CN118326191A - Alumina ceramic grinding ball with adjustable specific gravity and preparation method thereof - Google Patents
Alumina ceramic grinding ball with adjustable specific gravity and preparation method thereof Download PDFInfo
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- 238000000227 grinding Methods 0.000 title claims abstract description 127
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 230000005484 gravity Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 201
- 239000000919 ceramic Substances 0.000 claims abstract description 112
- 238000010438 heat treatment Methods 0.000 claims abstract description 74
- 229910052751 metal Inorganic materials 0.000 claims abstract description 66
- 239000002184 metal Substances 0.000 claims abstract description 66
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000462 isostatic pressing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 25
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 22
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 22
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 22
- 239000005642 Oleic acid Substances 0.000 claims description 22
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 22
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 22
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 22
- 239000001993 wax Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 235000013871 bee wax Nutrition 0.000 claims description 11
- 239000012166 beeswax Substances 0.000 claims description 11
- 239000012188 paraffin wax Substances 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 11
- 230000006698 induction Effects 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000011224 oxide ceramic Substances 0.000 claims 2
- 229910052574 oxide ceramic Inorganic materials 0.000 claims 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000005245 sintering Methods 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract 1
- 239000005995 Aluminium silicate Substances 0.000 description 12
- 235000012211 aluminium silicate Nutrition 0.000 description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 12
- 239000010453 quartz Substances 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 230000009286 beneficial effect Effects 0.000 description 7
- 238000007731 hot pressing Methods 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910000954 Medium-carbon steel Inorganic materials 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
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- 238000010304 firing Methods 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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Abstract
The invention provides an alumina ceramic grinding ball with adjustable specific gravity and a preparation method thereof, wherein the preparation method comprises the following steps: mixing metal powder and alumina ceramic powder in proportion to obtain spherical core powder, and preparing spherical cores after heat treatment; coating the spherical cores by using alumina ceramic powder to obtain green bodies; and (3) sintering the green body after isostatic pressing and drying treatment to obtain the ceramic grinding ball. The invention takes metal powder with large specific gravity as raw material, prepares ball core powder according to proportion with Al 2O3 ceramic formula, and obtains metal ceramic ball core with certain porosity through heat treatment. The porous structure is favorable for the bonding strength between the sphere core and the sphere shell, and finally, the surface layer of the sphere core is coated with the Al 2O3 ceramic formula powder, so that the defect that the thermal expansion coefficients of metal powder and ceramic powder are greatly different is overcome, and the wear-resistant Al 2O3 ceramic grinding ball with low cost, no grinding pollution and adjustable specific gravity is obtained after high-temperature sintering.
Description
Technical Field
The invention relates to the technical field of ceramic grinding balls, in particular to an alumina ceramic grinding ball with adjustable specific gravity and a preparation method thereof.
Background
Ceramic grinding balls are widely used in industrial powder and slurry grinding processes. Compared with metal grinding balls, the ceramic grinding balls have the remarkable advantages of high hardness, small abrasion, corrosion resistance and the like, and the ceramic grinding balls have the advantages of less heating, no static electricity and low noise in the grinding process. In addition, as the density of the ceramic grinding balls is smaller, the loading capacity of the ball mill can be reduced, the overall load is obviously reduced, and the ceramic grinding balls have good energy-saving effect. However, as such, the ceramic grinding balls have low kinetic energy and low grinding efficiency under the same conditions. Taking the most widely used Al 2O3 ceramic grinding balls in industry as an example, the density of the ceramic grinding balls is only 2.95-3.85 g/cm 3, and the density of the ceramic grinding balls is much lower than that of the most common steel grinding balls, namely, the density of the ceramic grinding balls is 7.75-8.0 g/cm 3. The density of the ZrO 2 ceramic grinding balls can reach 6.0 g/cm 3, and the density of the ZTA grinding balls is 4.0-6.0 g/cm 3, but the material grinding balls are expensive, so that the wider application of the ceramic grinding balls is limited.
The invention patent (CN 202310819423.5) discloses a wear-resistant ceramic grinding ball with high iron content. The wear-resistant ceramic grinding ball with large specific gravity (3.86-4.33 g/cm 3) is prepared by introducing high-proportion ferric oxide (20-60 wt%) into a formula and converting the ferric oxide into spinel group minerals. However, since the iron oxide component of the grinding balls is high, iron impurities are easily introduced during the ball milling process, resulting in lower purity of the discharged material.
