CN1123413C - Method for making refractory zirconia stem bar - Google Patents
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- CN1123413C CN1123413C CN 00100878 CN00100878A CN1123413C CN 1123413 C CN1123413 C CN 1123413C CN 00100878 CN00100878 CN 00100878 CN 00100878 A CN00100878 A CN 00100878A CN 1123413 C CN1123413 C CN 1123413C
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Abstract
The present invention relates to a method for making a refractory zirconia stem bar and particularly a refractory stem bar obtained by a mixing step, an ejection forming step, a solvent degreasing step, a hot degreasing step and a sintering step. In the mixing step of the present invention, zirconia powder, paraffin wax (PW), magnesium stearate (SAM) and magnesia powder are respectively added step by step in batches at certain times, and the zirconia powder and polypropylene (PP) are added so as to obtain an ejection raw material; the present invention enables the refractory stem bar to have the advantages of precise size, complicated shape, uniform pore space and density, low making cost, and preferable resistance to hot cracking and molten steel erosion.
Description
Technical field
The present invention is a kind of method for making of fire-resistant stem bar, is meant a kind of method for making of refractory zirconia stem bar especially.
Background technology
Press the new technology of ceramic powders injection molding (Ceramic Injcction Molding) in conjunction with ceramic last processing procedure and plastic cement shaping, nearest 15 years just in advanced country, the frontier of national developments such as U.S., day, moral (be seen in as " Powder Injection Molding; " R.M.German Metal PowderIndustries Federation, (1990) Priceton NJ), be used for making:
1. hard-to-machine material, for example, pottery, Jie's metal material;
2. complex-shaped;
3. size Control strictness (＜0.3%), injection part have nearly clean shape (near-net-shape) characteristic;
4. hole and micro-structural are even;
5. quantity big (single gauge＞10,000); And
6. surface smoothing, the element that apparent weight is wanted.
Compared to other ceramic processing method, casting, dry pressing and coldly all be pressed into shape, " powder injection molding " technology is being good than other processing procedures aspect component size precision, volume production possibility, complex-shaped property and the density uniformity etc. four.
And ceramic injection molding processing procedure comprises the following steps: mixing and granulation, ejaculation, degreasing, five steps of sintering, at first be with macromolecule carrier plastics [polypropylene (polypropylene for example, P P) or polyethylene (Polyethylene, P E)] mix with ceramic powder, mixing in the above temperature of the melting point of plastics.For the mixed effect that improves compound and follow-up processing characteristics, need to add interfacial agents (Interfacial Agent) and plasticiser (Plasticizer) usually, to improve the productive rate that penetrates finished product.Now is with compound granulation (Granulation), in the feeding ejaculator, the temperature of pressure, injection material is penetrated in control, and parameters such as pressure time are held in ejaculation, can penetrate the green compact body that forms pottery/plastics in mould, its shape or size are similar to commercially available plastic cement finished product at present, and only these green compact contain up to the ceramic powder particle more than the 50vol%, therefore on the characteristic that penetrates rheology, the ejaculation of pottery and the ejaculation of its plastics are far from it.
Ceramic green body is before high temperature sintering, want earlier high molecule plastic to be removed, the method of removing has two kinds of hot degreasing (Thermal Debinding) and solvent degreasings (Solvent Dedinding) at present, and the defatting technology that is developing in addition has " vacuum degreasing method " to reach " supercritical liq degreasing method ".The programming rate that hot degreasing is used is everlasting 1-2 ℃/hour, and therefore required degreasing time often reaches 40-120 hour, and thickness of sample needs less than five centimetres, to avoid producing in the skimming processes defective in bubble, crack.In order to improve degreasing efficient, reduce degreasing time, just began development " solvent degreasing method " in nearly ten years, this kind method is to use the solvent of solvable high molecule plastic, as acetone, alkanes, green compact sample is immersed, remove most of low-molecular-weight plastics earlier, and make and produce suitable micropore in the sample that implement hot degreasing again, whole degreasing time can shorten more than 3/4.The technology of fast defat is the key technology that is developing at present.
