CN1249287A - Ceramic block gauge material and its making technology - Google Patents

Ceramic block gauge material and its making technology Download PDF

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Publication number
CN1249287A
CN1249287A CN 98112267 CN98112267A CN1249287A CN 1249287 A CN1249287 A CN 1249287A CN 98112267 CN98112267 CN 98112267 CN 98112267 A CN98112267 A CN 98112267A CN 1249287 A CN1249287 A CN 1249287A
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ceramic block
block gauge
sintering
stablizer
zro
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王钊
丁培道
余承杰
周泽华
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YULUN HIGH-TECHNOLOGY CERAMIC Co Ltd CHONGQING
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YULUN HIGH-TECHNOLOGY CERAMIC Co Ltd CHONGQING
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Abstract

A ceramic block gauge contains stabilizer (ZrO2 or Y2O3) or composite stabilizer (Y2O3 and MgO or Y2O3, MgO and CaO) and combustion improver containing one or more alkali-earth metal oxide or rare-earth metal oxide. It is prepared by modifying ordinary ceramic making technology in such areas that granulating more times, transverse-then-longitudinal pressing in cold pressing, and ordinary-pressure sintering in high-temp sintering kiln. Its advantages are high strength and antiwear nature, durable size stability, and high resistance aqainst oxidation, corrosion and electromagnetic interference.

Description

A kind of ceramic block gauge material and manufacture craft thereof
The present invention relates to a kind of standard metering material, particularly a kind of ceramic block gauge material and manufacture craft thereof.
Present slip gauge material adopts steel or steel alloy material usually, and not only manufacturing process is loaded down with trivial details for the steel slip gauge, and in use easy to wear, get rusty, cause the precise decreasing of slip gauge, shorten the defective of complicated maintenance work-ing life; Need pass through a series of processing such as forging, annealing, modified, quenching for the steel alloy material, labour intensity is big, and wherein heat treated waste liquid causes severe contamination to environment.
As everyone knows, zirconia ceramics have high-density, good toughness, nonmagnetic, wear resistance is high, thermal expansivity and the very approaching characteristics of metallic substance, it is contemplated that in view of the above it is an ideal material of making slip gauge.Abroad; Japan, the U.S. carried out research to ceramic block gauge; it mainly is to adopt Zirconia-alumina system's pottery or carbide ceramics; though their hardness height; but preparation is difficult, sintering temperature is high, and Zirconia-alumina system ceramic density is low, and the carbide ceramics sintering needs atmosphere protection; the cost height is not easy mass production.
The object of the present invention is to provide a kind of anticorrosive, the high-performance ceramic slip gauge material of anti-electro permanent magnetic and easy, free of contamination normal pressure manufacture craft thereof.
The present invention is achieved in that a kind of ceramic block gauge material, and it mainly contains ZrO 2, Y 2O 3Stablizer or Y 2O 3, the compound stablizer of MgO or Y 2O 3, the compound stablizer of CaO and the sintering agent that contains one or more alkaline earth metal oxides or rare-earth oxide at least.
Above-mentioned ZrO 2Material adopts be average particulate diameter less than 0.5 μ m, specific surface area is greater than 7m 2/ g based on four directions ZrO mutually 2, content is 95.0mol%-97.2mol%.The ZrO that the present invention is selected 2Be to have oblique side to exist mutually, a small amount of cube of phase can be arranged, if cube many mutually, the slip gauge bad mechanical strength that finally makes.
The content of aforementioned stable agent or compound stablizer is 2.8mol%-5.0mol%.
Above-mentioned sintering agent middle-weight rare earths metal oxide can be selected from following several compounds: La 2O 3, CeO 2, Gd 2O 3, Yb 2O 3, Lu 2O 3, Nb 2O 5, it adds to add form, and its addition is 0.1mol%-1.0mol%.
The manufacture craft of above-mentioned ceramic block gauge material, it comprises batch mixing applying glue-granulation-coldmoulding-binder removal-sintering, it is characterized in that: described granulating working procedure also promptly is no less than secondary granulation for granulation repeatedly; Laterally pressurization earlier, vertically pressurization again in the described coldmoulding operation; Described sintering circuit is carried out normal pressure segmentation short period of time heat preservation sintering in the high temperature sintering kiln.