The invention patent (CN 201710586743.5) discloses a metal and ceramic composite grinding medium for a ball mill and a preparation method thereof, wherein the grinding medium comprises a metal inner core and an outer ceramic layer coated on the outer peripheral surface of the metal inner core. Because the compact metal ball is adopted as the inner core, although the transition layer is designed, the bonding property between the compact surface of the metal ball core and the ceramic ball shell is still weaker; more importantly, the thermal expansion coefficients of the metal spherical core and the ceramic spherical shell are not matched, and obvious thermal stress exists at the joint part of the metal spherical core and the ceramic spherical shell during sintering and cooling, so that the strength of the joint part is further reduced.
Thus, the prior art has the following drawbacks:
1. The alumina ceramic grinding ball has small specific gravity and low grinding efficiency; the ceramic grinding ball with high specific gravity is usually made of ZrO 2 material, and has high cost;
2. The proportion of the ceramic grinding balls is increased by directly adding metal components into the ingredients, but metal impurities are introduced in the ball milling process, so that grinding pollution is caused;
3. The composite ceramic grinding ball is directly manufactured by taking metal as an inner core, the problem of poor combination of the metal inner core and a ceramic shell layer exists, the thermal expansion coefficients are not matched, and obvious thermal stress exists during sintering and cooling, so that the strength of a combination part is further deteriorated.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an alumina ceramic grinding ball with adjustable specific gravity and a preparation method thereof, wherein large-specific-gravity metal powder is used as a raw material to be mixed with alumina ceramic powder to obtain ball core powder, the ball core powder is subjected to heat treatment to obtain metal ceramic ball cores with certain porosity, and the coated ceramic powder is matched with the ball core powder to be beneficial to improving the bonding strength of the ball cores and ceramic shell layers, so that the wear-resistant Al 2O3 ceramic grinding ball with low cost, no grinding pollution and adjustable specific gravity is obtained.
The invention provides the following technical scheme:
the invention provides a preparation method of an alumina ceramic grinding ball with adjustable specific gravity, which comprises the following steps:
mixing metal powder and alumina ceramic powder in proportion to obtain spherical core powder, and preparing spherical cores from the spherical core powder after heat treatment;
coating the spherical cores by using alumina ceramic powder to obtain green bodies;
the green body is sintered after being subjected to isostatic pressing and drying treatment, and the ceramic grinding ball is obtained;
The mass ratio of the alumina ceramic powder to the metal powder is 1:1-1:9; the ratio of the diameter of the ball core to the diameter of the green body is 2:5-4:5.
According to the invention, the metal powder and the alumina ceramic powder are mixed, the spherical core powder obtained after forming and heat treatment is of a porous structure (with a certain porosity), and the porous structure is beneficial to mutual 'penetration' between the spherical core and the spherical shell, so that an 'occlusion' structure is formed at an interface, the interface bonding strength is improved, and the bonding strength between the spherical core and the spherical shell is improved.
Because the expansion coefficients of the metal and the ceramic are greatly different, if the ball is manufactured by adopting the preparation method of CN201710586743.5, on one hand, in the heating stage of the sintering process, the excessive thermal expansion of the metal ball core can lead to the cracking of the ceramic ball shell which is not yet sintered; on the other hand, in the cooling stage, the metal sphere core is obviously contracted relative to the ceramic sphere shell, so that the strength of a bonding interface between the metal sphere core and the ceramic sphere shell is obviously reduced, and even peeling occurs.
The porous structure ball core prepared by proportioning the metal powder and the ceramic powder can overcome the defect caused by large difference of expansion coefficients of the metal and the ceramic, and is beneficial to the strength of the grinding ball. This is because, on the one hand, the porous structure has good volume stability, i.e.: excessive volume changes can be accommodated, thereby overcoming the above-mentioned drawbacks due to thermal expansion mismatch; on the other hand, the thermal expansion coefficient of the metal ceramic formula is between that of the metal and the ceramic, so that the performance matching between the ball core and the ball shell is favorably coordinated.
Further, the step of preparing the spherical core powder into spherical cores comprises the following steps: mixing the ball core powder with paraffin, oleic acid and beeswax, heating, stirring, vacuumizing to obtain ball core wax slurry, forming the ball core wax slurry by using a hot-press injection forming process, and then performing wax removal to obtain the ball core.
Further, the spherical core powder: paraffin wax: oleic acid: the mass ratio of the beeswax is 100: (12-15): (0.4-0.8): (0.6-0.8).
Further, the temperature is raised to 1000 ℃ at a heating rate of 1.5 ℃/min for wax removal, and the temperature is kept for 30min ℃ and then cooled to room temperature.
The step of preparing the spherical core powder into the spherical core in the invention can also adopt another mode, and the step comprises the following steps: the method comprises the steps of rolling ball core powder into balls by taking polyvinyl alcohol solution as a binder, and preparing the ball cores through high-frequency induction heating treatment.
