes TI value.
TI value=η b/ η a
The not special regulation of the numerical value of shear rate a, b, but get more than 1 to be set as TI valueValue is advisable. TI value more approaches 1, just more approaches the behavior of Newtonian fluid, imply this be not cohesion,Or condense the slip of very weak high dispersive. In this case, make to set a=6 thereby adjust(1/s), TI value when b=60 (1/s) is got 1.0～2.0 numerical value. In addition, s represents second. Pass throughUse such hybrid mode, the hexagonal crystal α-SiAlON crystallization can effectively carry out sintering timeGrain growth uniformly.
Then, in the raw mixture that alpha-silicon nitride powders and sintering aid powder are mixed, addAdding additives. The mixing of raw mixture and binding agent is pulverized and granulation on one side as required,Use on one side ball mill etc. to be implemented. Raw mixture is configured as to desirable shape. Be shapedOperation is by enforcements such as moulding press and cold isostatic presses (CIP). Forming pressure is preferably 100MPaAbove. Then, the formed body obtaining is carried out to degreasing in forming process. Degreasing process preferably existsAt the temperature of the scope of 300～600 DEG C, implement. Degreasing process is in atmosphere or in non-oxidizing atmosphereImplement, there is no particular limitation for atmosphere.
Then the degreasing that, sintering obtains in degreasing process at the temperature of 1600～1900 DEG C of scopesBody. If sintering temperature is lower than 1600 DEG C, the grain growth of crystalline silicon nitride particle likely becomesObtain insufficient. That is to say, from α-Si3N4To β-Si3N4Reaction insufficient, likely cannotObtain fine and close tissue of sintered body. In this case, reliable as material of silicon nitride sinterProperty reduces. If sintering temperature exceedes 1900 DEG C, it is raw that crystalline silicon nitride particle too carries out crystal grainLong, likely cause strength decreased, or likely make the ratio of Grain-Boundary Phase be in outside scope.
In above-mentioned sintering circuit, can be in addition real by any in normal pressure-sintered and pressure sinteringExecute. Sintering circuit is preferably implemented in non-oxidizing atmosphere. As non-oxidizing atmosphere, Ke YilieEnumerate blanket of nitrogen and argon atmospher.
After sintering circuit, preferably in non-oxidizing atmosphere, implement high temperature insostatic pressing (HIP) more than 30MPa(HIP) process. As non-oxidizing atmosphere, can list blanket of nitrogen and argon atmospher. HIP placeReason temperature is preferably the scope of 1500～1900 DEG C. Process by implementing HIP, can eliminate silicon nitridePore in sintered body. If HIP processing pressure, lower than 30MPa, cannot obtain so fullyEffect.
For the silicon nitride sinter of such manufacture, implement attrition process at necessary position and makeSliding component. Attrition process is preferably implemented with diamond abrasive grain. Due to the silicon nitride of embodimentSintered body has good processability, makes sliding component so can reduce by silicon nitride sinterTime processing cost. In addition, can obtain surface roughness (Ra) is that 0.5 μ m is following, Jin ErweiTabular surface below 0.1 μ m, below 0.05 μ m.
(embodiment 1)
(embodiment 1～13 and comparative example 1～2)
As alpha-silicon nitride powders, preparing oxygen content is that 1.2 quality %, average grain diameter are 0.7 μ m, α-Si3N4Ratio be the powder of 99 quality %. Then,, as sintering aid, the sintering that preparation table 1 represents helpsAgent. In addition, all to use average grain diameter be the powder below 1.3 μ m to sintering aid powder.
Table 1
Then, coordinate above-mentioned alpha-silicon nitride powders and sintering aid powder, undertaken 50 little by ball millTime wet mixed. Thereby mixing the TI value making is at this moment 1.0～2.0. Then, from solutionAfter taking out and being dried, mix with binding agent, carry out the mixed processes of 20 hours by ball mill, fromAnd mix respectively mixed material powder.
Then, by moulding press, each raw mixture is formed, then carry out degreasing at 460 DEG C.Then, in blanket of nitrogen, under 1700～1800 DEG C × 4～6 hours, degreasing body is carried out to sintering.
Then the sintered body obtaining being implemented to HIP processes. HIP process under the pressure of 100MPa,Under the condition of 1600 DEG C × l～2 hour, implement. Just produce thus embodiment 1～13 and comparative example 1～2Silicon nitride sinter. In addition, 3 bending strengths are measured with test portion (silicon nitride sinter) processingBecome the size of 3mm × 4mm × 50mm to use.
