CN106083186A - Porous ceramics block, metal-base composites and preparation method thereof - Google Patents
Porous ceramics block, metal-base composites and preparation method thereof Download PDFInfo
- Publication number
- CN106083186A CN106083186A CN201610447394.4A CN201610447394A CN106083186A CN 106083186 A CN106083186 A CN 106083186A CN 201610447394 A CN201610447394 A CN 201610447394A CN 106083186 A CN106083186 A CN 106083186A
- Authority
- CN
- China
- Prior art keywords
- ceramic
- organic foam
- porous ceramics
- foam
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention provides a kind of porous ceramics block, metal-base composites and preparation method thereof, described porous ceramics block is obtained, wherein: described organic foam is polystyrene foam plastics or polyurethane foam plastics after overworking organic foam drying, evaporation and the sintering processes of ceramic size；Described ceramic size is made up of ceramic powder, binding agent and solvent, described ceramic powder be aluminium oxide or/and chromic oxide, described binding agent is organic binder bond or inorganic binder, and described solvent is water or organic solvent.The preparation method of the porous ceramics block of the present invention is simple, pore size distribution in ceramic block uniformly, the size in hole is easily controlled, the porous ceramics block using the present invention is prepared metal-based compound high-abrasive material and is more prone to, simplify the preparation process of composite abrasion resistance material, and be more convenient for controlling the distribution of pottery in metal base.
Description
Technical field
The present invention relates to be applied to the field of compound material of disintegrating machine, be specifically related to a kind of porous ceramics block, Metal Substrate multiple
Condensation material and preparation method thereof.
Background technology
Metallurgical mine, building materials, build the road, in chemistry and silicate industry, disintegrating machine is the capital equipment that material is broken.With
China's rapid development of economy, these industries need to be that geometrical progression increases through the material that disintegrating machine processes every year, and impact is broken
Broken process a lot of because have, but be all associated with the performance of disintegrating apparatus.In the disintegrating machines such as liner plate, tup, roller and roller tooth
Easy-abrasion part, the performance of disintegrating machine is had a significant impact by the quality of its wearability.
The subject matter that at present disintegrating machine development exists has that application abrasion resistance material is less, the manufacturing process water of disintegrating machine
Flat poor etc..Disintegrating machine often selects the rich chromium cast iron of routine, ultra-high manganese steel etc. as high-abrasive material, the high-abrasive material of this quasi-tradition
Due to limited capacity, frequently with the use time of the method prolongation disintegrating machine of periodic replacement wearing piece, thereby result in work strong
The problems such as degree increase and inefficiency.
Summary of the invention
It is an object of the invention to provide a kind of porous ceramics block, metal-base composites and preparation method thereof, the present invention
The preparation method of porous ceramics block is simple, pore size distribution in ceramic block uniformly, the size in hole be easily controlled, use the present invention's
Porous ceramics block is prepared metal-based compound high-abrasive material and is more prone to, and simplifies the preparation process of composite abrasion resistance material, Er Qiegeng
It is easy to control the distribution of pottery in metal base.
To achieve these goals, the present invention provides following technical scheme:
The preparation method of a kind of porous ceramics block, overworks organic foam drying, evaporation and the sintering processes of ceramic size
After obtain described porous ceramics block, wherein:
Described organic foam is polystyrene foam plastics or polyurethane foam plastics；
Described ceramic size is made up of ceramic powder, binding agent and solvent, and described ceramic powder is aluminium oxide or/and three oxygen
Changing two chromium, described binding agent is organic binder bond or inorganic binder, and described solvent is water or organic solvent.
Preferably, in above-mentioned preparation method, comprise the steps:
Step 1, the pretreatment of described organic foam
Described organic foam through water, detergent, bronsted lowry acids and bases bronsted lowry immersion treatment, obtains pretreated organic foam successively；
Step 2, the preparation of described ceramic size
By described ceramic powder, described binding agent and described solvent mix homogeneously, obtain described ceramic size, wherein: institute
State the 10%-40% that content is described ceramic size gross weight of solvent, it is preferable that described ceramic powder, described binding agent and
The part by weight of described solvent is: ceramic powder: binding agent: solvent=13: (2-3): (4-6)；
Step 3, hanging processes: is immersed in described ceramic size by described pretreated organic foam, obtains after taking-up
Overwork the organic foam of ceramic size；
Step 4, sintering processes: the described organic foam overworking ceramic size is dried, then be evaporated with by organic bubble
Foam evaporates, and is then sintered the ceramic batch evaporating organic foam, thus obtains described porous ceramics block, its
In, when sintering processes, described sintering is that the ceramic batch evaporating organic foam is continuously heating to 700 DEG C-1000 DEG C also
Insulation 50-60min；Preferably, when described sintering processes, described programming rate is 5-10 DEG C/min.
Preferably, in above-mentioned preparation method, in described step 1, comprise the steps:
Step 1.1, is immersed in described organic foam in water, and the temperature of water is 80-100 DEG C, soak time≤two hour,
Step 1.2, washs the described organic foam detergent obtained through step 1.1,
Step 1.3, is immersed in the described organic foam obtained through step 1.2 in acid solution, described acid solution dense
Degree is 10wt%-20wt%, and soak time is 6-10 hour,
Step 1.4, is immersed in the described organic foam obtained through step 1.3 in aqueous slkali, described aqueous slkali dense
Degree is 10wt%-20wt%, and soak time is 6-10 hour；
In described step 2, the granularity of described ceramic powder is 10-40 μm；
In described step 3, the time that described pretreated organic foam immerses in described ceramic size is 1-3h；
In described step 4, described be dried for dry or naturally dry, the temperature of described drying is 100 DEG C-130 DEG C,
After moisture is dried, continue insulation 20-40 minute；
Described evaporation is the dried organic foam overworking ceramic size to be warming up to 650 DEG C-750 DEG C and is incubated 50-
60min；Preferably, in described evaporation process, the speed of described intensification is 0.5-1 DEG C/min；
Described sintering is the ceramic batch evaporating organic foam to be continuously heating to 700 DEG C-800 DEG C and is incubated 50-
60min。
Preferably, in above-mentioned preparation method, the PPI of described polyurethane foam plastics is between 20～30.