Wherein said batch mixing applying glue operation is meant with distilled water or deionized water as dispersion medium, with the ZrO of average particulate diameter less than 0.5 μ m 2Powder, stablizer or compound stablizer, sintering agent is evenly mixed, drying; Add the poly (vinyl alcohol) binder of 1.5-3.0wt.% then, and adjust its pH value for neutral; Poly (vinyl alcohol) binder adds with aqueous solution form.The pH value of adjusting batch mixing in this operation is that neutrality is for the ease of granulation.
Described average particulate diameter is less than the ZrO of 0.5 μ m 2Powder, the acquisition of stablizer or compound stablizer are to adopt the chemical co-precipitation method preparation, also are about to ZrO 2Powder, stablizer or compound stablizer and ammoniacal liquor reaction form complex compound with co-precipitation, fully clean to solution PH=7-8 with distilled water, filter then, use the dehydrated alcohol absorbent drying, are sintered into ZrO at last 2/ Y 2O 3Cubic phase crystallization powder; It adopts mechanical wet ball-milling to mix with sintering agent is mixed.
The powder that wherein said repeatedly granulation is promptly sieved after the powder process granulation for the first time of batch mixing applying glue is 5-10KN/cm at pressure 2Under be pressed into bulk, and then pulverize, sieve, carry out secondary granulation; The moulding pressure of described coldmoulding operation is 18KN/cm 2-25KN/cm 2
Wherein said binder removal operation is meant 750 ℃ of the highest dump temperatures, and the binder removal time is 24-35 hour, and average heating speed is no more than 25 ℃/hour.
Wherein said sintering circuit is meant the firing mode that adopts the insulation of segmentation short period of time, and temperature-rise period is respectively 1150-1250 ℃, 1350-1450 ℃, 1580-1650 ℃, and soaking time was respectively 30 minutes, 40-60 minute, 1-3 hour; The high temperature sintering kiln is selected high temperature silicon molybdenum kiln for use.
The present invention adopts based on four directions ZrO mutually 2Be main raw material, add the Y of certain content 2O 3Stablizer or Y 2O 3, the compound stablizer of MgO or Y 2O 3, the compound stablizer of MgO, CaO, make the thermal expansivity of ceramic block gauge similar to the thermal expansivity of metallic substance; The present invention adds sintering agent in order to improve its characteristic, improves ceramic smooth finish, acceleration of sintering.
The inventor uses three-point bending method, the bending strength that records the ceramic block gauge that makes according to technology of the present invention on the WE-5 universal testing machine is 798MPa, and the bending strength of hard alloy steel is usually in the 100-200MPa scope, and visible this ceramic block gauge material is than common hard alloy blocks gauge material intensity height; The inventor also once compared GCr15 steel alloy and the ceramic block gauge material of using as metal gauge of the present invention, deposited naturally simultaneously, after three months, surveyed its dimensional change, and the steel alloy dimensional change can reach 60 μ m/100mm, and ZrO 2The pottery gauge size is very stable; And ZrO 2The wear resistance of ceramic block gauge is 4-5 a times of WC Wimet gauge; It is anti-oxidant and resistance to corrosion is also strong, and especially anti-electromagnetic performance aspect has more distinctive feature, and in a word, it is the ideal material of linear measure measurer.
This ceramic block gauge manufacture craft is improved at conventional ceramic preparation technology's committed step and proposed: in the base of colding pressing the repeatedly granulation of row of advancing, different order numbers sieve, and are to guarantee quality product, particularly make the slip gauge sintered density greater than 6.00g/cm 2One of gordian technique, because repeatedly granulation, between the granulation of front and back, become big part base substrate in axial pressure with lower pressure, smash the powder that granulation once more and different meshes sieve then to pieces and have spheroid form, good flowability is arranged, and on size, have differential, mean particle size is between the 0.5-1.0mm, fill up all corners of mould in the time of can making the powder moulding like this, can interiorly to greatest extent get rid of gas, guarantee that the blank density after the coldmoulding reaches more than 50% of theoretical density; Pressing direction carries out special setting laterally pressurization earlier in the cold pressing forming process, after vertically pressurization, can guarantee that base substrate is stressed evenly; Adopt segmentation short period of time heat preservation sintering mode, can suitably reduce crystal boundary and crystal grain translational speed in the sintering process, help gas purging in the base substrate, improve sintered density, do not need complicated hot pressing or gas pressure sintering like this, just can make the ceramic body density behind the sintering be not less than 6.00g/cm 2, reach as high as 6.10g/cm 2Fine and close ceramic block gauge material uniformly, again through mach grinding, have fabulous surface smoothness after refining, color and luster is evenly pure white.What deserves to be mentioned is that this ceramic block gauge size can do greatlyyer, also form easily and produce in batches that cost is lower than metal slip gauge.In a word, this preparation technology is easy, can directly burn till in atmosphere, condition of normal pressure, does not need the special atmosphere protection just can obtain fine and close ceramic block gauge material.