For the test portion (silicon nitride sinter) of embodiment 1～13 and comparative example 1～2, surface is thickRugosity (Ra) grinds to form below 0.1 μ m. Afterwards, measured Vickers hardness (Hv), rupture toughProperty value (K1C), 3 bending strengths, can process coefficient Mc. Vickers hardness (Hv) is with 20kgfLoading of pressing in, adopt measure according to the method for JIS-R-1610. Fracture Toughness is with 20kgfLoading of pressing in, measure according to the indentation method of JIS-R-1607 (IF method), and by new formerFormula is obtained. In addition, 3 bending strengths adopt and measure according to the method for JIS-R-1601. ItsResult is as shown in table 2.
Table 2
Shown by the result shown in above-mentioned each table 1～2: in the silicon nitride sinter of each embodiment,Vickers hardness (Hv) is more than 1500, Fracture Toughness (K1c) be 6.0MPam1/2Above, 3Point bending strength is more than 900MPa, can process coefficient Mc in 0.100～0.120 scope. DoFor the calculated example of Mc, the coefficient processed of embodiment 1 is hard with loading of pressing in Fn=20kgf, VickersDegree Hv=1592, Fracture Toughness K1c＝6.6MPa·m1/2, pass through Mc=209/8/(6.61/2·15925/8) value that calculates.
In addition, use the abradant surface of section, the peak value of having obtained each crystallization by XRD analysis is strongDegree ratio. Its result is as shown in table 3.
Table 3
Then, use the SEM photo of the abradant surface of section, obtain per unit area 100 μ m × 100 μ mThe Area Ratio of Grain-Boundary Phase. The Area Ratio of Grain-Boundary Phase has been measured 5 place's unit are 100 μ m × 100 μ m,Record its upper and lower bound. In addition, according to tem analysis, investigated in Grain-Boundary Phase and had or not " Hf-Y-OBased compound crystallization " and " Y-Al-O based compound amorphous phase ". Its result as described in Table 4.
Table 4
Shown by the result shown in above-mentioned table 4: in the silicon nitride sinter of each embodiment, Grain-Boundary PhaseArea Ratio in 25～40% scope.
(embodiment 1B～13B and comparative example 1B～2B)
With the manufacture method manufacture same with embodiment 1～13 and comparative example 1～2 as sliding componentBearing ball. Grinding and making the diameter of bearing ball is 9.525mm, surface roughness (Ra)Be 0.01 μ m.
About attrition process, preparation surface roughness (Ra) attrition process becomes the examination before 0.01 μ mMaterial, as test portion, has compared surface when use ciamond grinder (#120) carries out attrition processRoughness. About attrition process condition, make the working (finishing) area of test portion constant, load is set as to 40N,Be that 300rpm processes by the speed setting of grinding disc, measured and processed until do not showSurface roughness (Ra) after the time of the variation of surface roughness (Ra). By this attrition processCan measure threshing state. Threshing state and surface roughness have correlation, and numerical value is larger, meaningTaste and is more easily produced threshing, thereby it is contemplated that reliability in rolling life test is in reducingTendency.
In addition, measured the variation of roll life-span and the crushing strength before and after the life-span of rolling. EnteringWhen row rolls the measurement of life-span and crushing strength, use to have bearing ball surface grinding is processed intoSurface roughness (Ra) is the bearing ball of the polished surface of 0.01 μ m.
In addition, the life-span of rolling is the bearing ball of preparing 3 each embodiment, is being set in bearing steelThe diameter of SUJ2 upper surface is 3 above-mentioned bearing balls of the first-class arranged spaced of the track of 40mm. ?Under the bath lubrication condition of steam turbine oil, thereby make the Maximum Contact stress of 5.9GPa at imposed loadAct under the state of bearing ball, with under rotating speed 1200rpm until bearing ball surface shellFrom time measurement the rolling life-span. In addition, the measurement in rolling life-span is taking continuous 800 hours as the upper limitAnd carry out.
In addition, about the crushing strength before and after rolling test, the 2 ball crushing methods of employing are obtained bearing ballThere is the load of destroying. Its result is as shown in table 5.
Table 5
Shown by the result shown in above-mentioned table 5: the bearing ball of each embodiment demonstrate 700 hours withOn good sliding properties. Distinguish and particularly possessed the crystallization of Hf-Y-O based compound and interpolationMo2C, as the embodiment 1～6 of sintering aid, is still maintaining good spy after reaching 800 hoursProperty.
Bearing ball is that the whole surface of use sintered body is as the sliding component of sliding surface. Therefore,If as the characteristic good of bearing ball, be used in other sliding component, too performanceGo out good characteristic. Therefore, the silicon nitride sinter of embodiment goes for cunning miscellaneousMoving member.