Preferably, in above-mentioned preparation method, the thickness of the ceramic size being suspended on described organic foam is 1-3mm.
Preferably, in above-mentioned preparation method, also include the pre-treatment step extruded by described organic foam.
Preferably, in above-mentioned preparation method, between described step 3 and step 4, also include the step removing additional size
Suddenly, i.e. remove described step 3 obtain described in overwork slurry unnecessary in the organic foam of ceramic size；Preferably, hands is used
Work rubs method or mechanical roller platen press removes described unnecessary slurry.
On the other hand, it is provided that a kind of porous ceramics block using said method to prepare, the PPI of described porous ceramics block exists
Between 20～30.
On the other hand, it is provided that a kind of metal-base composites, by the porous ceramics block described in claim 8 and inflow institute
The metallic matrix stating in the hole of porous ceramics block and formed after the molten metal solidification of peripheral part is constituted.
On the other hand, it is provided that a kind of method preparing above-mentioned metal-matrix composite material, comprise the steps:
Step 1, inserts in the die cavity of common sand mold by described cellular ceramic block, and preheated rear casting of molten metal is described
Molten metal is full of in the hole of described porous ceramics block and peripheral part, and pouring temperature is 1500 DEG C-1600 DEG C；
Step 2, cooling and the demoulding.
Metal-base composites is with metal or alloy as matrix, the composite wood with high performance second as reinforcement
Material, it can retain the main characteristics of former composition material, and obtain the performance not available for stock blend by coincidence effect.With biography
The metal material of system is compared, and it has higher specific strength and specific stiffness；Compared with polymer matrix composites, it has again excellent
Heat conductivity and thermostability, compared with ceramic material, it has again higher toughness and higher shock resistance.
With pottery as reinforcing material, metal be the metal matrix ceramic composites that matrix material is made have specific strength high,
The premium properties such as specific modulus is high, wear-resistant, high temperature resistant, are applied to disintegrating apparatus, it is possible to be effectively improved grinding apparatus work
Efficiency, optimizes comminution operation.
It is an object of the invention to porous ceramics as reinforcing material, metal is that matrix material is made and had that specific strength is high, ratio
The metal matrix ceramic composites of the premium properties such as modulus is high, wear-resistant, and be applied in crusher.The porous of the present invention
The preparation method of ceramic block is simple, pore size distribution in ceramic block uniformly, the size in hole be easily controlled, use the porous pottery of the present invention
Porcelain block is prepared metal-based compound high-abrasive material and is more prone to, and simplifies the preparation process of composite abrasion resistance material, and is more convenient for controlling
The distribution of pottery in metal base processed.
Accompanying drawing explanation
The Figure of description of the part constituting the application is used for providing a further understanding of the present invention, and the present invention shows
Meaning property embodiment and explanation thereof are used for explaining the present invention, are not intended that inappropriate limitation of the present invention.Wherein:
Fig. 1 is Foam dipping method pore-forming principle schematic；
In Fig. 1, porous ceramics block has two kinds of holes, and a kind of is that the through hole that foam plastics burning hole prepares is (i.e. organic during hanging
The hole of unfilled slurry on foam), another kind is the hole stayed after organic foam evaporates.
Fig. 2 is the hanging effect that polyurethane foam plastics processes through hot-water soak；
Fig. 3 is the hanging effect that polyurethane foam plastics processes through hot-water soak, aqueous slkali soaking；
Fig. 4 is that polyurethane foam plastics is through hot-water soak, detergent, acid, the hanging effect of alkali immersion treatment；
By in Fig. 2 to Fig. 4 it can be seen that the hanging effect that is substantially better than in Fig. 2 and Fig. 3 of hanging effect in Fig. 4.
Fig. 5 is the sintering effect using the relatively polyurethane foam plastics in fractional value 0.8mm aperture；
Fig. 6 is the sintering effect of the polyurethane foam plastics using bigger numerical 5mm aperture；
By in Fig. 5 to Fig. 6 it can be seen that the sintering effect of Fig. 6 is substantially better than the sintering effect of Fig. 5, i.e. polyurethane foam
The aperture of plastics is satisfactory for result when being 5mm, if dead hole occurs in aperture too little Yi, aperture, at the bottom of porosity, if aperture is the biggest
Time, porous ceramics intensity difference, frangible.
Fig. 7 is the sintering effect of the ceramic particle using granularity to be 60-150 μm；
Fig. 8 is the sintering effect of the ceramic particle using granularity to be 10-40 μm.
From Fig. 7 and 8 it can be seen that the porous ceramics block of Fig. 8 is substantially better than Fig. 7, through-hole rate is significantly higher, many after sintering
The surface in the hole of hole ceramic block is the brightest and the cleanest, flawless, phenomenon of rupture, has preferable intensity.
Detailed description of the invention
Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.It should be noted that in the feelings do not conflicted
Under condition, the embodiment in the application and the feature in embodiment can be mutually combined.