Below in conjunction with drawings and Examples the present invention and effect thereof are further described:
Fig. 1: ceramic block gauge material manufacture craft schema of the present invention;
Fig. 2: the binder removal graphic representation of ceramic body of the present invention;
Fig. 3: the sintering curve figure of ceramic block gauge material of the present invention;
Fig. 4: main material is Zr 2O 3/ 2.5Y 2O 3Thermal expansion TMA graphic representation, be used to illustrate main material Zr 2O 3/ 2.5Y 2O 3Thermal expansivity;
Fig. 5: main material is Zr 2O 3/ 5Y 2O 3Thermal expansion TMA graphic representation, be used to illustrate main material Zr 2O 3/ 4Y 2O 3Thermal expansivity;
Fig. 6: main material is Zr 2O 3/ 2.5Y 2O 3The X-ray diffraction XRD figure, be used to illustrate main material Zr 2O 3/ 2.5Y 2O 3Phase structure;
Fig. 7: main material is Zr 2O 3/ 5Y 2O 3The X-ray diffraction XRD figure, be used to illustrate main material Zr 2O 3/ 5Y 2O 3Phase structure;
Fig. 8: the average grain granularity of the used zirconia material of the present invention and the distribution figure of particle size;
Fig. 9: the thermal process of zirconia ceramics base substrate is reacted the DTA graphic representation, is used to illustrate the crossing situation of zirconia ceramics.
Embodiment 1: with 95.5Zr 2O 3/ 3Y 2O 3+ 1.5MgO+0.5La 2O 3Be example, the invention will be further described referring to process flow sheet shown in Figure 1:
1. batch mixing applying glue operation:
(1): the preparation of raw material, mixing:
Raw material 95.5ZrO 2/ 3Y 2O 3Be to adopt the chemical co-precipitation method preparation; MgO is an admixture, and it is with MgCl 26H 2The O mode is introduced; Sintering agent is selected La for use 2O 3, adopt the form that adds to add.
95.5ZrO wherein 2/ 3Y 2O 3The primary process of preparation is: with purity greater than 99% starting materials ZrOCl 2/ YCl 3With ammoniacal liquor reaction, form complex compound with co-precipitation, with distilled water fully clean to the solution pH value be 7-8, filter then, filter residue dehydrated alcohol absorbent drying is sintered into ZrO at last 2/ Y 2O 3Cubic phase crystallization powder.The powder that obtains is through the particle size of LA-910 type laser particle analysis-e/or determining compound, and its mean particle size meets through the impurity atom analysis: Na less than 0.5 μ m 2O＜0.01%, CaO＜0.01%, Al 2O 3＜0.02%, SiO 2＜0.02%, other impurity should be less than 0.001%.
Sintering agent La 2O 3Purity is greater than 99.9%, and the powder mean particle size is less than 0.5 μ m, and foreign matter content requires identical with the stabilizing zirconia material, and addition is 0.5mol%.
With 95.5molZrO 2/ 3molY 2O 3And 1.5molMgCl 26H 2O powder and 0.5molLa 2O 3Mix with mechanical process (ball milling).Do dispersion medium with distilled water, in material: ball: the ratio of water=1: 2: 1, wet ball-milling 12 hours mixes.
(2): drying:
Mix finish after, with slip by 100 mesh sieves, then in hot air drier, under 120 ℃ of temperature, dry.
(3): calcining:
To dry compound and slightly pulverize, the high purity aluminium oxide crucible of packing into, (Al by 60 mesh sieves 2O 3Content is greater than 99%), in the cabinet-type electric furnace of sealing type of heating, 850 ℃ of sintering 2 hours.The intensification condition: insulation is 1 hour after the room temperature to 500 ℃, continues to be warming up to 850 ℃ of insulations 2 hours, cools to room temperature then with the furnace.Every section all heats up with 250 ℃/speed at one hour rating.
(4): wet ball-milling mixes:
Therefore powder after the calcining presents pure white color lump body, needs wet-milling again, and dispersion medium is still used distilled water, by expecting: ball: the ball grinder fine grinding 20 hours of packing into of the ratio of water=1: 3: 0.8.Ball milling finishes slip is passed through 100 mesh sieves, follows in hot air drier, dries under 120 ℃ of temperature, powder is pulverized by 80 mesh sieves again.