For the ceramic body that reaches after the degreasing has even and fine hole, in follow-up sintering process, guarantee the rerum natura homogeneous of sintered body, before and after penetrating, have at least 14 essential factors to note.So, good injection molding process is added quick, intact degreasing and sintering process, is only the committed step that guarantees the ceramic product quality.Because the size Control of injection molding finished product and reappearance be good (industrial boundary treaty can reach 6/1000ths size reappearance) quite, the assembly mechanical lapping processing capacity after burning till is few, and processing cost can reduce, and its product price has competitiveness.
The aspect zirconia is because high-melting-point (m in addition
p=about 2700 ℃), low-heat passes, and the characteristic that corrodes of anti-molten steel, as far back as the fifties just with being the refractory material of iron and steel processing procedure, but its use amount many far away from its raw ore zircon (Zircon).Nearly 15 years, because zirconia reaches the research of " abnormal mutually " and obtains important breakthrough at " crystalline phase is stable ", zirconic intensity, toughness are significantly promoted, in structural ceramics (Structural Ceramics) application of room temperature, obtain certainly, therefore past twenty year (after 1978) are come, and the every industry and the people's livelihood are used successively and launched.
Pure zirconia is the structure of a cube (Cubic, C phase) more than 2400 ℃ the time.In the time of 2370 ℃, there is an abnormal mutually reaction, change square (Tetragonal, T phase) structure into by cube structure.When temperature is lower, there is another phase allergy to take place at 950 ℃, form trapezoid body (Monoclinic, M phase) structure, can follow this moment the expansion of outstanding volume about 6% to 7%, and might cause the crack or cause the pulverizing of workpiece.(saw E.C.Subbarao since 1975, " Zirconia-An Overview; " in Advances in Ceramics, Vol.3, Science andTechnology of Zirconia, ed.by 3.A.H.Heuer and L.W.Hobbs (1981) pp.1-24), Garvie is at first at calcium oxide-zirconia (CaO-ZrO
2) metasystem in, find that regular crystal zirconia phase (T phase) is to the diffusing phase transformation (MartensiticTransformation) in the numb field of monoclinic zirconia phase (M phase), after can obviously improving the destruction toughness (Fractre Toughness) of ceramic material, this material just causes extensive studies and application.
Common zirconia material is divided into into four classes, be respectively PSZ (Partial Stabilixed Zirconia), TZP (Tetragonal Zirconia Polycrystalline), FSZ (Fully Stabilized Zirconia) and ZTC (Zirconia Toughened Ceramlcs).By the interpolation (for example magnesia) of phase stabiliser, we can make zirconic high temperature phase (C phase) remain into room temperature or lower temperature, but its strength and toughness is still very poor, and are not extensive on using.If add a spot of stabilizing agent, make when zirconia forms the state of partly stable (PSZ), that is by the heat treated process of control, separate out some T phases at C in mutually, form the zirconia ceramics that a two-phase is mixed.Its strength and toughness of zirconia workpiece of this kind bipolar mixture all than one-component ceramic come good, and 1420 ℃ of heat treatments that surpass two hours, it is excessive that T grows up mutually, the idiopathic M phase that transfers to, when the M that generates surpasses 25% mutually, its toughness is by 9Mpam
1/2Drop to general value 4Mpam
1/2See also W.J.Buykx and M V.Swain, " ThermalDiffilsivity ot Zirconia Partially and Fully Stabilized with Magnesia; " inAdvances in Ceramics Vol.12, Science and Technology of Zirconia II, ed.byN.Claussen and M.Ruhel (1984) pp.518-527 document.