As shown in Figures 1 to 8, according to embodiments of the invention, it is provided that the preparation method of a kind of porous ceramics block, by having
Machine foam and ceramic size are made, wherein:
Organic foam is polystyrene foam plastics or polyurethane foam plastics；
Ceramic size is made up of ceramic powder, binding agent and solvent, and binding agent is organic binder bond or inorganic binder,
Solvent is water or organic solvent.Ceramic powder is the mixture (embodiment at other of commercial alumina and chromic oxide
In, it is also possible to only select the one of which of aluminium oxide and chromic oxide as ceramic powder)；Inorganic binder be silicate,
One or several mixture in borate, phosphate, aluminum hydroxide sol and Ludox, it is preferable that inorganic binder
Mixture for aluminum phosphate or aluminum sulfate with aluminum phosphate；Solvent i.e. can be used as water and also can be used as organic solvent, and organic solvent can
With selecting such as industrial alcohol etc..Ceramic size needs have higher solid concentration, the content of solvent (water or organic solvent)
It is preferably the 10%-40% (such as 15%, 20%, 25%, 30%, 35%) of ceramic size gross weight.
Porous ceramics block flawless prepared by the preparation method of the porous ceramics block provided by the embodiment of the present invention and through hole
Uniformly, in porous ceramics block, the aperture of through hole is preferably 4-6mm (the porous ceramics bulk strength in this aperture is higher), is suitable as gold
The composite of the reinforcement of metal-matrix composite material so that metal-base composites can retain the main characteristics of Metal Substrate, and
The performance that original metal_based material does not possesses is obtained by complex effect.With porous ceramics block as reinforcing material, metal is matrix
The metal matrix ceramic composites that material is made has the premium properties such as specific strength is high, specific modulus is high, wear-resistant, high temperature resistant, will
It is applied to disintegrating apparatus, it is possible to be effectively improved the work efficiency of disintegrating apparatus, optimizes crushing operation.
Further, the preparation method of porous ceramics block comprises the steps:
Step 1, the pretreatment of organic foam
Step 1.1, is immersed in organic foam in water, the temperature of water be 80-100 DEG C (such as 85 DEG C, 90 DEG C, 95 DEG C, 98
DEG C), soak time≤two hour,
Step 1.2, washs the organic foam detergent obtained through step 1.1, and detergent selects commercially available washing
Hands liquid, such as commercially available handwashing liquid etc. of having a showdown by the blue moon,
Step 1.3, is immersed in the organic foam obtained through step 1.2 in acid solution, and the concentration of acid solution is
10wt%-20wt% (such as 13wt%, 15wt%, 17wt%, 19wt%), soak time is 6-10 hour,
Step 1.4, is immersed in the organic foam obtained through step 1.3 in aqueous slkali, and the concentration of aqueous slkali is
10wt%-20wt% (such as 13wt%, 15wt%, 17wt%, 19wt%), soak time is 6-10 hour；
Organic foam proportion by subtraction did not carry out before coated ceramic slurry water soaking, washing, acid solution soaks, aqueous slkali soaks
It is to improve the adhesiveness between organic foam and the ceramic size obtained in following step that bubbles etc. process.Fully after washing
The organic foam processed by acid solution, aqueous slkali soaking the most successively has preferable hanging effect, and hanging is uniform, and hanging amount is fitted
In.Detergent can wash the impurity on the plastic eyelet muscle surface of organic foam off, and can be one during washing is rubbed
A little voided films are washed off, and acid-alkali treatment is to make foam surface adhere to-OH base, makes foam and slurry be more easy to combine.
Step 2, the preparation of ceramic size
By ceramic powder, binding agent and solvent mix homogeneously, the granularity of ceramic powder is 10-40 μm (such as 15 μm, 20 μ
M, 25 μm, 30 μm, 35 μm), i.e. the granularity of the aluminium oxide in ceramic powder and chromic oxide be 10-40 μm (such as 15 μm, 20
μm、25μm、30μm、35μm)；Preferably charging sequence is ceramic powder, binding agent, solvent to be sequentially added into, ceramic powder, viscous
The part by weight of knot agent and solvent is: ceramic powder: binding agent: solvent=13: (2-3): (4-6)；Oxidation in ceramic powder
The part by weight of aluminum and chromic oxide is preferably: aluminium oxide: chromic oxide=10: 3, the benefit of this ratio setting is slurry
Viscosity is moderate, hanging amount is moderate, sintering after intensity preferable.
In preparing ceramic size, add binding agent, not only facilitate and improve that to overwork the organic foam of ceramic size dried
Intensity, and can prevent the organic foam overworking ceramic size from subsiding in organic foam exclusion process, thus after ensure that
The porous ceramics block that continuous sintering step obtains has enough mechanical strengths.Use aluminum phosphate as binding agent ceramic size with
The adhesiveness of organic foam matrix is substantially better than aluminum sulfate and does the ceramic size of binding agent.The granularity of ceramic powder is more than 40 μm
Time, the ceramic size poor stability of preparation, have partly precipitated thing after long-time placement and separate out, the uniformity of slurry becomes therewith
Difference, and then cause it poor with the adhesiveness of organic foam matrix.Granularity is ceramic size tool prepared by 10-40 μm ceramic powder
Having preferable stability, after the ceramic size long period places, the phenomenon of precipitation will not occur to separate out, slurry still keeps uniform
State, preferable with the adhesiveness of organic foam plastic matrix, hanging is uniform, and hanging amount is moderate, and through-hole rate is significantly higher, after sintering
The surface in hole of porous ceramics block the brightest and the cleanest, flawless, phenomenon of rupture, there is preferable intensity.