(5) applying glue
The above-mentioned powder that sieves is regulated its pH value near neutral with the 2N water acetic acid aqueous solution, add 1-2wt.% usually and can reach requirement.Then adding the PVA aqueous solution that polyvinyl alcohol content is 1.5-3.0wt.% lentamente, also is that PVA aqueous solution add-on is the heavy 15wt.% of dry mash.
2. granulating working procedure:
When adding PVA solution, to constantly stir, roll the stranding granulation.In order to guarantee that blank density reaches more than 50% of theoretical value, after rolling for the first time the stranding granulation, earlier with lower pressure 10KN/cm 2Add at axial direction due and to be pressed into big part base substrate, smash granulation once more then to pieces, before producing moulding in batches, the granulation powder was mixed on ball mill 10-20 minute, in order to the acquisition spherical particles.
After the granulation, sieve by 40 orders, 60 orders, 80 mesh sieves respectively, it is differential to make it have a particle.
3. coldmoulding operation:
Base substrate is coldmoulding on side compression machine, laterally pressurization earlier, and vertically pressurization then, stressed evenly to guarantee base substrate.
Moulding should be to place more than 12 hours in physical environment with powder, and the moisture content of powder is between 2-3%.Blank forming pressure is selected 25KN/cm 2, pressing blank is checked on the quality with simple microscope, comprises surface contamination, peripheral integrity, has or not defectives such as zig-zag burr, layering and crackle.Last rough calculation blank density should reach more than 50% of theoretical density.
4. binder removal operation:
Base substrate after the compacting is placed more than 10 hours under field conditions (factors), carries out binder removal then, promptly gets rid of the intravital PVA of base, improves the base substrate physical strength simultaneously.The heating curve of binder removal technology as shown in Figure 2, whole process need more than 30 hour, 750 ℃ of the highest dump temperatures, the average heating speed of whole process are 25 ℃/hour.
The binder removal curve of this technology is to arrange according to thermal process response curve DTA shown in Figure 9, only in this way just can prevent the ceramic block gauge blank cracking, improves sintered density.
5. firing process:
Because the basic demand of ceramic block gauge is that sintered density reaches 6.00g/cm 2More than, the material crystals structure behind the sintering should be the cubic phase near 100%, or four directions and a small amount of cube of microtexture that coexists mutually; The open porosity that requires porcelain spare is zero, and closed porosity is controlled at below 3/1000ths, therefore in the base substrate sintering process, prevent that pore is absorbed within the crystal grain and secondary recrystallization occurs, take the firing mode of the segmentation short period of time insulation shown in Fig. 3 sintering curve, at 1200 ℃, 1400 ℃, 1650 ℃, soaking time is respectively 30min, 60min, 60min respectively for 1650 ℃ of maximum sintering temperatures, temperature-rise period.
In order to prevent of the pollution of each volatilization gas of high temperature, to feed an amount of oxygen when burning till to material.When producing larger-size slip gauge, should be after process of cooling will be controlled cooling rate, burn till with 30 ℃/hour speed cooling, be cooled to 1000 ℃ after powered-downs, furnace cooling is then reduced to below 150 ℃ when temperature and can be taken out product.
6. grinding and cutting, precision work, performance test:
Burn till the base substrate that finishes, after surface grinding, polished finish, carry out following several measuring physical properties:
A: surface observation, with LIETZ powerful microscope master meter plane defect, pollution and pore situation.
B: with Archimeder drainage bulk density.
C: measure hardness, loading 20KN, 20 seconds loading time with the AVK-CL Vickers hardness tester.
D: adopt pressing in method to measure fracture toughness property, load 20KN, 20 seconds hold-times, use following formula calculating K 1c value:
K 1c＝0.113Hv 1/2(1+a/2c) -3/2
Wherein: Hv-Vickers' hardness (GDP)
C-impression catercorner length
The a-crack length
E: with the TMA curve of Dn.pont 200 type thermal analyzers mensuration material, 10 ℃/min of rate of heating.
F: measure crystalline structure with xrd method.