The thermal shock resistance of Mg-PSZ is best in the zirconia material, R.C.Gravie for example, " Structure Application of ZrO
2-Bending Materials; " in Advances in CeramicsVol.12, Scicnce and Technology of Zirconia II, the record of ed.by N.Claussen and M.Ruhel (1984) pp.465-479 document, Garvie was once measured to the initial strength (holding warm different time at 1100 ℃) of this material and through the retained strength of thermal shock, the heat treatment of discovery in eight hours can obtain best breakdown strength value (being about 600MPa), but a few noresidue intensity after its thermal shock, and retained strength is 400MPa after the best thermal shock.
Because T at room temperature is a metasable state mutually, when being subjected to applied stress, just produce the abnormal mutually of the diffusing type in numb field, form the bigger low temperature phase (M phase) of volume, this but is favourable to workpiece, when workpiece produces the crack because of external force, produce abnormally mutually in meet stress field because of crack front of the T of crack front, form the M phase, and then produce local body strain and cut distortion, eliminate the stress intensity of crack front, so the ability of growing up in the opposing crack can improve.Above-mentioned phenomenon is exactly so-called phase toughness (Transformation Toughening), and successfully the characteristic of zirconia particles malleableize is applied on the engineering composite ceramics (Engineering Ceramic), comprise that aluminium oxide, mullite (Mullite), cordierite (Cordierite), silicon nitride are the ceramic material of substrate.And at magnesia part stabilized zirconia (Mg-PSZ) material, because of having high toughness and intensity, so become one of important engineering pottery.
The steel mouth character of zirconia system concern continuous casting smooth and easy and cost to the hard iron, because the pyroconductivity of zirconia material has only aluminium oxide or magnesian 1/10 to 1/20, thus be a splendid heat insulation material material, when being applied to continuous casting, guarantor's thermal effect the best is difficult for because of the cooling consent; But there is its weakness the aspect in addition, and the thermal stress that the internal and external temperature distributional difference of stem bar section causes causes hot tearing (Thermo-cracking) or thermal spalling (Thermo-spalling) to be avoided far above other material.The aspect zirconia material should add the phase stabiliser of different amounts below 1000 ℃ in addition, and the different marquensite phase change temperature of height is arranged.There is not the zirconic example of interpolation, its Ms and As are respectively at-910 ℃ or-1100 ℃, all present about 1.0% linear expansion rate (approximating 3%), therefore add magnesia or other phase stabiliser of appropriate amount, the Ms temperature is transferred to below the room temperature, and use preheat temperature before more than the As temperature, so can success in the application of continuous casting.
Adopt the coarse granule zirconia to be shaped (hot forming) in the past, the temperature of required sintering may be up to 1750 ℃, and resulting sintered density has only 4.6g/cm
3, residual apparent porosity is 18%, though its anti-thermal shock character is good, but the ability of against corrosion and abrasion resisting (Erosion) is poor far beyond other stem bar.
The character of long-time slag corrosion resistance and abrasion resisting depends on silica (SiO in the slag ingredient
2) with the speed of zirconia reaction rate, because the characteristic of porosity communication, what of void content, the height of molten steel temperature (mild steel exceeds 60 ℃ approximately), and the base (Basicity) in the slag (Slag) (the slag charge base of mild steel is in 1.2, and higher carbons steels is by low) is influenced.
Bullard report high-purity mangesium oxide zirconium stem bar [R.L.Bullard, and P.C.Cheng, " LongTerm Casting with Zirconia Nozzles, " I﹠amp; SM., vol.19[6] (1992) PP.19-26], it is preferable containing and being less than 1% silica; Bullard report stem bar hole is less in addition, and the infiltration of molten steel of the reduction degree of depth is arranged, and this has wetting effect preferably with low alkali slag charge to zirconium surface again, produces higher abrasion rate and is stranded fruit each other.
Therefore desirable zirconia stem bar should have more careful grainiess (hole is less also more even), and lower hole helps to increase stem bar to be used for a long time, but is easy to thermal shock, produces the fast breakaway of meaning and deterioration.Therefore, have with the improvement necessity.