Step 3, immerses the organic foam obtained through step 1 in the ceramic size that step 2 obtains, soak time
For 1-3h (such as 1.5h, 1.8h, 2h, 2.3h, 2.8h), obtain overworking the organic foam of ceramic size, be coated in organic foam
On the thickness of ceramic size be preferably 1-3mm (such as 1.5mm, 2mm, 2.2mm, 2.5mm, 2.8mm).Hanging thickness is suitable,
The intensity of porous ceramics block can be ensured well.
Step 4, sintering
Step 4.1, dries the organic foam overworking ceramic size obtained through step 3 or naturally dries, preferably
Use Muffle furnace is dried, and drying temperature is 100 DEG C-130 DEG C (such as 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C), dries
Two to three hours time；Continue insulation 20-40min (such as 25min, 30min, 35min) after drying, be preferably incubated 30min；
When ceramic size uses waterglass to be binding agent, when it is dried, temperature can not be the highest, if the higher waterglass of temperature can be with moisture
Evaporation overflow, the surface of organic foam formed tympanites phenomenon, i.e. ceramic size use waterglass be preferably to adopt during binding agent
Subsequent step is carried out again after naturally drying.
Step 4.2, the organic foam evaporation in the organic foam overworking ceramic size that will obtain through step 4.1,
To porous ceramics blank, described evaporation is that the dried organic foam overworking ceramic size is warming up to 650 DEG C-750 DEG C (ratios
Such as 670 DEG C, 690 DEG C, 700 DEG C, 720 DEG C, 735 DEG C) and it is incubated 50-60min (such as 52min, 55min, 58min)；Preferably,
In described evaporation process, the speed of described intensification is 0.5-1 DEG C/min.Organic foam 120 DEG C-750 DEG C (such as 200 DEG C,
300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C) in the range of all can evaporate, say, that in whole temperature-rise period, organic foam all exists
Evaporation, the heating-up time is preferably controlled in 1000-1200min (such as 1050min, 1100min, 1150min), if now heated up
Excessive velocities, the evaporation of organic foam can be very violent, causes sintered skeleton crackle or pore occur, so will heat up speed control
System is in the range of 0.5-1 DEG C/min.In order to ensure that foam matrix evaporates safely, also need to when being warming up to higher temperature protect
Temperature a period of time, foam plastics is made to evaporate completely, so porous ceramics blank is incubated 50-60min at 650 DEG C-750 DEG C.
Step 4.3, the porous ceramics blank high temperature sintering that will obtain through step 4.2, obtain porous ceramics block, described burning
Knot be by evaporate the ceramic batch of organic foam from evaporation holding temperature be continuously heating to 700 DEG C-1000 DEG C (such as 750 DEG C,
800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C) and it is incubated 50-60min (such as 52min, 55min, 58min)；Preferably, in described burning
Knot process time, described programming rate be 3-10 DEG C/min (such as 4 DEG C/min, 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/
Min, 9 DEG C/min), it is preferable that by the holding temperature after the evaporation from step 4.2 of the porous ceramics blank with 5-10 DEG C/min's
Speed is warming up to 700 DEG C-800 DEG C (such as 720 DEG C, 730 DEG C, 750 DEG C, 770 DEG C, 790 DEG C) and is incubated 50-60min (such as
52min、55min、58min)；If programming rate is too fast, can cause the ceramic batch evaporating organic foam that crackle occurs.
Further, it is preferable to the PPI of polyurethane foam plastics is between 20～30, such as PPI is 22,25,28 etc., PPI
Numerical expression be the pore quantity gone up per square inch.When being 25 such as PPI, per square inch on polyurethane foam plastics
Pore quantity is 25.
Polyurethane foam plastics is made up of the aggregated foaming of isocyanates and hydroxy compounds.The value of PPI is 20～30
Between be gross porosity polyurethane foam plastics.Gross porosity polyurethane foam plastics has uniform pore space structure, and its hole, hole is mutually passed through
Lead to and in open.Gross porosity polyurethane foam plastics typically has splendid elasticity, flexibility, percentage elongation and compressive strength；Change
Learn good stability, resistance to many solvents and oils, during heating, can gasify in a large number at about 400 DEG C gross porosity polyurethane foam plastics, its
Peroxide decomposition exotherm occurs mainly in 220-600 DEG C of temperature range, and produces a large amount of gas.It is 20,25 and that PPI is preferably used
The gross porosity polyurethane foam plastics of 30 is as matrix.
The benefit of selection PPI polyurethane foam plastics between 20～30 is:
(1) it is open mesh material, it is ensured that ceramic size can free permeation, mutually bond so that after burning till
Porous ceramics block can form stephanoporate framework；
(2) it has certain hydrophilic, it is possible to absorbent ceramic slurry securely；
(3) it has enough resiliences, it is ensured that can promptly return to the original form after extrusion additional size；
(4) it volatilizees at a temperature of less than ceramic firing, and does not pollute pottery.
When organic foam selects polystyrene foam plastics, polystyrene foam plastics is based on polystyrene resin
Body, adds what the additives such as foaming agent were made.Preferably by block polystyrene foam plastics burning hole, i.e. with the iron wire of heating
Each surface, top to bottom, left and right, front and rear of block polystyrene foam plastics pierces through hole, prepares cellular porous and gather
Styrofoam matrix, then proceeds by above-mentioned steps 1 and the process of every step afterwards.
Further, before step 1.1, also include the step extruded by organic foam, air can be got rid of, be beneficial to
The process of subsequent step 1.1 to 1.4.
Further, between step 3 and step 4, also include the step removing additional size, remove what step 3 obtained
Overwork slurry unnecessary in the organic foam of ceramic size, make to rub method by hand or mechanical roller platen press removes additional size.
The purpose removing additional size is that in the base substrate making organic foam, slurry is evenly distributed and without dead hole.