Further, the high-frequency induction heating treatment process conditions are as follows: the heating time is 10-30 s, the heat preservation time is 5-30 s, and the cooling time is 5-10 s.
Further, the alumina ceramic powder comprises 80-97wt% of Al 2O3,1-10wt% SiO2 and 2-10wt% of CaO, and the alumina ceramic powder can be doped and substituted by tetragonal zirconia powder, wherein the substitution amount is 0-50wt%. The toughness of the Al 2O3 ceramic can be effectively improved by introducing the Tetragonal Zirconia Powder (TZP) component, so that the material has stronger impact resistance and excellent toughness and wear resistance.
Further, the metal powder is any one of iron powder, steel powder or tungsten powder.
Further, after mixing the metal powder and the alumina ceramic powder, adding a grinding aid, and performing ball milling to obtain spherical core powder, wherein the spherical core powder passes through a 200-mesh sieve with the residue of less than 0.1 wt%.
Further, the green body is isostatically pressed at 200 Mpa, then dried at 90 ℃, and then heated to 1350-1800 ℃ for firing.
The invention also provides the alumina ceramic grinding ball with adjustable specific gravity prepared by the preparation method.
The invention has the following beneficial effects:
1. according to the invention, the metal powder and the alumina ceramic powder are mixed to prepare the spherical core with a pore structure, so that the bonding strength of the spherical core and the shell is improved, the defect caused by large difference of thermal expansion coefficients of metal and ceramic is overcome, and the strength of the grinding ball is improved;
2. the invention can effectively adjust the specific gravity of the grinding ball by controlling the adding proportion of the metal powder and the duty ratio of the inner core, and is applicable to ball milling scenes with different requirements;
3. Compared with the metal grinding ball, the grinding ball prepared by the invention has lower abrasion and higher loading capacity, and as the metal is in the inner core, no metal impurity is introduced in the ball milling process, and the discharge is cleaner; the ceramic grinding balls have a greater specific gravity than alumina ceramic grinding balls, lower cost and greater hardness than zirconia grinding balls.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of one embodiment of the present invention;
FIG. 2 is a process flow diagram of another embodiment of the present invention;
FIG. 3 is a graph of the internal micro-morphology of the grinding ball produced in example 1 of the present invention;
FIG. 4 is a graph of the internal micro-morphology of the grinding ball produced in example 2 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of an alumina ceramic grinding ball with adjustable specific gravity, which comprises the following steps:
Mixing metal powder and alumina ceramic powder in proportion to obtain spherical core powder, and preparing spherical core powder into spherical cores;
coating the spherical cores by using alumina ceramic powder to obtain green bodies;
and (3) sintering the green body after isostatic pressing and drying treatment to obtain the ceramic grinding ball.
Wherein the mass ratio of the alumina ceramic powder to the metal powder is 1:1-1:9; the ratio of the diameter of the sphere core to the diameter of the microsphere green body is 2:5-4:5, the ratio can be adjusted according to the density requirement of the product, and the prepared ceramic sphere has a wide specific gravity range and can be suitable for different scenes.
In a specific embodiment, the metal powder may be any one of iron powder, steel powder, or tungsten powder, but is not limited to the above, and other metals may be considered according to the application, cost, and the like.
In a specific embodiment, the alumina ceramic powder comprises 80-97wt% of Al 2O3,1-10wt% SiO2 and 2-10wt% of CaO, and the alumina ceramic powder can be doped and replaced by Tetragonal Zirconia (TZP) powder, wherein the replacement amount is 0-50wt%.
In a specific embodiment, after metal powder and alumina ceramic powder are mixed, grinding aid (substances such as oleic acid) is added, ball milling is carried out, and ball core powder is obtained, wherein the residue of the ball core powder is less than 0.1 wt percent after passing through a 200-mesh sieve.
In a specific embodiment, the green body is isostatically pressed at 200 Mpa, then dried at 90 ℃, and then fired at 1350-1800 ℃.
According to the invention, the metal powder and the alumina ceramic powder are mixed, the spherical core obtained by heat treatment of the obtained spherical core powder has a porous structure with a certain porosity, and the porous structure is beneficial to the mutual penetration between the spherical core and the spherical shell, so that a 'biting' structure is formed at the interface, the bonding strength between the spherical core and the spherical shell is improved, and the thermal expansion coefficients of the spherical core and the spherical shell are matched, thereby being beneficial to the strength of the grinding ball.
The preparation of the ball core in the invention can adopt various modes:
Referring to FIG. 1, in one embodiment, the spherical core powder is dried and then mixed with paraffin, oleic acid and beeswax according to a certain proportion (the spherical core powder is prepared by heating and stirring at 75 ℃ and vacuumizing, wherein the mass ratio of paraffin to oleic acid to beeswax is 100 (12-15) (0.4-0.8) (0.6-0.8)); then, the ball core wax slurry is prepared into ball cores by a hot-pressing injection molding machine, and then the wax is removed at about 1000 ℃ to obtain the metal ceramic ball cores with certain porosity.