Through the ceramic block gauge base substrate of above-mentioned explained hereafter, it is as follows to record performance index:
Density: 6.01-6.05g/cm 2
Hardness (HV): 12-14Gpa
Fracture toughness property (K 1c): 7-8Mpam 1/2
Thermal expansivity line (room temperature-200 ℃): 8.5 ± 1.0 * 10 -6/ ℃
Crystalline phase: based on the four directions mutually, its scope is at 90-95%.
Embodiment 2-3 verifies Y 2O 3The mean particle size of powder is to ZrO 2The influence of ceramic performance: with reference to embodiment 1 described processing step, Y 2O 3Choose mean particle size and be 0.5 μ m and greater than the powder of 1.0 μ m, with the La of 0.5mol% 2O 3As sintering agent, make ceramic block gauge respectively, and test its performance must table 1:
Material ?Y 2O 3Mean particle size (μ m Moulding pressure (KN/cm 2) Blank density (g/cm 2) Sintering temperature (℃) Density (g/cm 2) Hardness Hv (GPa) Toughness K1c (Mpam 1/2)
??2：ZrO 2/4Y 2O 3 ??0.5 ?????25 ???3.29 ????1600 ?????6.05 ????14.54 ????6.52
??3：ZrO 2/4Y 2O 3 Greater than 1.0 ?????26 ???3.28 ????1600 ?????5.97 ????13.75 ????6.13
As known from Table 1: the average grain as stablizer also is one of important measures that guarantee the ceramic block gauge good characteristic less than 0.5 μ m.
Embodiment 4-11:
From Fig. 6 and Fig. 7 as can be seen: Y 2O 3To ZrO 2The crystal phase structure of material is influential.Fig. 6 main material is Zr 2O 3/ 2.5Y 2O 3The X-ray diffraction XRD figure in the X diffraction peak find out: when stabiliser content is 2.5mol%, main material Zr 2O 3Except also there is oblique side's phase in the four directions mutually; Fig. 7 main material is Zr 2O 3/ 5Y 2O 3The X-ray diffraction XRD figure in the X diffraction peak in find out: when stabiliser content is 5.0mol%, main material Zr 2O 3Do not have almost tiltedly that the side occurs mutually, therefore, in the time of can inferring that tentatively stabiliser content is between 2.5mol%-5.0mol%, obtain the ceramic block gauge dimensional stabilizing, sintered density height, good mechanical performance.
It can also be seen that from the TMA curve of Fig. 4 and Fig. 5: Y 2O 3Content to ZrO 2α is influential for the ceramic block gauge linear expansivity, according to curve, and adopts following equation:
α＝(L t-L rt)/L rt×(1/ΔT)
The sample length that Lt, Lrt are respectively when being heated to T degree and room temperature in the formula obtains consisting of ZrO 2/ 2.5Y 2O 3The α of material Rt-200 ℃=6.75 * 10 -6/ ℃, consist of ZrO 2/ 4Y 2O 3The α of material=7.91 * 10 -6/ ℃.Illustrate and change Y 2O 3Addition can realize adjusting the purpose of linear expansivity α, be complementary thereby the thermal expansivity of ceramic block gauge is reached with measured material as far as possible.
For the addition that confirms stablizer or one package stabilizer is the best in 2.8mol%-5.0mol%.Prepare following sample with reference to embodiment 1 described technology and testing method, to its performance test table 2: table 2:
Sequence number Sample is formed (mol%) Density d (g/cm 3) Hardness Hv (Gpa) Toughness K1c (Mpam 1/2) Linear expansivity α line (* 10 -6/℃) Sintering temperature T (℃)
??ZrO 2 ??Y 2O 3 ???MgO ??CaO ??La 2O 3
??4 ??97.2 ??2.8 ???/ ??/ ???/ ????6.09 ??12.4 ?????6.64 ???????8.5 ????1650
??5 ??97.5 ??2.5 ???0.2 ??/ ???/ ????5.78 ??11.75 ?????7.1 ???????- ????1600
??6 ??97.0 ??3.0 ???0.2 ??/ ???/ ????6.07 ??14.17 ?????5.79 ???????6.6 ????1580
??7 ??97.0 ??3.0 ???0.2 ??/ ???0.1 ????6.08 ??15.46 ?????6.00 ???????- ????1600
??8 ??96.0 ??4.0 ???0.2 ??/ ???0.1 ????6.04 ??14.54 ?????6.50 ???????7.5 ????1580
??9 ??96.0 ??4.0 ???0.2 ??/ ???0.0 ????6.00 ??13.75 ?????6.13 ???????- ????1600
??10 ??95.0 ??5.0 ???0.2 ??/ ???/ ????5.96 ??14.48 ?????5.55 ???????7.9 ????1600
??11 ??97.0 ??3.0 ???/ ??1.0 ???/ ????6.01 ??11.78 ?????6.83 ???????- ????1650
Embodiment 12-20: must select for use sintering agent and sintering agent in multiple oxide compound, to select for the present invention is described, with reference to embodiment 1 described processing step and performance test methods, select for use the listed sintering agent of following table to prepare ceramic block gauge, and its performance tested, test result sees Table 3:
