CN115490509A - Low-cost modification treatment method for magnesia-alumina spinel powder - Google Patents
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- 239000000843 powder Substances 0.000 title claims abstract description 130
- 239000011029 spinel Substances 0.000 title claims abstract description 99
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 99
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 230000004048 modification Effects 0.000 title claims abstract description 26
- 238000012986 modification Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 51
- 239000002270 dispersing agent Substances 0.000 claims abstract description 43
- 238000000498 ball milling Methods 0.000 claims abstract description 35
- 239000011230 binding agent Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- -1 magnesium aluminate Chemical class 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 28
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
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- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 4
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- C04B35/44—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 aluminates
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Abstract
The invention discloses a low-cost modification treatment method for magnesium aluminate spinel powder. Sintering aid, dispersant and binder are used, high-purity magnesia-alumina spinel powder (the purity is more than or equal to 99.9%) is used as raw material, and the process route is as follows: (1) Firstly, putting weighed sintering aid and magnesia-alumina spinel powder into an organic container filled with a dispersant in sequence, and carrying out ball milling for 8-10h; (2) Secondly, putting a certain amount of binder into slurry containing sintering aid, magnesia-alumina spinel powder and dispersant, and ball-milling for 12-24 h; (3) And finally, drying, ball milling and sieving the slurry subjected to ball milling. The invention has the advantages of simple process flow, low production cost, high utilization rate of raw materials, good sintering activity of powder and easy batch preparation. By selecting a proper dispersant, the rheological property of the high-purity powder can be effectively increased, biscuit molding is easy, and biscuit density can be improved; the size of the modified powder can be controlled by adding a proper amount of binder.
Description
Technical Field
The invention relates to a low-cost modification treatment method for magnesia-alumina spinel powder, belonging to the technical field of ceramic material treatment.
Background
The magnesia-alumina spinel transparent ceramic serving as an excellent intermediate infrared material not only has the performances of high temperature resistance, corrosion resistance, abrasion resistance, impact resistance, high hardness, high strength, good electrical insulation and the like of a ceramic material, but also has the excellent optical performances of optical glass and optical crystals in visible light and infrared bands, and is widely applied to military fields of bulletproof windows, spacecraft protective windows, submarine infrared sensors and the like, and civil fields of ceramic protective films of metal products, fine ceramic utensils and the like. In order to meet the great demand of the military field and the civil field for the magnesia-alumina spinel transparent ceramics, it is necessary to accelerate the commercialization of the magnesia-alumina spinel transparent ceramics, and the main factors hindering the mass production of the magnesia-alumina spinel transparent ceramics with low cost and high quality at present are the synthesis of magnesia-alumina spinel powder, and in the aspect of powder modification, the magnesia-alumina spinel powder faces the problems of difficult biscuit forming, poor particle size uniformity, poor sintering activity and the like.
Conventional powder modification methods are accomplished by some form of mechanical mixing of the sintering aid particles with the spinel powder, such as mortar and pestle, ball milling, mill grinding, or high shear wet milling. The method is very prone to contamination problems using mechanical mixing techniques, which can result in opaque or hazy areas in the product even when the level of impurities produced by abrasion of the grinding media is low. In addition, the authors proposed a modification method by spray drying spinel particles dispersed in a sintering aid solution, but this was at the expense of spinel powder, which was found to give a powder-treated yield of not more than 68%, which means that up to 32% of the spinel powder treated by the spray dryer was eventually lost.
Disclosure of Invention
The invention aims to solve the problems of difficult powder biscuit forming, high powder agglomeration degree and poor particle size uniformity, and provides a low-cost modification treatment method for magnesia-alumina spinel powder.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low-cost modification treatment method for magnesia-alumina spinel powder comprises the following steps:
(1) Putting the weighed sintering aid and the magnesia-alumina spinel powder into an organic container filled with a dispersant in sequence, and carrying out ball milling for 8-10h;
(2) Putting a certain amount of binder into slurry containing sintering aid, magnesia-alumina spinel powder and dispersant, and ball-milling for 12-24 h;
(3) And drying, ball-milling and sieving the ball-milled slurry.
Preferably, the purity of the magnesia-alumina spinel powder is more than or equal to 99.9 percent, and the average grain diameter is 200nm to 300nm; the sintering aid is LiF, the purity is more than or equal to 99.99 percent, and the addition amount of the sintering aid is as follows: sintering aid/(sintering aid + magnesia alumina spinel powder) =1wt% -4wt%.