In addition, be illustrated with regard to several embodiments of the present invention above, but these embodimentsPointed out as an example, it does not seek to limit scope of invention. The enforcement of these noveltiesMode can be implemented with other variety of way, not departing from the scope of invention main idea, and canCarry out various omissions, displacement and change. These embodiments and distortion thereof are included in the model of inventionEnclose with main idea in, and be included in the invention of recording in claims and be equal to the scope of displacementIn.
Utilizability in industry
According to silicon nitride sinter of the present invention and use the sliding component of this silicon nitride sinter,About sliding properties, can provide the silicon nitride sinter that can give long-term reliability. In addition,Can process coefficient owing to having adjusted, so even if carry out surface grinding processing, also owing to reducingThreshing, so easily obtain smooth sliding surface. Therefore, about the slip structure that uses this sintered bodyPart, also can obtain long-term reliability.
Symbol description:
1 bearing ball (silicon nitride sinter, sliding component)

Claims (13)

1. a silicon nitride sinter, is characterized in that: divide silicon nitride sinter is carried out to XRDWhile analysing, when locating corresponding to 29.6 ± 0.3 ° and 31.0 ± 0.3 ° of hexagonal crystal system α-SiAlON crystallizationThe highest peak value intensity detecting is set as I29.6°、I31.0°, on the other hand will be corresponding to β-Si3N4Knot33.6 ± 0.3 °, 36.1 ± 0.3 ° brilliant highest peak value intensity of locating to detect are set as I33.6°、I36.1°Time,Each highest peak value intensity meets following relational expression:
(I29.6°+I31.0°)/(I33.6°+I36.1°)＝0.10～0.30(1)
In the arbitrary cross-section of described silicon nitride sinter, the crystalline substance of per unit area 100 μ m × 100 μ mThe Area Ratio of boundary's phase is 25～40%, and can process coefficient is 0.100～0.120.
2. silicon nitride sinter according to claim 1, is characterized in that: to silicon nitrideWhen sintered body carries out XRD analysis, corresponding to Y4Si2O7N2Locate to detect for 39.5 ± 0.3 ° that are J phaseHighest peak value intensity I39.5°Meet following relational expression:
(I39.5°)/(I33.6°+I36.1°)＝0.03～0.10(2)。
3. silicon nitride sinter according to claim 1, is characterized in that: to silicon nitrideWhen sintered body carries out XRD analysis, corresponding to Y2Si3O12N is H phase, YSiO2N be K phase orY2Si3O3N4In any 31.9 ± 0.3 ° of above highest peak value intensity I of locating to detect31.9°FullFoot is stated relational expression:
(I31.9°)/(I33.6°+I36.1°)＝0.05～0.15(3)。
4. silicon nitride sinter according to claim 2, is characterized in that: to silicon nitrideWhen sintered body carries out XRD analysis, corresponding to Y2Si3O12N is H phase, YSiO2N be K phase orY2Si3O3N4In any 31.9 ± 0.3 ° of above highest peak value intensity I of locating to detect31.9°FullFoot is stated relational expression:
(I31.9°)/(I33.6°+I36.1°)＝0.05～0.15(3)。
5. according to the silicon nitride sinter described in any one in claim 1～4, it is characterized in that:XRD analysis carries out at the arbitrary cross-section of silicon nitride sinter.
6. according to the silicon nitride sinter described in any one in claim 1～4, it is characterized in that:Possesses the Grain-Boundary Phase of the amorphous phase that comprises the crystallization of Hf-Y-O based compound and contain Y-Al-O.
7. according to the silicon nitride sinter described in any one in claim 1～4, it is characterized in that:Possesses average grain diameter and is any the above grain in oxide below 2 μ m, carbide, nitrideSon.
8. silicon nitride sinter according to claim 7, is characterized in that: described particle isMolybdenum compound particle.
9. according to the silicon nitride sinter described in any one in claim 1～4, it is characterized in that:The Al that contains 5～10 quality % in oxide scaled value, contains 1～10 in oxide scaled valueMore than any in the rare earth element of quality %, contain 1～5 quality % in oxide scaled value4A, 5A, 6A element in any more than, and the mol of Al and rare earth element is than being A1﹕ rare earth element=1 ﹕ 1～8 ﹕ 1.
10. according to the silicon nitride sinter described in any one in claim 1～4, it is characterized in that:Vickers hardness Hv is more than 1500, Fracture Toughness K1CFor 6.0MPam1/2Above, and 3 pointsBending strength is more than 900MPa.
11. 1 kinds of sliding components, is characterized in that: it has used any one in claim 1～10Described silicon nitride sinter.
12. sliding components according to claim 11, is characterized in that: sliding component is axleHold ball.
13. according to the sliding component described in claim 11 or 12, it is characterized in that: sliding surfaceThat surface roughness Ra is the abradant surface below 0.5 μ m.
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