Referring to fig. 2, in another embodiment, a 1wt% polyvinyl alcohol (PVA) solution is used as a binder, and a disk granulator is used to roll the spherical core powder into spherical cores until the diameter of the spherical cores meets the requirement; the high-frequency induction heating mode is adopted for heating treatment, the metal powder is melted and sintered with the alumina ceramic powder to form spherical cores, the heating time is set to be 10-30 s according to the size and the composition of the spherical cores, the heat preservation time is 5-30 s, and the cooling time is 5-10 s. In the heat treatment mode, the spherical cores are incompletely sintered and compact, and can form a porous structure, compared with the former mode, the preparation of wax slurry is not needed, the cost is saved, the subsequent wax removal process is not needed, the one-time sintering process is adopted, the process is simpler, and the production period is greatly shortened.
The invention is further illustrated by the following examples.
Example 1
The preparation process of the alumina ceramic grinding ball in this embodiment is as follows:
(1) The Al 2O3 ceramic formula is 92 ceramic formula, which takes alpha-Al 2O3 powder, quartz powder, caO powder and kaolin (the component contains alpha-Al 2O3) as raw materials. Then mixing the alpha-Al 2O3, quartz powder, caO powder and kaolin=88:3:4:5 according to the mass ratio;
(2) Introducing reduced iron powder as large specific gravity metal, weighing the reduced iron powder=1:9 according to the mass ratio Al 2O3 ceramic formula, adding a proper amount of oleic acid as a grinding aid, and performing ball milling to obtain spherical core powder with certain fineness (200 mesh screen residue <0.1 wt percent);
(3) Mixing the dried spherical core powder with paraffin, oleic acid and beeswax according to the mass ratio of 100:13:0.5:0.65, heating and stirring at 75 ℃, and vacuumizing to obtain spherical core wax slurry;
(4) Preparing a spherical core by adopting a hot-pressing injection molding machine from the spherical core wax slurry, wherein the diameter of the spherical core is 1.0 cm, then heating to 1000 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 30: 30min, and then cooling to room temperature to obtain a metal ceramic spherical core with a certain porosity;
(5) Coating the spherical cores in the step (4) by using the Al 2O3 ceramic formula powder in the step (1) by adopting a disc granulator until the spherical diameter of the grinding spherical green body reaches 2.0 cm;
(6) And (3) isostatic pressing the grinding ball green body at 200 Mpa, drying at 90 ℃, then heating to 1380 ℃ at a heating rate of 5 ℃/min, preserving heat for 90: 90 min, and naturally cooling to room temperature to obtain the high-specific-gravity wear-resistant Al 2O3 ceramic grinding ball.
Example 2
The preparation process of the alumina ceramic grinding ball in this embodiment is as follows:
(1) The Al 2O3 ceramic formula is 92 ceramic formula, which takes alpha-Al 2O3 powder, quartz powder, caO powder and kaolin as raw materials. Then mixing the alpha-Al 2O3, quartz powder, caO powder and kaolin=88:3:4:5 according to the mass ratio;
(2) Introducing reduced iron powder as large specific gravity metal, weighing the reduced iron powder=1:9 according to the mass ratio Al 2O3 ceramic formula, adding a proper amount of oleic acid as a grinding aid, and performing ball milling to obtain spherical core powder with certain fineness (200 mesh screen residue <0.1 wt percent);
(3) Using 1 wt% PVA solution as a binder, and adopting a disc granulator to roll the spherical core powder into a spherical core green body, wherein the diameter of the spherical core green body is 1.0 cm;
(4) Heating the ball core green body by adopting a high-frequency induction heating mode to obtain a ball core, wherein the heating time is set to be 10 s, the heat preservation time is set to be 20 s, and the cooling time is set to be 5 s;
(5) Coating the spherical cores in the step (4) by using the Al 2O3 ceramic formula powder in the step (1) by adopting a disc granulator until the spherical diameter of the grinding spherical green body reaches 2.0 cm;
(6) And (3) isostatic pressing the grinding ball green body at 200 Mpa, drying at 90 ℃, then heating to 1380 ℃ at a heating rate of 5 ℃/min, preserving heat for 90: 90 min, and naturally cooling to room temperature to obtain the high-specific-gravity wear-resistant Al 2O3 ceramic grinding ball.