In the invention, the sintering aid LiF can be completely melted at 850 ℃, the formed liquid is uniformly distributed on the surface of the powder through the capillary action, the early densification and the grain growth of the ceramic can be effectively promoted through the particle rearrangement and the liquid phase sintering, and the addition amount of the sintering aid is insufficient to play a role in wetting the powder particles and promoting the early densification and the grain growth by the liquid phase LiF; because LiF has very high vapor pressure between 1000-1400 ℃, the sintering aid can be completely volatilized through high-temperature sintering, the generation of a second phase is avoided, but when the addition amount of LiF is too high, liF which is not completely volatilized can also be gathered at a crystal boundary to generate an amorphous phase, the growth of crystal grains is limited, light scattering is caused, and the defect of partial opaqueness is formed. Therefore, the addition amount of the sintering aid is preferably 1wt% to 4wt%.
Preferably, the dispersant is one or more of water, ammonium polyacrylate and normal hexane. The mass ratio of the dispersing agent to the magnesium aluminate spinel powder is preferably 2-6.
The dispersant is mainly used for adsorbing the surface of solid particles and reducing the interfacial tension between liquid and liquid or between solid and liquid. When the mass ratio of the dispersing agent to the magnesia-alumina spinel powder is less than 2, ions ionized by the dispersing agent are not enough to cover all particles, the ion distribution on the particle surface is uneven, the spatial inhibition mechanism is weak, the suspension has high viscosity, is unstable and easy to agglomerate, and the particle size and the density uniformity of a biscuit are influenced. If the amount of the dispersing agent is excessive, ionized ions are remained in the suspension, and the excessive ions compress an electric double layer to reduce the Zeta potential absolute value, so that the stabilizing effect generated by electrostatic repulsion is reduced, the stability of slurry is influenced, powder agglomeration is easily caused, and the particle size and biscuit density uniformity are influenced.
Preferably, the binder is one or two of polyvinyl alcohol (PVA) and polyvinyl butyral, and the addition amount is as follows: binder/(binder + magnesia alumina spinel powder) =3wt% -10wt%. Further preferably, the binder is polyvinyl alcohol, and the addition amount is 3wt% to 6wt%.
Wherein, the addition amount of the binder is less than 3wt%, the powder granularity and the specific surface area of the powder particles have small change degree, which is not beneficial to compact and stack-up molding of the powder particles and is easy to cause the fragmentation of the prepressed blank. When the addition amount of the binder is more than 10wt%, the powder particle size is increased, and the specific surface area is reduced, so that the sintering activity of the ceramic powder is reduced. In addition, excessive binder reduces powder fluidity, and is easy to agglomerate, so that slurry cannot be mixed uniformly, and ceramic porosity is easy to increase due to binder volatilization at the initial sintering stage.
Preferably, in the step (3), the slurry after ball milling is dried in vacuum at the temperature of 100-120 ℃ for 24-48h; then ball milling is carried out for 12-24h, and finally the mixture is sieved by a 20-40 mesh sieve.
The invention has the beneficial effects that:
(a) The invention directly uses the commercialized high-purity magnesia-alumina spinel powder for powder modification treatment, and has the advantages of simple process flow, low production cost, high raw material utilization rate, good powder sintering activity and easy batch preparation. The modified powder has the characteristics of less agglomeration, good fluidity, uniform and controllable size and the like.
(b) According to the powder modification method provided by the invention, through selecting a proper dispersant, the rheological property of the high-purity powder can be effectively increased, biscuit molding is easy, and biscuit density can be improved.
(c) The powder modification method provided by the invention can realize the size control of the modified powder by adding a proper amount of the binder.
(d) The magnesia-alumina spinel transparent ceramic prepared by hot-pressing and sintering the magnesia-alumina spinel powder obtained by the powder modification method provided by the invention has an average transmittance of more than or equal to 75% in a range of 390nm to 780nm and an average transmittance of more than or equal to 83% in a range of 3 mu m to 5 mu m.
Drawings
FIG. 1 is a particle size distribution diagram of the high-purity magnesium-aluminum spinel powder after the powder modification treatment in example 1.
FIG. 2 is a particle size distribution diagram of the high-purity magnesium-aluminum spinel powder after the powder modification treatment in example 2.
FIG. 3 is a particle size distribution diagram of the high-purity magnesium-aluminum spinel powder after the powder modification treatment in example 3.
FIG. 4 is a scanning electron microscope image of the high purity magnesium-aluminum spinel powder after the powder modification treatment in example 1.
FIG. 5 is a scanning electron micrograph of a hot-pressed ceramic according to example 1.
FIG. 6 is a scanning electron micrograph of a hot-pressed ceramic in example 2.
FIG. 7 is a scanning electron microscope image of the high purity Mg-Al spinel powder after the powder modification treatment in example 4.