The invention also discloses a kind of porous ceramics block prepared by said method, the aperture PPI of porous ceramics block is 20
～between 30.
The invention also discloses a kind of metal-base composites, by above-mentioned porous ceramics block and this porous ceramics block of inflow
In hole, the molten metal solidification with peripheral part forms, and molten metal can be the melt of cast steel, cast iron or non-ferrous metal.
The invention also discloses a kind of method preparing metal-base composites, comprise the steps:
Step 1, inserts in the die cavity of common sand mold by cellular ceramic block, pours into a mould after preheated to 1100 DEG C-1200 DEG C
Molten metal, molten metal is full of hole and the peripheral part of porous ceramics block, and pouring temperature is 1500 DEG C-1600 DEG C.
Step 2, Slow cooling and the demoulding；Slow cooling can select stove cold, carries out the demoulding after cooling.
The metal-base composites that the embodiment of the present invention obtains has the Optimalities such as specific strength is high, specific modulus is high, wear-resistant
Can, it is applied to disintegrating apparatus, for improving disintegrating apparatus work efficiency, optimizes crushing operation, thus improve related industries
The economic benefit of department has very important realistic meaning.
Embodiment 1:
Prepare porous ceramics block
Select PPI be the polyurethane foam plastics of 20 as organic foam,
Step 1, the pretreatment of organic foam
Step 1.1, is immersed in organic foam in water, and the temperature of water is 80 DEG C, and soak time is two hours,
Step 1.2, washs the organic foam obtained through step 1.1 with commercially available blue moon handwashing liquid,
Step 1.3, is immersed in the organic foam obtained through step 1.2 in acid solution, and the concentration of acid solution is
10wt%, soak time is 6 hours,
Step 1.4, is immersed in the organic foam obtained through step 1.3 in aqueous slkali, and the concentration of aqueous slkali is
10wt%, soak time is 6 hours；
Step 2, the preparation of ceramic size
By ceramic powder, binding agent and solvent mix homogeneously, the particle mean size of ceramic powder is 10 μm,
The part by weight of ceramic powder, binding agent and solvent is: be 10 μm ceramic powder 65g (aluminium oxidies by particle mean size
50g+ chromic oxide 15g), aluminum phosphate 10g, water 30g are sequentially added into；
Step 3, immerses the organic foam obtained through step 1 in the ceramic size that step 2 obtains, soak time
Being 2 hours, obtain overworking the organic foam of ceramic size, the coating thickness of ceramic size is 1.5mm；
Step 4, sintering
Step 4.1, dries the organic foam Muffle furnace overworking ceramic size obtained through step 3 two hours, with
After again 120 DEG C be incubated 30min,
Step 4.2, carries out plastics machine evacuator body by the porous ceramics blank obtained through step 4.1, starts to rise from 120 DEG C
Temperature, the heating-up time is 1140min, makes temperature rise to 700 DEG C and be incubated 60min, and programming rate is 0.5-0.6 DEG C/min,
Step 4.3, the porous ceramics blank high temperature sintering that will obtain through step 4.2, start to warm up sintering from 700 DEG C,
Being incubated 60min after then proceeding to intensification 30min to 800 DEG C, obtain intensity relatively preferable, flawless is without the porous ceramics of fracture
Block.
Prepare metal-base composites
Above-mentioned porous ceramics block is inserted in the die cavity of common sand mold, be preheated to 1100 DEG C, then casting of molten metal,
To hole and the peripheral part of this porous ceramics block full, cast molten steel composition used: C content 0.25%, Si content 1.1%, Mn contain
Amount 0.83%, pouring temperature is 1550 DEG C.This experiment moulding uses roughing sand waterglass Composite modelling, is sample to prevent in cast
Product are floated by molten iron, and sample is fixed on cavity bottom.
Embodiment 2:
Prepare porous ceramics block
Select PPI be the polyurethane foam plastics of 23 as organic foam,
Step 1, the pretreatment of organic foam
Step 1.1, is immersed in organic foam in water, and the temperature of water is 90 DEG C, and soak time is two hours,
Step 1.2, washs the organic foam obtained through step 1.1 with commercially available blue moon handwashing liquid,
Step 1.3, is immersed in the organic foam obtained through step 1.2 in acid solution, and the concentration of acid solution is 10%,
Soak time is 8 hours,
Step 1.4, is immersed in the organic foam obtained through step 1.3 in aqueous slkali, and the concentration of aqueous slkali is 10%,
Soak time is 8 hours；
Step 2, the preparation of ceramic size
By ceramic powder, binding agent and solvent mix homogeneously, the particle mean size of ceramic powder is 20 μm,
The part by weight of ceramic powder, binding agent and solvent is: be 20 μm ceramic powder 65g (aluminium oxidies by particle mean size
50g+ chromic oxide 15g), aluminum phosphate 15g, water 20g are sequentially added into；
Step 3, immerses the organic foam obtained through step 1 in the ceramic size that step 2 obtains, soak time
For 2h, obtaining overworking the organic foam of ceramic size, the coating thickness of ceramic size is 3mm；
Step 4, sintering
Step 4.1, dries the organic foam Muffle furnace overworking ceramic size obtained through step 3 two hours, and
It is incubated 60min at 120 DEG C,
Step 4.2, the organic foam the overworking ceramic size organic foam therein evaporation that will obtain through step 4.1,
Obtaining porous ceramics blank, be warming up to 500 DEG C from 120 DEG C and be incubated 60min, programming rate is 1-1.1 DEG C/min,
Step 4.3, the porous ceramics blank high temperature sintering that will obtain through step 4.2, it is warming up to 1000 DEG C also from 500 DEG C
Insulation 60min, heating-up time 60min, obtain intensity relatively preferable, flawless is without the porous ceramics block of fracture.