Be to be this in all the year round observation with nearly 1 year research with, inventor, the phase can overcome aforesaid disappearance, through testing repeatedly, and then invents out " method for making of refractory zirconia stem bar " of the present invention.
Summary of the invention
The object of the present invention is to provide a kind of method for making of refractory zirconia stem bar, the product that obtains according to this method for making has: size accurately, hole and density evenly, heat resistanceheat resistant is split and anti-molten steel aggressivity is good, cost of manufacture is cheap, can shorten delivery date and reduce inventory cost.
The method for making of a kind of refractory zirconia stem bar of the present invention, it comprises:
One mixing step is that first temperature with mixing roll transfers to 80-120 ℃, the zirconia powder of 20-80 percentage by weight is poured in the hopper with the stage gradation stirred; Slowly pour the paraffin wax of 4-8wt% into hopper again, in the time of 4-6 minute, add dolomol 0.2-1wt%, the magnesia powder that in the time of 8-11 minute, adds 1-2wt%, add remaining zirconia powder in the time of 13-18 minute, add polypropylene (PP) 2-3wt% in the time of 23-26 minute, and begin to be warming up to 200 ℃; In the time of 40-120 minute, the mixing roll temperature is set at 50 ℃ at last, begins cooling, and automatic granulating, in plastic body, there is no when finding diameter, with the raw material taking-up of injection molding greater than the 10mm particle;
One injection molding step, be that material that aforementioned mixing step is obtained is inserted in the jetting mold prefabricated in the emission forming machine, its mould temperature is that penetrating temperature is between 140-200 ℃ with room temperature to 80 ℃, penetrate pressure then for not being higher than 150Mpa, form product to obtain base;
One solvent degreasing step, be aforementioned base to be formed product place apparent porosity to spare on the porous ceramics substrate of 20-30% approximately, immersion fills in the container of normal heptane, entire container is inserted in the solvent degreasing groove again, the water proof heating, be warming up to 40-60 ℃ from normal temperature with heating rate 0.5-0.7 ℃/minute, and held warm 0.5-12 hour; Used normal heptane can reclaim fully;
One hot defatting step, be after the aforementioned solvents degreasing, the product that again base formed move in the thermal debinding furnace, be warming up to 160-260 ℃ with 1-3 ℃ of/minute clock rate, held warm 10-120 minute, be warming up to 300-480 ℃ with 0.1-3 ℃/minute again, held warm 5-300 minute, now is warming up to 900-1100 ℃ with 4-6 ℃/minute, is cooled to room temperature again in stove, can remove whole adhesives; Degreasing time needs 24-36 hour approximately, decides on the speed of furnace cooling of debinding furnace;
One sintering step, be will finish the base of degreasing form product with the heating rate be about 10-20 ℃/minute to sintering temperature, temperature range is about 1650 ℃-1750 ℃, adopts normal pressure-sinteredly, holds cooling and taking-up and must the stem bar finished product in stove warmer 1-16 hour.
Wherein the solid concentration of component prescription is more than 40vol%, and the content of plastics is below 60vol%.
Wherein said solid phase comprises zirconia and magnesia composition, and wherein magnesian content is 0.1 to 3.5wt%.
Wherein said plastics comprise polypropylene and two kinds of adhesives of paraffin wax, and one or more than one interfacial agents, and the weight rate of its content is, polypropylene content is 5-50wt%, and paraffin wax is 45-90wt%, and interfacial agents is 0-15wt%.
Wherein said interfacial agents is dolomol or stearic acid, or both mixtures.
Wherein said mixing operating temperature is below 220 ℃, and the preheated ceramic powder adds plastic components more in advance.
Wherein said cooling granulation can be finished in mixing roll or in the extrusion shaper.