FIG. 8 is a scanning electron microscope image of the high purity Mg-Al spinel powder after powder modification treatment in example 5.
FIG. 9 is a graph showing the transmittance curves of the magnesia alumina spinel transparent ceramic prepared by hot-press sintering of the magnesia alumina spinel powder obtained in example 3 in the ranges of 390nm to 780nm (FIG. 9 a) and 3 μm to 5 μm (FIG. 9 b).
Detailed Description
For a better understanding of the invention, the contents of the invention are further illustrated below by means of the figures and the detailed description, without the invention being limited solely to the following examples.
In the following examples, the amounts of the sintering aid and the binder added were calculated as follows: the addition amount of the sintering aid = sintering aid/(sintering aid + magnesium aluminate spinel powder); the addition amount of the binder = binder/(binder + magnesium aluminate spinel powder).
In the following examples, the process of preparing hot-pressed ceramics by hot-pressing sintering is as follows: putting biscuit in a graphite mold with the diameter of 80mm, covering the upper contact surface and the lower contact surface of the biscuit with graphite sheets with the same specification, and placing the biscuit in a hot pressing cavity for hot pressing after the biscuit and the graphite mold are assembled, wherein the hot pressing process comprises the following steps: heating and boosting pressure at room temperature for 1h → 800 ℃ (vacuumizing), and cooling and relieving pressure to normal temperature and normal pressure at 35MPa (constant temperature and constant pressure for 4 h) → at 3h → 1680 ℃, and performing optical processing to obtain the hot-pressed magnesia-alumina spinel ceramic plate.
The transmission performance test method for the hot-pressed magnesia-alumina spinel ceramic sheet refers to JC/T185-2013 (2017) optical quartz glass article 6.3:
the spectral transmittance of the sample in each spectral range was measured using a two-optical-path spectrophotometer with a measurement accuracy of not less than ± 1%. The test specimens should be polished parallel planes in the measurement direction, and the test areas should be free of noticeable texture, bubbles and inclusions. The parallelism of the two parallel surfaces is not more than 2'.
Example 1
The embodiment provides a low-cost magnesium aluminate spinel powder modification treatment method, which comprises the following steps:
firstly, 240g of commercial high-purity magnesia-alumina spinel powder (with the purity of 99 percent and the D (50) of 0.28 mu m), 4.90g of sintering aid LiF (with the purity of 99.99 percent and the addition amount of 2 weight percent), 12.63g (5 weight percent) of binder polyvinyl alcohol, 960g of dispersant water (with the mass ratio of the dispersant to the magnesia-alumina spinel high-purity powder of 4) are weighed,
secondly, sequentially putting the sintering aid and the magnesia-alumina spinel powder into an organic container filled with a dispersant, and carrying out ball milling for 8 hours;
thirdly, putting the binder into slurry containing a sintering aid, magnesia-alumina spinel powder and a dispersant, and performing ball milling for 12 hours;
fourthly, drying the slurry subjected to ball milling in a vacuum drying oven at the temperature of 120 ℃ for 10 hours;
and fifthly, ball-milling the dried powder for 24 hours, and then sieving the powder by a 40-mesh sieve to obtain the modified magnesia-alumina spinel powder.
Water is selected as a dispersing agent during the modification treatment, and as shown in figure 1, the particle size D (50) of the magnesium aluminate spinel powder is obtained (D (50) represents the corresponding particle size when the cumulative particle size distribution percentage of a sample reaches 50 percent), and is 5.7104 mu m. As shown in fig. 4, the particle size is mainly in the range of 80nm-110 nm.
The water is selected as the dispersant, the particle size D (50) of the magnesia-alumina spinel powder is increased, the rheological property of the powder is increased, the pre-pressing forming difficulty is reduced, and the density of the ceramic biscuit is increased.
As shown in FIG. 5, the hot-pressed ceramic prepared from the magnesia-alumina spinel powder has pores inside the hot-pressed ceramic, more inclusions are in the grain boundary, and the cloud phenomenon exists inside the hot-pressed ceramic. The density is 3.57g/cm by testing 3 Slightly less than the theoretical density of spinel, 3.58g/cm 3 。
Example 2
The embodiment provides a low-cost magnesium aluminate spinel powder modification treatment method, which comprises the following steps:
firstly, weighing 240g of commercial high-purity magnesia-alumina spinel powder (with the purity of 99 percent and the D (50) of 0.28 mu m), 4.90g of sintering aid LiF (with the purity of 99.99 percent and the addition of 2 weight percent), 12.63g (5 weight percent) of binder polyvinyl alcohol and 960g of dispersant n-hexane (the mass ratio of the dispersant to the magnesia-alumina spinel high-purity powder is 4);
secondly, sequentially putting the sintering aid and the magnesia-alumina spinel powder into an organic container filled with a dispersant, and carrying out ball milling for 8 hours;
thirdly, putting the binder into slurry containing a sintering aid, magnesia-alumina spinel powder and a dispersant, and performing ball milling for 12 hours;
fourthly, drying the slurry subjected to ball milling in a vacuum drying oven at the temperature of 120 ℃ for 10 hours;
and fifthly, ball-milling the dried powder for 24 hours, and then sieving the powder by a 40-mesh sieve to obtain the modified magnesia-alumina spinel powder.