Prepare metal-base composites
Above-mentioned porous ceramics block is inserted in the die cavity of common sand mold, be preheated to 1100 DEG C, then casting of molten metal,
To the hole of this porous ceramics block full, cast molten steel composition used: C content 0.20%, Si content 0.5%, Mn content 0.80%,
Ni content 0.30%, Cu content 0.3%, Mo content 0.2%, pouring temperature is 1550 DEG C.This experiment moulding uses roughing sand water glass
Glass Composite modelling, is that sample is floated by molten iron to prevent in cast, sample is fixed on cavity bottom.
Embodiment 3:
Prepare porous ceramics block
Select PPI be the polyurethane foam plastics of 30 as organic foam,
Step 1, the pretreatment of organic foam
Step 1.1, is immersed in organic foam in water, and the temperature of water is 100 DEG C, and soak time is two hours,
Step 1.2, washs the organic foam obtained through step 1.1 with commercially available blue moon handwashing liquid,
Step 1.3, is immersed in the organic foam obtained through step 1.2 in acid solution, and the concentration of acid solution is 20%,
Soak time is 10 hours,
Step 1.4, is immersed in the organic foam obtained through step 1.3 in aqueous slkali, and the concentration of aqueous slkali is 20%,
Soak time is 10 hours；
Step 2, the preparation of ceramic size
By ceramic powder, binding agent and solvent mix homogeneously, the particle mean size of ceramic powder is 40 μm,
The part by weight of ceramic powder, binding agent and solvent is: be 40 μm ceramic powder 65g (aluminium oxidies by particle mean size
50g+ chromic oxide 15g), aluminum phosphate 7.5g, aluminum sulfate 7.5g, water 30g are sequentially added into；
Step 3, immerses the organic foam obtained through step 1 in the ceramic size that step 2 obtains, soak time
For 2h, obtaining overworking the organic foam of ceramic size, the coating thickness of ceramic size is 1mm；
Step 4, sintering
Step 4.1, dries the organic foam Muffle furnace overworking ceramic size obtained through step 3 two hours, and
It is incubated 30min at 120 DEG C,
Step 4.2, the organic foam the overworking ceramic size organic foam therein evaporation that will obtain through step 4.1,
Obtaining porous ceramics blank, evaporating temperature is warmed up to 700 DEG C from 120 DEG C, and the heating-up time is 1140min, and programming rate is 0.5-
0.6 DEG C/min, 700 DEG C of insulation 60min,
Step 4.3, the porous ceramics blank high temperature sintering that will obtain through step 4.2, it is warming up to 800 DEG C of guarantors from 700 DEG C
Temperature 60min, heating-up time 30min, obtain intensity relatively preferable, and flawless is without the porous ceramics block of fracture.
Prepare metal-base composites
Above-mentioned porous ceramics block is inserted in the die cavity of common sand mold, be preheated to 1100 DEG C, then casting of molten metal,
To the hole of this porous ceramics block full, cast molten steel composition used: C content 0.6%, Si content 0.6%, Mn content 0.9%, Mo
Content 0.2%, pouring temperature is 1550 DEG C.This experiment moulding uses roughing sand waterglass Composite modelling, in order to prevent in cast being
Sample is floated by molten iron, and sample is fixed on cavity bottom.
Embodiment 4:
Prepare porous ceramics block
Select PPI be the polyurethane foam plastics of 20 as organic foam,
Step 1, the pretreatment of organic foam
Step 1.1, is immersed in organic foam in water, and the temperature of water is 90 DEG C, and soak time is two hours,
Step 1.2, washs the organic foam obtained through step 1.1 with commercially available blue moon handwashing liquid,
Step 1.3, is immersed in the organic foam obtained through step 1.2 in acid solution, and the concentration of acid solution is 20%,
Soak time is 8 hours,
Step 1.4, is immersed in the organic foam obtained through step 1.3 in aqueous slkali, and the concentration of aqueous slkali is 20%,
Soak time is 80 hours；
Step 2, the preparation of ceramic size
By ceramic powder, binding agent and solvent mix homogeneously, the particle mean size of ceramic powder is 30 μm,
The part by weight of ceramic powder, binding agent and solvent is: be 40 μm ceramic powder 65g (aluminium oxidies by particle mean size
50g+ chromic oxide 15g), aluminum phosphate 10g, water 30g are sequentially added into；
Step 3, immerses the organic foam obtained through step 1 in the ceramic size that step 2 obtains, soak time
For 2h, obtaining overworking the organic foam of ceramic size, the coating thickness of ceramic size is 2mm；
Step 4, sintering
Step 4.1, dries the organic foam Muffle furnace overworking ceramic size obtained through step 3 two hours, and
It is incubated 60min at 120 DEG C,
Step 4.2, the organic foam the overworking ceramic size organic foam therein evaporation that will obtain through step 4.1,
Obtaining porous ceramics blank, be warming up to 500 DEG C from 120 DEG C and be incubated 60min, the heating-up time is 360min, and programming rate is 1-
1.1 DEG C/min,
Step 4.3, the porous ceramics blank high temperature sintering that will obtain through step 4.2, it is warming up to 1000 DEG C also from 500 DEG C
Insulation 60min, heating-up time 120min, obtain intensity relatively preferable, and flawless is without the porous ceramics block of fracture.