Mixing step wherein is that first temperature with mixing roll transfers to 100 ℃, the coarse grain zirconia powder of 44.5 percentage by weights (wt%) poured in the hopper stir, routine feed chute again blows slowly the paraffin wax of 6.56wt%, in the time of the 5th minute, add dolomol 0.47wt%, the magnesia powder that in the time of the 10th minute, adds 1.56wt%, the particulate zirconia powder that adds 44.5wt% in the time of the 15th minute, in the time of the 25th minute, add polypropylene 2.34wt%, and begin to be warming up to 200 ℃, at last in the time of 50 minutes, the mixing roll temperature is set at 50 ℃, begin cooling, and automatic granulating, in plastic body, there is no when finding that diameter is greater than 10mm powder, the raw material of injection molding is taken out form.
The heating rate of solvent degreasing step wherein is 0.6 ℃/minute and is warming up to 50 ℃, and held temperature 3 hours.
Hot defatting step wherein is base to be formed product move in the debinding furnace, is warming up to 220 ℃ with 0.5 ℃ of/minute clock rate, holds temperature 6 hours, be warming up to 450 ℃ with 0.5 ℃/minute again, held temperature 10 minutes, and then be warming up to 1000 ℃, in stove, be cooled to room temperature again with 5 ℃/minute.
Description of drawings
Be further to disclose concrete technology contents of the present invention, at first see also graphic, wherein:
Fig. 1 is the manufacturing flow chart of refractory zirconia stem bar of the present invention.
The specific embodiment
As shown in Figure 1, basically, method for making of the present invention is to comprise a mixing step 1, an injection molding step 2, and a solvent degreasing step 3, a hot defatting step 4 and a sintering step 5 form.
Wherein, mixing step 1 is earlier the temperature of mixing roll to be transferred to 100 ℃, and the zirconia powder DK7 of 44.5 percentage by weights (wt%) (Japanese Daiichi Kigenso company produce) is poured in the hopper and stirs.At this moment, paraffin wax (PW with 6.56wt%, Japan Nippon serio company product) pours hopper slowly into, in the time of the 5th minute, add dolomol (SAM, Japan Hayashi Pure Chemical Industries Ltd produces) 0.47wt%, the magnesia powder that adds 1.56wt% in the time of the 10th minute, the zirconia powder SF (U.S. Z-Tech company product) that adds 44.5wt% in the time of the 15th minute, add polypropylene (PP in the time of the 25th minute, TaiwanPolypropylene Co produces) 2.34wt%, and begin to be warming up to 200 ℃ (can reach 200 ℃ in about 9 minutes).In the time of 50 minutes, the mixing roll temperature is set at 50 ℃ at last, begins cooling, and automatic granulating, in plastic body, there is no when finding diameter, with the raw material taking-up of injection molding greater than the 10mm particle.
Injection molding step 2 be with aforementioned mixing and material, insert in the jetting mold prefabricated in the emission forming machine, its mould temperature is with room temperature to 80 ℃, penetrating temperature is between 140-200 ℃, penetrates pressure then for not being higher than 150Mpa, to obtain base formation product.
Solvent degreasing step 3 is to place on the porous ceramics substrate (apparent porosity is about 26%) so that base is formed product, immersion fills normal heptane (n-Heptane, C7H10, in oily company produce) container in, entire container is inserted in the solvent degreasing groove again, the water proof heating is warming up to 50 ℃ from normal temperature for 0.6 ℃/minute with heating rate, and held 13 hours.Wherein the normal heptane consumption forms product 400cc in every base, and used normal heptane can reclaim fully, as the usefulness of fuel oil.
Hot defatting step 4 then is after the aforementioned solvents degreasing, and base forms in the product the only SA+PW of remaining small part, so base formed product and leaned on a little P P as intergranular adhesive this moment, intensity is very low.But because earlier through solvent degreasing, base forms leachable most of PW and SAM (accounting for the 80wt%-90wt% of plastic agent system) in the product, so can stay many continuous holes (can be observed by SEM); But belong to thick zirconia stem bar, then can residual pact half plastic components.