In the modification treatment, anhydrous n-hexane is selected as a dispersing agent, and as shown in figure 2, the particle size D (50) of the obtained magnesia-alumina spinel powder is 9.5029 μm.
The normal hexane is selected as the dispersing agent, the granularity D (50) of the magnesium aluminate spinel powder is increased, the rheological property of the powder is improved, compared with a biscuit formed by the original powder, the pre-pressing forming difficulty is reduced, and the density of the ceramic biscuit is increased.
As shown in FIG. 6, the hot-pressed ceramic prepared from the magnesia-alumina spinel powder has less internal pores and less inclusions at grain boundaries, and the internal cloud and mist of the hot-pressed ceramic are reduced. The density is 3.58g/cm through testing 3 In accordance with the theoretical density of 3.58g/cm 3 And the compactness is better.
The formation of mist inside the ceramic is mainly due to the high internal porosity, which increases the absorption. In addition, the cleanliness of the grain boundary is not high, and the existence of second phase grains can also increase the haze and reduce the transparency. The second-phase MgO grains precipitated from the magnesium-rich spinel sample are easy to aggregate at the grain boundary, so that the haze of the sample is increased; the Al-rich spinel sample also precipitates a second phase Al-rich in the rapid cooling stage 2 O 3 Phase, also causes an increase in haze of the sample.
Example 3
The embodiment provides a low-cost magnesium aluminate spinel powder modification treatment method, which comprises the following steps:
firstly, 240g of commercial high-purity magnesia-alumina spinel powder (with the purity of 99 percent and the D (50) of 0.28 mu m), 4.90g of sintering aid LiF (with the purity of 99.99 percent and the addition amount of 2 weight percent), 12.63g of binder polyvinyl alcohol (with the weight percent of 5 weight percent) and 960g of dispersant ammonium polyacrylate (with the mass ratio of the dispersant to the magnesia-alumina spinel high-purity powder of 4) are weighed;
secondly, sequentially putting the sintering aid and the magnesia-alumina spinel powder into an organic container filled with a dispersant, and carrying out ball milling for 8 hours;
thirdly, putting the binder into slurry containing a sintering aid, magnesia-alumina spinel powder and a dispersant, and performing ball milling for 12 hours;
fourthly, drying the slurry subjected to ball milling in a vacuum drying oven at the temperature of 120 ℃ for 10 hours;
and fifthly, ball-milling the dried powder for 24 hours, and then sieving the powder by a 40-mesh sieve to obtain the modified magnesia-alumina spinel powder.
During the modification treatment, ammonium polyacrylate is selected as a dispersing agent, and as shown in figure 3, the particle size D (50) of the obtained magnesia-alumina spinel powder is 7.2730 mu m.
The ammonium polyacrylate is selected as the dispersant, the particle size D (50) of the magnesium aluminate spinel powder is increased, the rheological property of the powder is good, the powder is easy to pre-press and form, the ceramic biscuit has good density, the inside of the hot-pressed ceramic has no cloud mist, and the transmittance is higher.
Example 4
The embodiment provides a low-cost magnesium aluminate spinel powder modification treatment method, which comprises the following steps:
firstly, weighing 240g of commercial high-purity magnesia-alumina spinel powder (with the purity of 99 percent and the D (50) of 0.28 mu m), 4.90g of sintering aid LiF (with the purity of 99.99 percent and the addition of 2 weight percent), 18.06g (7 weight percent) of binder polyvinyl alcohol and 960g of dispersant water (the mass ratio of the dispersant to the magnesia-alumina spinel high-purity powder is 4);
secondly, sequentially putting the sintering aid and the magnesia-alumina spinel powder into an organic container filled with a dispersant, and carrying out ball milling for 8 hours;
thirdly, putting the binder into slurry containing a sintering aid, magnesia-alumina spinel powder and a dispersant, and performing ball milling for 12 hours;
fourthly, drying the slurry subjected to ball milling in a vacuum drying oven at the temperature of 120 ℃ for 10 hours;
and fifthly, ball-milling the dried powder for 24 hours, and then sieving the powder by a 40-mesh sieve to obtain the modified magnesia-alumina spinel powder.