Sequence number Main material (mol%) Sintering agent Performance perameter
??ZrO 2 ????Y 2O 3 Composition Content mol% Density (g/cm 3) Vickers' hardness (Gpa) Fracture toughness property (Mpa.m 1/2
??12 ??95.0 ????5.0 ????0 ?????5.96 ?????12.0 ???????6.50
??13 ??95.5 ????4.5 ??MgO ????0.5 ?????6.02 ?????12.58 ???????6.74
??14 ??95.5 ????4.5 ??La 2O 3 ????0.5 ?????6.08 ?????12.59 ???????7.03
??15 ??95.5 ????4.5 ??CeO 2 ????0.5 ?????6.02 ?????13.83 ???????6.11
??16 ??95.5 ????4.5 ??Nb 2O 5 ????0.5 ?????6.06 ?????12.90 ???????6.43
??17 ??96.0 ????4.0 ??MgO ????0.2 ?????5.99 ?????12.48 ???????5.92
??18 ??96.0 ????4.0 ??MgO ????1.0 ?????6.01 ?????12.50 ???????5.92
??19 ??95.5 ????4.5 ??MgO ??Nb 2O 5 ????0.2 ????0.5 ?????6.06 ?????13.0 ???????6.40
??20 ??96.0 ????4.0 ??MgO ??La 2O 3 ????0.1 ????0.3 ?????6.04 ?????12.60 ???????6.50
Embodiment 21-26: in order to confirm the influence of granulating working procedure to blank density, starting material are all selected ZrO for use 2/ 4Y 2O 3+ 0.5MgO with reference to embodiment 1 described processing step, prepares following six samples respectively, all its blank density is tested after each granulation, and test result sees Table 4:
Sequence number A granulation blank density The secondary granulation blank density
??21 ????????2.89 ???????3.11
??22 ????????2.84 ???????3.27
??23 ????????2.75 ???????3.06
??24 ????????2.76 ???????3.13
??25 ????????2.75 ???????3.06
??26 ????????2.78 ???????3.14
If will guarantee that pressing blank density reaches the theoretical density of 50-55%, the compacting powder must carry out secondary granulation.The powder of a granulation is difficult to reach the density more than 50% in pressing process, when improving pressing pressure, though the blank density after the compacting can reach＞50% densification, base substrate is easy to generate tiny crack, causes the product behind the sintering crackle or fracture to occur.As can be known from Table 4, (20KN/cm under the not high situation of pressure 2), the powder behind secondary granulation has all reached＞density of 50% theoretical density.
Embodiment 27-31: in order to confirm that forming pressure is to the influence of blank density in the processing step, starting material are all selected ZrO for use 2/ 4Y 2O 3+ 0.5MgO with reference to embodiment 1 described processing step, only changes forming pressure and prepares ceramic block gauge, and to its performance test table 5:
Sequence number Moulding pressure (KN/cm 2) Blank density (g/cm 2)
??27 ???????15.5 ???????2.87
??28 ???????18.0 ???????2.97
??29 ???????25.0 ???????3.05
??30 ???????29.4 ???????3.11
??31 ???????38.6 ???????3.21
As known from Table 5: forming pressure is little, and blank density is low, and lower blank density can make ceramic block gauge spare density descend; Forming pressure is big, blank density height, but hypertonia, and the easy layering of base substrate or cause release to move back the mould difficulty, therefore when pressing blank, shaping pressure should be got 18-25KN/cm 2
In fact, the contriver adopted preparation technology of the present invention to carry out small serial production (material consists of ZrO2/5Y 2O 3+ 0.2MgO) and obtained use, in these products, carry out sampling Detection, detected result sees Table 6:
Sample number Density (g/cm 2) Hardness Hv (Gpa) Toughness K1c (Mpam 1/2) 1/ ℃ of thermal expansivity
???1 ?????6.04 ?????12.12 ????????7.12 ????8.1×10 -6
???2 ?????6.00 ?????12.37 ????????7.32 ????8.1×10 -6
???3 ?????6.00 ?????12.14 ????????7.27 ????8.1×10 -6
???4 ?????5.99 ?????12.55 ????????7.98 ????8.1×10 -6
???5 ?????6.02 ?????12.29 ????????7.52 ????8.1×10 -6
???6 ?????6.02 ?????12.19 ????????6.90 ????8.1×10 -6
From the data that table 6 lists as can be seen: the product that adopts preparation technology of the present invention to make has satisfied the requirement that slip gauge is used, has proved absolutely its practicality.