Example 3
The preparation process of the alumina ceramic grinding ball in this embodiment is as follows:
(1) The Al 2O3 ceramic formula is 92 ceramic formula, which takes alpha-Al 2O3 powder, quartz powder, caO powder and kaolin as raw materials. Adopting TZP powder to replace alpha-Al 2O3 powder according to the proportion of 25 wt percent, namely mixing the TZP powder, quartz powder and CaO powder according to the mass ratio of alpha-Al 2O3 to kaolin=66:22:3:4:5 to obtain ZTA ceramic formula powder;
(2) Introducing reduced iron powder as large specific gravity metal, weighing the reduced iron powder=1:4 according to a mass ratio ZTA ceramic formula, adding a proper amount of oleic acid as a grinding aid, and performing ball milling to obtain spherical core powder with certain fineness (200 mesh screen residue <0.1 wt percent);
(3) Mixing the dried spherical core powder with paraffin, oleic acid and beeswax according to the mass ratio of 100:15:0.7:0.75, heating and stirring at 75 ℃, and vacuumizing to obtain spherical core wax slurry;
(4) Preparing a spherical core by adopting a hot-pressing injection molding machine from the spherical core wax slurry, wherein the diameter of the spherical core is 1.5 cm, then heating to 1000 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 30: 30min, and then cooling to room temperature to obtain a metal ceramic spherical core with a certain porosity;
(5) Coating the spherical cores in the step (4) by adopting a disc granulator by using the ZTA ceramic formula powder in the step (1) until the spherical diameter of the grinding spherical green body reaches 2.0 cm;
(6) And (3) isostatic pressing the grinding ball green body at 200 Mpa, drying at 90 ℃, then heating to 1410 ℃ at a heating rate of 5 ℃/min, preserving heat for 90 min, and naturally cooling to room temperature to obtain the high-specific-gravity wear-resistant ZTA ceramic grinding ball.
Example 4
(1) The Al 2O3 ceramic formula is 92 ceramic formula, which takes alpha-Al 2O3 powder, quartz powder, caO powder and kaolin as raw materials. Adopting TZP powder to replace alpha-Al 2O3 powder according to the proportion of 25 wt percent, namely mixing the TZP powder, quartz powder and CaO powder according to the mass ratio of alpha-Al 2O3 to kaolin=66:22:3:4:5 to obtain ZTA ceramic formula powder;
(2) Introducing reduced iron powder as large specific gravity metal, weighing the reduced iron powder=1:4 according to a mass ratio ZTA ceramic formula, adding a proper amount of oleic acid as a grinding aid, and performing ball milling to obtain spherical core powder with certain fineness (200 mesh screen residue <0.1 wt percent);
(3) Using 1 wt% PVA solution as a binder, and adopting a disc granulator to roll the spherical core powder into spherical core green bodies, wherein the diameter of the spherical core green bodies is 1.5cm;
(4) Heating the spherical core green body by adopting a high-frequency induction heating mode to obtain a spherical core, wherein the heating time is set to be 30s, the heat preservation time is 10 s, and the cooling time is 10 s;
(5) Coating the spherical cores in the step (4) by adopting a disc granulator by using the ZTA ceramic formula powder in the step (1) until the spherical diameter of the grinding spherical green body reaches 2.0 cm;
(6) And (3) isostatic pressing the grinding ball green body at 200 Mpa, drying at 90 ℃, then heating to 1410 ℃ at a heating rate of 5 ℃/min, preserving heat for 90 min, and naturally cooling to room temperature to obtain the high-specific-gravity wear-resistant ZTA ceramic grinding ball.
Example 5
The preparation process of the alumina ceramic grinding ball in this embodiment is as follows:
(1) The Al 2O3 ceramic formula is a 95 ceramic formula, and is prepared from alpha-Al 2O3 powder, quartz powder, caO powder and kaolin. Then mixing the alpha-Al 2O3, quartz powder, caO powder and kaolin powder in a ratio of (93:1:3:3) by mass ratio;
(2) The method comprises the steps of introducing medium carbon steel powder as large specific gravity metal, weighing the medium carbon steel powder=1:9 according to a mass ratio Al 2O3 ceramic formula, adding a proper amount of oleic acid as a grinding aid, and performing ball milling to obtain spherical core powder with certain fineness (200 mesh screen residue is less than 0.1 wt percent);
(3) Mixing the dried spherical core powder with paraffin, oleic acid and beeswax according to the mass ratio of 100:12:0.4:0.6, heating and stirring at 75 ℃, and vacuumizing to obtain spherical core wax slurry;
(4) Preparing a spherical core by adopting a hot-pressing injection molding machine from the spherical core wax slurry, wherein the diameter of the spherical core is 1.5 cm, then heating to 1000 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 30: 30min, and then cooling to room temperature to obtain a metal ceramic spherical core with a certain porosity;
(5) Coating the spherical cores in the step (4) by using the Al 2O3 ceramic formula powder in the step (1) by adopting a disc granulator until the spherical diameter of the grinding spherical green body reaches 2.0 cm;
(6) And (3) isostatic pressing is carried out on the grinding ball green body at 200 Mpa, then drying is carried out at 90 ℃, then the temperature is increased to 1480 ℃ at the heating rate of 5 ℃/min, the grinding ball green body is naturally cooled to room temperature after heat preservation of 90 min, and the high-specific-gravity wear-resistant Al 2O3 ceramic grinding ball is obtained.