Base forms product and moves in the debinding furnace, is warming up to 250 ℃ with 2 ℃ of/minute clock rate, holds temperature 1 hour, is warming up to 450 ℃ with 2 ℃/minute again, holds temperature 10 minutes, and now is warming up to 1000 ℃ with 5 ℃/minute, is cooled to room temperature again in stove, can remove whole adhesives; Degreasing time needs 24-36 hour approximately, decides on debinding furnace stove cooling velocity.
Be base to be formed product place on the porous lightweight substrate during hot degreasing, and in box-type furnace with air suction mode, the gas that drives after macromolecule decomposes leaves furnace chamber, makes decomposition gas be unlikely to be deposited on billet surface, cause the obstruction of follow-up macromolecule decomposition, and form the defective of bubbling, be full of cracks etc.Though the base substrate that hot degreasing finishes is through 1000 ℃ of pre-burnings, idiosome intensity is still low, and this moment, the ZrO2 particle only had the small part sintering.
5 of sintering steps be will finish the base of degreasing form product with heating rate be 10 ℃/minute to sintering temperature, temperature range is 1650 ℃-1720 ℃, adopts normal pressure-sinteredly, holds warm 1-7 hour, cools off in stove again, promptly gets the stem bar finished product.
Via enforcement of the present invention, the enhancement of the effect that it is obtained, hold in respect of following number:
(1) size is accurate, learns that through actual measurement the reappearance of its size is ± 0.4%, this for stem bar under the known method for making can't reach.
(2) hole and density are even, and via adjustment, it burns till density can be in the 4.6-5.2g/ml scope, and stem bar upper-lower position density is less than 0.06g/ml, also be much better than the stem bar under the known method for making, and its thickness with density can reach 11-13m/m, also far above known 5m/m.
(3) heat resistanceheat resistant of stem bar is split and anti-molten steel aggressivity also is known as good.
(4) cost of manufacture is cheap, especially compares to present import stem bar speech, can shorten delivery date and reduce inventory cost.
Disclosed person is a kind of of preferred embodiment, Ju Bu change or modification and come from technological thought of the present invention and be easy to the person of knowing by inference such as by the people who has the knack of this skill, and tool does not take off patent right category of the present invention.
Claims (10)
1. the method for making of a refractory zirconia stem bar is characterized in that, it comprises:
One mixing step is that first temperature with mixing roll transfers to 80-120 ℃, the zirconia powder of 20-80 percentage by weight is poured in the hopper with the stage gradation stirred; Slowly pour the paraffin of 4-8wt% into hopper again, in the time of 4-6 minute, add dolomol 0.2-1wt%, the magnesia powder that in the time of 8-11 minute, adds 1-2wt%, add remaining zirconia powder in the time of 13-18 minute, add polypropylene 2-3wt% in the time of 23-26 minute, and begin to be warming up to 200 ℃; In the time of 40-120 minute, the mixing roll temperature is set at 50 ℃ at last, begins cooling, and automatic granulating, in plastic body, there is no when finding diameter, with the raw material taking-up of injection molding greater than the 10mm particle;
One injection molding step, be that material that aforementioned mixing step is obtained is inserted in the jetting mold prefabricated in the emission forming machine, its mould temperature is that penetrating temperature is between 140-200 ℃ with room temperature to 80 ℃, penetrate pressure then for not being higher than 150MPa, form product to obtain base;
One solvent degreasing step, be aforementioned base to be formed product place apparent porosity to be about on the porous ceramics substrate of 20-30%, immersion fills in the container of normal heptane, entire container is inserted in the solvent degreasing groove again, the water proof heating, be warming up to 40-60 ℃ from normal temperature with heating rate 0.5-0.7 ℃/minute, and held warm 0.5-12 hour; Used normal heptane can reclaim fully;
One hot defatting step, be after the aforementioned solvents degreasing, the product that again base formed move in the thermal debinding furnace, be warming up to 160-260 ℃ with 1-3 ℃ of/minute clock rate, held warm 10-120 minute, be warming up to 300-480 ℃ with 0.1-3 ℃/minute again, held warm 5-300 minute, then be warming up to 900-1100 ℃, in stove, be cooled to room temperature again, can remove whole adhesives with 4-6 ℃/minute; Degreasing time needs 24-36 hour approximately, decides on the speed of furnace cooling of debinding furnace;
One sintering step, be will finish the base of degreasing form product with the heating rate be about 10-20 ℃/minute to sintering temperature, temperature range is about 1650 ℃-1750 ℃, adopts normal pressure-sinteredly, holds cooling and taking-up and must the stem bar finished product in stove warmer 1-16 hour.