In order to illustrate that this preparation technology has outstanding substantive distinguishing features and obvious improvement, be the ceramic block gauge sample that adopts general ceramic process preparation below, its performance to be tested, test result sees Table 7:
Material is formed ??ZrO 2/2.5Y 2O 3??+0.8MgO ??ZrO 2/2.5Y 2O 3??+1.0MgO ??ZrO 2/3Y 2O 3??+0.8MgO ??ZrO 2/4Y 2O 3??+1.0MgO
Firing temperature (℃) ??1600 ??1600 ??1580 ??1650
Density (g/cm 3) ??5.89 ??5.78 ??5.98 ??5.96
Vickers' hardness (Gpa) ??9.25 ??11.75 ??11.01 ??11.48
Fracture toughness property (Mpa.m 1/2) ??6.12 ??- ??5.71 ??5.92
Apparent from table 7: adopting the ceramic block gauge performance of general ceramic process preparation, is the requirement that does not reach the slip gauge product, and by the contrast of table 6 with table 7 data, it is creative to further illustrate preparation technology of the present invention.

Claims (10)

1. ceramic block gauge material, it is characterized in that: it mainly contains ZrO 2, Y 2O 3Stablizer or Y 2O 3, the compound stablizer of MgO or Y 2O 3, the compound stablizer of CaO and the sintering agent that contains one or more alkaline earth metal oxides or rare-earth oxide at least.
2. ceramic block gauge material as claimed in claim 1 is characterized in that: described ZrO 2Material adopts be average particulate diameter less than 0.5 μ m, specific surface area is greater than 7m 2The four directions of/g is main ZrO mutually 2, its content is 95mol%-97.2mol%.
3. ceramic block gauge material as claimed in claim 1 is characterized in that: the content of described stablizer or compound stablizer is 2.8mol%-5.0mol%.
4. ceramic block gauge material as claimed in claim 1 is characterized in that: described sintering agent middle-weight rare earths metal oxide can be selected from following several compounds: La 2O 3, CeO 2, Gd 2O 3, Yh 2O 3, Lu 2O 3, Nb 2O 5, it adds to add form, and its addition is 0.1mol%-1.0mol%.
5. the manufacture craft of ceramic block gauge material as claimed in claim 1, it comprises batch mixing applying glue-granulation-coldmoulding-binder removal-sintering, it is characterized in that: described granulating working procedure also promptly is no less than secondary granulation for granulation repeatedly; Laterally pressurization earlier, vertically pressurization again in the described coldmoulding operation; Described sintering circuit is carried out normal pressure segmentation short period of time heat preservation sintering in the high temperature sintering kiln.
6. the manufacture craft of ceramic block gauge material as claimed in claim 5 is characterized in that: described batch mixing applying glue operation is meant with distilled water or deionized water as dispersion medium, with the ZrO of average particulate diameter less than 0.5 μ m 2Powder, stablizer or compound stablizer, sintering agent is evenly mixed, and dry back adds the poly (vinyl alcohol) binder of 1.5-3.0wt.%, and adjusts its pH value for neutral; Poly (vinyl alcohol) binder adds with aqueous solution form.
7. the manufacture craft of ceramic block gauge material as claimed in claim 6, it is characterized in that: described average particulate diameter is less than the ZrO of 0.5 μ m 2Powder, the acquisition of stablizer or compound stablizer are to adopt the chemical co-precipitation method preparation, also are about to ZrOCl 2With YCl 3Powder and ammoniacal liquor reaction form complex compound with co-precipitation, fully clean to solution PH=7-8 with distilled water, filter then, use the dehydrated alcohol absorbent drying, are sintered into ZrO at last 2/ Y 2O 3Cubic phase crystallization powder; They adopt mechanical wet ball-milling to mix with sintering agent is mixed.