Example 6
(1) The Al 2O3 ceramic formula is a 95 ceramic formula, and is prepared from alpha-Al 2O3 powder, quartz powder, caO powder and kaolin. Then mixing the alpha-Al 2O3, quartz powder, caO powder and kaolin powder in a ratio of (93:1:3:3) by mass ratio;
(2) The method comprises the steps of introducing medium carbon steel powder as large specific gravity metal, weighing the medium carbon steel powder=1:9 according to a mass ratio Al 2O3 ceramic formula, adding a proper amount of oleic acid as a grinding aid, and performing ball milling to obtain spherical core powder with certain fineness (200 mesh screen residue is less than 0.1 wt percent);
(3) Using 1 wt% PVA solution as a binder, and adopting a disc granulator to roll the spherical core powder into a spherical core green body, wherein the diameter of the spherical core green body is 1.5 cm;
(4) Heating the spherical core green body by adopting a high-frequency induction heating mode to obtain a spherical core, wherein the heating time is set to be 30s, the heat preservation time is set to be 20 s, and the cooling time is set to be 8 s;
(5) Coating the spherical cores in the step (4) by using the Al 2O3 ceramic formula powder in the step (1) by adopting a disc granulator until the spherical diameter of the grinding spherical green body reaches 2.0 cm;
(6) And (3) isostatic pressing is carried out on the grinding ball green body at 200 Mpa, then drying is carried out at 90 ℃, then the temperature is increased to 1480 ℃ at the heating rate of 5 ℃/min, the grinding ball green body is naturally cooled to room temperature after heat preservation of 90 min, and the high-specific-gravity wear-resistant Al 2O3 ceramic grinding ball is obtained.
Example 7
The preparation process of the alumina ceramic grinding ball in this embodiment is as follows:
(1) The Al 2O3 ceramic formula is a 99 ceramic formula, and is prepared from alpha-Al 2O3 powder and CaO powder as raw materials. Adopting TZP powder to replace alpha-Al 2O3 powder by 50 wt percent, namely mixing the TZP powder with CaO powder=45:44:1 according to the mass ratio of alpha-Al 2O3 to obtain ZTA ceramic formula powder;
(2) Tungsten powder is introduced as large specific gravity metal, the tungsten powder=2:3 is weighed according to the mass ratio ZTA ceramic formula, a proper amount of oleic acid is added as a grinding aid, and ball milling is carried out to obtain spherical core powder with certain fineness (200 meshes of screen residue is less than 0.1 wt percent);
(3) Mixing the dried spherical core powder with paraffin, oleic acid and beeswax according to the mass ratio of 100:13:0.5:0.65, heating and stirring at 75 ℃, and vacuumizing to obtain spherical core wax slurry;
(4) Preparing a spherical core by adopting a hot-pressing injection molding machine from the spherical core wax slurry, wherein the diameter of the spherical core is 1.5 cm, then heating to 1000 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 30: 30min, and then cooling to room temperature to obtain a metal ceramic spherical core with a certain porosity;
(5) Coating the spherical cores in the step (4) by adopting a disc granulator by using the ZTA ceramic formula powder in the step (1) until the spherical diameter of the grinding spherical green body reaches 2.0 cm;
(6) And (3) isostatic pressing the grinding ball green body at 200 Mpa, drying at 90 ℃, then heating to 1780 ℃ at a heating rate of 5 ℃/min, preserving heat for 90: 90 min, and naturally cooling to room temperature to obtain the high-specific-gravity wear-resistant ZTA ceramic grinding ball.