7wt% of polyvinyl alcohol as a binder is selected during the modification treatment, and as shown in FIG. 7, the particle size of the obtained magnesia-alumina spinel powder is mainly in the range of 110nm-150 nm.
Example 5
The embodiment provides a low-cost magnesium aluminate spinel powder modification treatment method, which comprises the following steps:
firstly, 240g of commercial high-purity magnesia-alumina spinel powder (with the purity of 99 percent and the D (50) of 0.28 mu m), 4.90g of sintering aid LiF (with the purity of 99.99 percent and the addition of 2 weight percent), 23.74g (9 weight percent) of binder polyvinyl alcohol and 960g of dispersant water (the mass ratio of the dispersant to the magnesia-alumina spinel high-purity powder is 4) are weighed;
secondly, sequentially putting the sintering aid and the magnesia-alumina spinel powder into an organic container filled with a dispersant, and carrying out ball milling for 8 hours;
thirdly, putting the binder into slurry containing a sintering aid, magnesia-alumina spinel powder and a dispersant, and performing ball milling for 12 hours;
fourthly, drying the slurry subjected to ball milling in a vacuum drying oven at the temperature of 120 ℃ for 10 hours;
and fifthly, ball-milling the dried powder for 24 hours, and then sieving the powder through a 40-mesh sieve to obtain the modified magnesia-alumina spinel powder.
9wt% of polyvinyl alcohol as a binder is selected during the modification treatment, and as shown in FIG. 8, the particle size of the obtained magnesia-alumina spinel powder is mainly in the range of 200nm-260 nm.
Example 6
The magnesium aluminate spinel transparent ceramic prepared by hot-pressing and sintering the magnesium aluminate spinel powder obtained in the embodiment 3 has a diameter of 80mm.
And carrying out a transmission performance test on the hot-pressed magnesium aluminate spinel ceramic wafer. The transmission curve is shown in fig. 9, the average transmission rate of the hot-pressed magnesia-alumina spinel ceramic sheet in the range of 390nm to 780nm is more than or equal to 75%, and the average transmission rate in the range of 3 μm to 5 μm is more than or equal to 83%.
Claims (6)
1. A low-cost magnesium aluminate spinel powder modification treatment method is characterized by comprising the following steps:
(1) Putting the weighed sintering aid and the magnesia-alumina spinel powder into an organic container filled with a dispersant in sequence, and carrying out ball milling for 8-10h;
(2) Putting a certain amount of binder into slurry containing sintering aid, magnesia-alumina spinel powder and dispersant, and ball-milling for 12-24 h;
(3) And drying, ball milling and sieving the slurry subjected to ball milling.
2. The method for modifying and processing the low-cost magnesia-alumina spinel powder according to claim 1, wherein the purity of the magnesia-alumina spinel powder is more than or equal to 99.9%, and the average particle size is 200nm to 300nm; the sintering aid is LiF, the purity is more than or equal to 99.99 percent, and the addition amount of the sintering aid is as follows: sintering aid/(sintering aid + magnesia alumina spinel powder) =1wt% -4wt%.
3. The method for modifying and treating the low-cost magnesia-alumina spinel powder according to claim 1, wherein the dispersant is one or more of water, ammonium polyacrylate and n-hexane, and the mass ratio of the dispersant to the magnesia-alumina spinel powder is 2 to 6.
4. The method for modifying and processing low-cost magnesia alumina spinel powder according to claim 1, wherein the binder is one or two of polyvinyl alcohol and polyvinyl butyral, and the addition amount of the binder is as follows: binder/(binder + magnesia alumina spinel powder) =3wt% -10wt%.
5. The method of claim 4, wherein the binder is polyvinyl alcohol and is added in an amount of 3wt% to 6wt%.
6. The low-cost magnesium aluminate spinel powder modification treatment method of claim 1, wherein in the step (3), the ball-milled slurry is dried under vacuum at 100-120 ℃ for 24-48h; the ball milling time is 12h-24h, and the mixture is sieved by a 20-40 mesh sieve.
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| Title |
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| 李法荟等: "LiF对镁铝尖晶石透明陶瓷红外透过率的影响", vol. 27, no. 4, pages 417 - 421 * |
| 杨桂馥 等编著， 天津科学技术出版社: "《粉体技术词典——汉英日对照》", vol. 2, pages: 185 - 312 * |
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