8. the manufacture craft of ceramic block gauge material as claimed in claim 5 is characterized in that: the powder of 80 mesh sieves is promptly crossed in described repeatedly granulation after the powder of batch mixing applying glue is through granulation for the first time, at low pressure 5-10KN/cm 2Axial briquetting shape, and then pulverizing down sieves, and carries out secondary granulation; The moulding pressure 18KN/cm of described coldmoulding operation 2-25KN/cm 2
9. the manufacture craft of ceramic block gauge material as claimed in claim 5, it is characterized in that: described binder removal operation is meant 750 ℃ of the highest dump temperatures, and the binder removal time is 24-35 hour, and average heating speed is for being not less than 25 ℃/hour.
10. the manufacture craft of ceramic block gauge material as claimed in claim 5, it is characterized in that: described sintering circuit is to adopt the firing mode of segmentation short period of time insulation, temperature-rise period is respectively 1150 ℃-1250 ℃, 1350 ℃-1450 ℃, 1580 ℃-1650 ℃, and soaking time was respectively 30 minutes, 40-60 minute, 60-180 minute.
CN 98112267 1998-09-25 1998-09-25 Ceramic block gauge material and its making technology Pending CN1249287A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993243A (en) * 2009-08-12 2011-03-30 株式会社村田制作所 Dielectric ceramic and method for producing dielectric ceramic and laminated ceramic capacitor
CN102803181A (en) * 2009-12-24 2012-11-28 法商圣高拜欧洲实验及研究中心 Powder comprising zirconia granules
CN104619933A (en) * 2012-07-11 2015-05-13 科森蒂诺研究与开发有限公司 Method for the production of solid surfaces for construction
CN105130429A (en) * 2015-07-30 2015-12-09 重庆卓田齿克科技有限公司 Zirconia ceramic block production technology
CN108503356A (en) * 2018-05-22 2018-09-07 中国原子能科学研究院 A kind of zirconia oxygen analyzer zirconium pipe and preparation method thereof
CN109503185A (en) * 2018-11-14 2019-03-22 安徽致磨新材料科技有限公司 The zirconia ceramics material of nano aluminium oxide toughening enhancing and products thereof forming method
CN111825449A (en) * 2020-07-29 2020-10-27 雅安远创陶瓷有限责任公司 Preparation process of zirconia ceramic block gauge
CN112552042A (en) * 2019-09-25 2021-03-26 比亚迪股份有限公司 Zirconia ceramic and preparation method and application thereof
CN116768620A (en) * 2023-06-05 2023-09-19 长江师范学院 Steel slag erosion resistant sizing nozzle and preparation method and application thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993243A (en) * 2009-08-12 2011-03-30 株式会社村田制作所 Dielectric ceramic and method for producing dielectric ceramic and laminated ceramic capacitor
CN101993243B (en) * 2009-08-12 2013-02-20 株式会社村田制作所 Dielectric ceramic and method for producing dielectric ceramic and laminated ceramic capacitor
CN102803181A (en) * 2009-12-24 2012-11-28 法商圣高拜欧洲实验及研究中心 Powder comprising zirconia granules
CN102803181B (en) * 2009-12-24 2014-11-12 法商圣高拜欧洲实验及研究中心 Powder comprising zirconia granules
CN104619933A (en) * 2012-07-11 2015-05-13 科森蒂诺研究与开发有限公司 Method for the production of solid surfaces for construction
CN105130429A (en) * 2015-07-30 2015-12-09 重庆卓田齿克科技有限公司 Zirconia ceramic block production technology
CN108503356A (en) * 2018-05-22 2018-09-07 中国原子能科学研究院 A kind of zirconia oxygen analyzer zirconium pipe and preparation method thereof
CN109503185A (en) * 2018-11-14 2019-03-22 安徽致磨新材料科技有限公司 The zirconia ceramics material of nano aluminium oxide toughening enhancing and products thereof forming method
CN112552042A (en) * 2019-09-25 2021-03-26 比亚迪股份有限公司 Zirconia ceramic and preparation method and application thereof
CN111825449A (en) * 2020-07-29 2020-10-27 雅安远创陶瓷有限责任公司 Preparation process of zirconia ceramic block gauge
CN116768620A (en) * 2023-06-05 2023-09-19 长江师范学院 Steel slag erosion resistant sizing nozzle and preparation method and application thereof
CN116768620B (en) * 2023-06-05 2024-06-07 长江师范学院 Steel slag erosion resistant sizing nozzle and preparation method and application thereof

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