Example 8
(1) The Al 2O3 ceramic formula is a 99 ceramic formula, and is prepared from alpha-Al 2O3 powder and CaO powder as raw materials. Adopting TZP powder to replace alpha-Al 2O3 powder by 50 wt percent, namely mixing the TZP powder with CaO powder=45:44:1 according to the mass ratio of alpha-Al 2O3 to obtain ZTA ceramic formula powder;
(2) Tungsten powder is introduced as large specific gravity metal, the tungsten powder=2:3 is weighed according to the mass ratio ZTA ceramic formula, a proper amount of oleic acid is added as a grinding aid, and ball milling is carried out to obtain spherical core powder with certain fineness (200 meshes of screen residue is less than 0.1 wt percent);
(3) Using 1 wt% PVA solution as a binder, and adopting a disc granulator to roll the spherical core powder into a spherical core green body, wherein the diameter of the spherical core green body is 1.5 cm;
(4) Heating the ball core green body by adopting a high-frequency induction heating mode to obtain a ball core, wherein the heating time is set to be 20 s, the heat preservation time is 30s, and the cooling time is 5 s;
(5) Coating the spherical cores in the step (4) by adopting a disc granulator by using the ZTA ceramic formula powder in the step (1) until the spherical diameter of the grinding spherical green body reaches 2.0 cm;
(6) And (3) isostatic pressing the grinding ball green body at 200 Mpa, drying at 90 ℃, then heating to 1780 ℃ at a heating rate of 5 ℃/min, preserving heat for 90: 90 min, and naturally cooling to room temperature to obtain the high-specific-gravity wear-resistant ZTA ceramic grinding ball.
Example 9
The preparation process of the alumina ceramic grinding ball in this embodiment is as follows:
(1) The Al 2O3 ceramic formula is a 99 ceramic formula, and is prepared from alpha-Al 2O3 powder and CaO powder as raw materials. Adopting TZP powder to replace alpha-Al 2O3 powder according to the proportion of 25 wt percent, namely mixing the TZP powder with CaO powder=75:24:1 according to the mass ratio of alpha-Al 2O3 to obtain ZTA ceramic formula powder;
(2) Tungsten powder is introduced as large specific gravity metal, the tungsten powder=5:5 is weighed according to the formula of the ZTA ceramic, a proper amount of oleic acid is added as a grinding aid, and ball milling is carried out to obtain spherical core powder with certain fineness (200 meshes of screen residue is less than 0.1 wt percent);
(3) Mixing the dried spherical core powder with paraffin, oleic acid and beeswax according to the mass ratio of 100:14:0.4:0.6, heating and stirring at 75 ℃, and vacuumizing to obtain spherical core wax slurry;
(4) Preparing a spherical core by adopting a hot-pressing injection molding machine from the spherical core wax slurry, wherein the diameter of the spherical core is 1.0 cm, then heating to 1000 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 30: 30min, and then cooling to room temperature to obtain a metal ceramic spherical core with a certain porosity;
(5) Coating the spherical cores in the step (4) by adopting a disc granulator by using the ZTA ceramic formula powder in the step (1) until the spherical diameter of the grinding spherical green body reaches 2.0 cm;
(6) And (3) isostatic pressing the grinding ball green body at 200 Mpa, drying at 90 ℃, then heating to 1760 ℃ at a heating rate of 5 ℃/min, preserving heat for 90 min, and naturally cooling to room temperature to obtain the high-specific-gravity wear-resistant ZTA ceramic grinding ball.
Example 10:
(1) The Al 2O3 ceramic formula is a 99 ceramic formula, and is prepared from alpha-Al 2O3 powder and CaO powder as raw materials. Adopting TZP powder to replace alpha-Al 2O3 powder according to the proportion of 25 wt percent, namely mixing the TZP powder with CaO powder=75:24:1 according to the mass ratio of alpha-Al 2O3 to obtain ZTA ceramic formula powder;
(2) Tungsten powder is introduced as large specific gravity metal, the tungsten powder=5:5 is weighed according to the formula of the ZTA ceramic, a proper amount of oleic acid is added as a grinding aid, and ball milling is carried out to obtain spherical core powder with certain fineness (200 meshes of screen residue is less than 0.1 wt percent);
(3) Using 1 wt% PVA solution as a binder, and adopting a disc granulator to roll the spherical core powder into a spherical core green body, wherein the diameter of the spherical core green body is 1.0 cm;
(4) Heating the ball core green body by adopting a high-frequency induction heating mode to obtain a ball core, wherein the heating time is set to be 10 s, the heat preservation time is 5 s, and the cooling time is 5 s;
(5) Coating the spherical cores in the step (4) by adopting a disc granulator by using the ZTA ceramic formula powder in the step (1) until the spherical diameter of the grinding spherical green body reaches 2.0 cm;
(6) And (3) isostatic pressing the grinding ball green body at 200 Mpa, drying at 90 ℃, then heating to 1760 ℃ at a heating rate of 5 ℃/min, preserving heat for 90 min, and naturally cooling to room temperature to obtain the high-specific-gravity wear-resistant ZTA ceramic grinding ball.