2. the method for making of refractory zirconia stem bar according to claim 1 is characterized in that, wherein the solid concentration of component prescription is more than 40vol%, and the content of plastics is below 60vo%.
3. the method for making of refractory zirconia stem bar according to claim 2 is characterized in that, wherein said solid phase comprises zirconia and magnesia composition, and wherein magnesian content is 0.1 to 3.5wt%.
4. the method for making of refractory zirconia stem bar according to claim 2, it is characterized in that, wherein said plastics comprise polypropylene and two kinds of adhesives of paraffin, and one or more than one interfacial agents, the weight rate of its content is, polypropylene content is 5-50wt%, and paraffin is 45-90wt%, and interfacial agents is 0-15wt%.
5. the method for making of refractory zirconia stem bar according to claim 4 is characterized in that, wherein said interfacial agents is dolomol or stearic acid, or both mixtures.
6. the method for making of refractory zirconia stem bar according to claim 1 is characterized in that, wherein said mixing operating temperature is below 220 ℃, and the preheated ceramic powder adds plastic components more in advance.
7. the method for making of refractory zirconia stem bar according to claim 1 is characterized in that, wherein said cooling granulation can be finished in mixing roll or in the extrusion shaper.
8. the method for making of refractory zirconia stem bar according to claim 1, it is characterized in that, mixing step wherein is that first temperature with mixing roll transfers to 100 ℃, the coarse grain zirconia powder of 44.5 percentage by weights poured in the hopper stir, slowly list the paraffin of 6.56wt% in hopper again, in the time of the 5th minute, add dolomol 0.47wt%, the magnesia powder that in the time of the 10th minute, adds 1.56wt%, the particulate zirconia powder that adds 44.5wt% in the time of the 15th minute, in the time of the 25th minute, add polypropylene 2.34wt%, and begin to be warming up to 200 ℃, in the time of 50 minutes, the mixing roll temperature is set at 50 ℃ at last, begin cooling, and automatic granulating, in plastic body, there is no when finding that diameter is greater than the 10mm particle, the raw material of injection molding is taken out form.
9. the method for making of refractory zirconia stem bar according to claim 1 is characterized in that, the heating rate of solvent degreasing step wherein is 0.6 ℃/minute and is warming up to 50 ℃, and held temperature 3 hours.
10. the method for making of refractory zirconia stem bar according to claim 1, it is characterized in that, hot defatting step wherein is base to be formed product move in the debinding furnace, be warming up to 220 ℃ with 0.5 ℃ of/minute clock rate, hold temperature 6 hours, and be warming up to 450 ℃ with 0.5 ℃/minute again, held temperature 10 minutes, then be warming up to 1000 ℃, in stove, be cooled to room temperature again with 5 ℃/minute.
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| CN 00100878 CN1123413C (en) | 2000-02-17 | 2000-02-17 | Method for making refractory zirconia stem bar |
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| CN104772464B (en) * | 2014-01-14 | 2017-03-01 | 朱晒红 | The preparation method of orthopaedics implant |
| TWI592386B (en) * | 2016-11-22 | 2017-07-21 | 財團法人金屬工業研究發展中心 | Method for manufacturing ceramic implant |
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