Prepare metal-base composites
Above-mentioned porous ceramics block is inserted in the die cavity of common sand mold, be preheated to 1100 DEG C, then casting of molten metal,
To the hole of this porous ceramics block full, cast molten steel composition used: C content 0.25%, Si content 1.1%, Mn content 0.83%,
Pouring temperature is 1550 DEG C.This experiment moulding uses roughing sand waterglass Composite modelling, is that sample is by molten iron to prevent in cast
Float, sample is fixed on cavity bottom.
The present invention is with pottery as reinforcing material, and metal is that the metal matrix ceramic composites that matrix material is made has ratio by force
The premium properties such as degree is high, specific modulus is high, wear-resistant, high temperature resistant, are applied to disintegrating apparatus, it is possible to be effectively improved disintegrating apparatus
Work efficiency, optimizes crushing operation.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for those skilled in the art
For Yuan, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of being made,
Equivalent, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. the preparation method of a porous ceramics block, it is characterised in that overwork the organic foam drying of ceramic size, evaporation and
Described porous ceramics block is obtained, wherein after sintering processes:
Described organic foam is polystyrene foam plastics or polyurethane foam plastics；
Described ceramic size is made up of ceramic powder, binding agent and solvent, and described ceramic powder is that aluminium oxide is or/and three aoxidize two
Chromium, described binding agent is organic binder bond or inorganic binder, and described solvent is water or organic solvent.
Preparation method the most according to claim 1, it is characterised in that comprise the steps:
Step 1, the pretreatment of described organic foam
Described organic foam through water, detergent, bronsted lowry acids and bases bronsted lowry immersion treatment, obtains pretreated organic foam successively；
Step 2, the preparation of described ceramic size
By described ceramic powder, described binding agent and described solvent mix homogeneously, obtain described ceramic size, wherein: described molten
The content of agent is the 10%-40% of described ceramic size gross weight, it is preferable that described ceramic powder, described binding agent and described
The part by weight of solvent is: ceramic powder: binding agent: solvent=13: (2-3): (4-6)；
Step 3, hanging processes: is immersed in described ceramic size by described pretreated organic foam, is overworked after taking-up
The organic foam of ceramic size；
Step 4, sintering processes: the described organic foam overworking ceramic size is dried, then be evaporated steaming organic foam
Send out, then the ceramic batch evaporating organic foam is sintered, thus obtains described porous ceramics block, wherein,
When sintering processes, described sintering is the ceramic batch evaporating organic foam to be continuously heating to 700 DEG C-1000 DEG C and is incubated
50-60min；Preferably, when described sintering processes, described programming rate is 5-10 DEG C/min.
Preparation method the most according to claim 2, it is characterised in that
In described step 1, comprise the steps:
Step 1.1, is immersed in described organic foam in water, and the temperature of water is 80-100 DEG C, soak time≤two hour,
Step 1.2, washs the described organic foam detergent obtained through step 1.1,
Step 1.3, is immersed in the described organic foam obtained through step 1.2 in acid solution, and the concentration of described acid solution is
10wt%-20wt%, soak time is 6-10 hour,
Step 1.4, is immersed in the described organic foam obtained through step 1.3 in aqueous slkali, and the concentration of described aqueous slkali is
10wt%-20wt%, soak time is 6-10 hour；
In described step 2, the granularity of described ceramic powder is 10-40 μm；
In described step 3, the time that described pretreated organic foam immerses in described ceramic size is 1-3h；
In described step 4, described be dried for dry or naturally dry, the temperature of described drying is 100 DEG C-130 DEG C, treats water
Divide after drying, continue insulation 20-40 minute；
Described evaporation is the dried organic foam overworking ceramic size to be warming up to 650 DEG C-750 DEG C and is incubated 50-
60min；Preferably, in described evaporation process, the speed of described intensification is 0.5-1 DEG C/min；
Described sintering is the ceramic batch evaporating organic foam to be continuously heating to 700 DEG C-800 DEG C and is incubated 50-60min.
Preparation method the most according to claim 1, it is characterised in that the PPI of described polyurethane foam plastics is 20～30
Between.
Preparation method the most according to claim 2, it is characterised in that in described step 3, is suspended on described organic foam
The thickness of ceramic size be 1-3mm.
Method the most according to claim 3, it is characterised in that before described step 1.1, also includes described organic bubble
The pre-treatment step of foam extruding.
Method the most according to claim 2, it is characterised in that between described step 3 and step 4, also includes removing many
The step of remaining slurry, i.e. remove described step 3 obtain described in overwork slurry unnecessary in the organic foam of ceramic size；Preferably
Ground, makes to rub method by hand or mechanical roller platen press removes described unnecessary slurry.
8. using porous ceramics block prepared by the arbitrary described method of claim 1-7, the PPI of described porous ceramics block is 20～30
Between.
9. a metal-base composites, it is characterised in that by the porous ceramics block described in claim 8 and the described porous of inflow
The metallic matrix formed in the hole of ceramic block and after the molten metal solidification of peripheral part is constituted.