Referring to fig. 3, the internal microstructure of the grinding ball prepared in example 1 is characterized, and it can be seen that the ball core has a porous structure with a certain porosity (fig. 3 a), and the porous structure facilitates mutual "penetration" between the ball core and the ball shell, so that a "snap-in" structure is formed at the interface (fig. 3b, which is an enlarged view within the range of the broken line in fig. 3 a), so that the bonding strength between the ball core and the ball shell can be effectively improved, and the thermal expansion coefficients of the two are matched, which is beneficial to the strength of the grinding ball. Referring to fig. 4, the internal microstructure of the grinding ball produced in example 2 was characterized, and it can be seen from the figure that there is a distinct interface between the core and shell portions, the core void ratio is higher than that of the dense shell, and a good transition region (bite region, dashed line region in fig. 4 b) is formed at the interface layer between the two.
The performance parameters of the ceramic grinding balls prepared in the above examples were tested, and the results are shown in table 1:
Table 1 Performance parameters of the products produced in the examples
The grinding balls prepared by the invention have wider specific gravity adjusting range, high wear resistance and high strength, and are more advantageous than metal grinding balls or zirconia grinding balls. According to the invention, the metal powder and the alumina ceramic powder are mixed, the spherical core obtained by heat treatment of the obtained spherical core powder is of a porous structure with pores, and the porous structure is favorable for mutual penetration between the spherical core and the spherical shell, so that a 'biting' structure is formed at an interface, the bonding strength between the spherical core and the spherical shell is improved, and the thermal expansion coefficients of the spherical core and the spherical shell are matched, thereby being favorable for the strength of the grinding ball.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The preparation method of the alumina ceramic grinding ball with adjustable specific gravity is characterized by comprising the following steps:
mixing metal powder and alumina ceramic powder in proportion to obtain spherical core powder, and preparing spherical cores after heat treatment;
coating the spherical cores by using alumina ceramic powder to obtain green bodies;
the green body is sintered after being subjected to isostatic pressing and drying treatment, and the ceramic grinding ball is obtained;
The mass ratio of the alumina ceramic powder to the metal powder is 1:1-1:9; the ratio of the diameter of the ball core to the diameter of the green body is 2:5-4:5.
2. The method for preparing alumina ceramic grinding ball with adjustable specific gravity according to claim 1, wherein: the preparation of the ball core comprises the following steps: mixing the ball core powder with paraffin, oleic acid and beeswax, heating, stirring, vacuumizing to obtain ball core wax slurry, forming the ball core wax slurry by using a hot-press injection forming process, and then performing wax removal to obtain the ball core.
3. The method for preparing alumina ceramic grinding ball with adjustable specific gravity according to claim 2, wherein: ball core powder: paraffin wax: oleic acid: the mass ratio of the beeswax is 100: (12-15): (0.4-0.8): (0.6-0.8).
4. The method for preparing alumina ceramic grinding ball with adjustable specific gravity according to claim 2, wherein: heating to 1000 ℃ at a heating rate of 1.5 ℃/min for wax removal, preserving heat for 30 min ℃ and cooling to room temperature.
5. The method for preparing alumina ceramic grinding ball with adjustable specific gravity according to claim 1, wherein: the preparation of the ball core comprises the following steps: the method comprises the steps of rolling ball core powder into balls by taking polyvinyl alcohol solution as a binder, and preparing the ball cores through high-frequency induction heating treatment.
6. The method for preparing alumina ceramic grinding ball with adjustable specific gravity according to claim 5, wherein: the high-frequency induction heating treatment process conditions are as follows: the heating time is 10-30 s, the heat preservation time is 5-30 s, and the cooling time is 5-10 s.
7. The method for preparing the alumina ceramic grinding ball with adjustable specific gravity according to any one of claims 1 to 6, which is characterized in that: the aluminum oxide ceramic powder comprises 80-97wt% of Al 2O3,1-10wt% SiO2 and 2-10wt% of CaO, and the aluminum oxide ceramic powder can be doped and substituted by tetragonal phase zirconium oxide powder, wherein the substitution amount is 0-50wt%.
8. The method for preparing the alumina ceramic grinding ball with adjustable specific gravity according to any one of claims 1 to 6, which is characterized in that: the metal powder is any one of iron powder, steel powder or tungsten powder.
9. The method for preparing the alumina ceramic grinding ball with adjustable specific gravity according to any one of claims 1 to 6, which is characterized in that: after mixing the metal powder and the alumina ceramic powder, adding a grinding aid, and performing ball milling to obtain spherical core powder, wherein the spherical core powder passes through a 200-mesh sieve with the residue of less than 0.1 wt percent.
10. An alumina ceramic grinding ball with adjustable specific gravity prepared by the preparation method of any one of claims 1-6.
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