10. the method for preparation metal-base composites described in claim 9, it is characterised in that comprise the steps:
Step 1, inserts in the die cavity of common sand mold by described cellular ceramic block, preheated rear casting of molten metal, described metal
Liquid is full of in the hole of described porous ceramics block and peripheral part, and pouring temperature is 1500 DEG C-1600 DEG C；
Step 2, cooling and the demoulding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610447394.4A CN106083186B (en) | 2016-06-20 | 2016-06-20 | Porous ceramics block, metal-base composites and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610447394.4A CN106083186B (en) | 2016-06-20 | 2016-06-20 | Porous ceramics block, metal-base composites and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106083186A true CN106083186A (en) | 2016-11-09 |
| CN106083186B CN106083186B (en) | 2019-02-22 |
Family
ID=57238113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610447394.4A Expired - Fee Related CN106083186B (en) | 2016-06-20 | 2016-06-20 | Porous ceramics block, metal-base composites and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106083186B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679325A (en) * | 2017-10-18 | 2019-04-26 | 江西鸿司远特种泡沫材料有限公司 | Porous ceramics Organic Foam Material and preparation method thereof |
| CN110714135A (en) * | 2019-10-29 | 2020-01-21 | 苏州同谊联擎动力科技有限公司 | Preparation method of porous impact-resistant high-temperature alloy material |
| CN113999044A (en) * | 2021-11-12 | 2022-02-01 | 郑州磨料磨具磨削研究所有限公司 | Porous ceramic plate and preparation method thereof |
| CN114349518A (en) * | 2022-01-11 | 2022-04-15 | 松山湖材料实验室 | Porous ceramic preform and preparation method thereof, and hammer head and preparation method thereof |
| CN115745657A (en) * | 2022-11-29 | 2023-03-07 | 江西工陶院精细陶瓷有限公司 | Method for preparing ceramic corrugated structured packing by using chromium slag |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848642A (en) * | 2012-11-29 | 2014-06-11 | 洛阳中苑陶瓷科技有限公司 | Preparation method of aluminum oxide porous foamed ceramic filter |
| CN104402517A (en) * | 2014-10-27 | 2015-03-11 | 武汉科技大学 | Al2O3-SiC foam ceramic and preparation method thereof |
-
2016
- 2016-06-20 CN CN201610447394.4A patent/CN106083186B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848642A (en) * | 2012-11-29 | 2014-06-11 | 洛阳中苑陶瓷科技有限公司 | Preparation method of aluminum oxide porous foamed ceramic filter |
| CN104402517A (en) * | 2014-10-27 | 2015-03-11 | 武汉科技大学 | Al2O3-SiC foam ceramic and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘志伟等: "多孔SiC陶瓷增强金属基复合材料的制备", 《稀有金属材料与工程》 * |
| 罗民华等: "泡沫陶瓷研制过程中影响因素的试验研究", 《陶瓷学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679325A (en) * | 2017-10-18 | 2019-04-26 | 江西鸿司远特种泡沫材料有限公司 | Porous ceramics Organic Foam Material and preparation method thereof |
| CN110714135A (en) * | 2019-10-29 | 2020-01-21 | 苏州同谊联擎动力科技有限公司 | Preparation method of porous impact-resistant high-temperature alloy material |
| CN113999044A (en) * | 2021-11-12 | 2022-02-01 | 郑州磨料磨具磨削研究所有限公司 | Porous ceramic plate and preparation method thereof |
| CN113999044B (en) * | 2021-11-12 | 2022-08-26 | 郑州磨料磨具磨削研究所有限公司 | Porous ceramic plate and preparation method thereof |
| CN114349518A (en) * | 2022-01-11 | 2022-04-15 | 松山湖材料实验室 | Porous ceramic preform and preparation method thereof, and hammer head and preparation method thereof |
| CN115745657A (en) * | 2022-11-29 | 2023-03-07 | 江西工陶院精细陶瓷有限公司 | Method for preparing ceramic corrugated structured packing by using chromium slag |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106083186B (en) | 2019-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106083186A (en) | Porous ceramics block, metal-base composites and preparation method thereof | |
| CN106588098B (en) | A kind of diffusion-type corundum-spinel air brick and preparation method thereof | |
| CN106244863A (en) | A kind of automotive light weight technology top cover Al-alloy casing and preparation method thereof | |
| CN102828073A (en) | Method for producing powder-coated aluminum alloy section | |
| CN105838952A (en) | Magnesium alloy kettle and manufacturing method thereof | |
| CN104060155B (en) | A kind of HT250 foundry goods and production method thereof | |
| CN105174976A (en) | Pouring method of straight tube furnace lining for vanadium iron alloy smelting | |
| CN104130428B (en) | Preparation method of glass fiber reinforced crosslinked polystyrene board | |
| CN106048302B (en) | A kind of founding materials for being applied to nuclear power and wind-powered electricity generation and preparation method thereof | |
| CN105234344B (en) | A kind of lost foam casting special cooling coating and preparation method thereof | |
| CN107556045B (en) | Foaming gypsum casting mold material, foaming gypsum casting mold and baking method | |
| CN112342416B (en) | Method for improving low-temperature mechanical property of cast Al-Si alloy | |
| CN102728818A (en) | Method for preparing SiCp enhanced AZ91D composite material blank | |
| CN101220424B (en) | Method for manufacturing foam aluminum alloy | |
| CN105397025A (en) | Nodular cast iron well lid lost foam casting method | |
| CN108543935A (en) | A kind of method that 3D printing combination lost foam prepares Metal Substrate SHS wear-resistant coatings | |
| CN109249019B (en) | Variable-temperature sintering process for 25% Cr high-chromium cast iron and product thereof | |
| CN107699777A (en) | A kind of bearing cap casting technique | |
| CN108033797A (en) | A kind of method for producing tundish dry vibratory material | |
| CN101396843B (en) | Processing method of dumbbell, disc for dumbbell or the like | |
| CN1911563A (en) | Method for casting large thin wall rotating body high strength aluminium alloy casting | |
| CN104630517B (en) | The preparation method of the aluminum matrix composite that a kind of in-situ particle strengthens | |
| CN107052230A (en) | A kind of alcohol radical anti-flaming dope for improving magnesium alloy mold-filling capacity and preparation method thereof | |
| CN103627898A (en) | Machine shaping method of magnetic separation powder, and application of finished product prepared by method | |
| CN1256207C (en) | Copper and copper alloy surface casting and penetrating process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190222 Termination date: 20210620 |