CN1049881C - Method for preparing transparent polycrystalline spinel - Google Patents
Method for preparing transparent polycrystalline spinel Download PDFInfo
- Publication number
- CN1049881C CN1049881C CN95117836A CN95117836A CN1049881C CN 1049881 C CN1049881 C CN 1049881C CN 95117836 A CN95117836 A CN 95117836A CN 95117836 A CN95117836 A CN 95117836A CN 1049881 C CN1049881 C CN 1049881C
- Authority
- CN
- China
- Prior art keywords
- spinel
- transparent polycrystalline
- powder
- polycrystalline spinel
- virahol
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to a method for preparing transparent polycrystalline spinel, which adopts a bimetal alkoxide method to obtain magnesium aluminate compounds, and spinel powder is directly prepared by vacuum drying and high-temperature calcination; then the transparent polycrystalline spinel is pressed once by a hot-pressing technology. The present invention has the advantages that a hot isostatic device which is expensive is saved, technological processes are simplified, and the preparing cost of materials is lowered.
Description
The invention belongs to transparent polycrystalline optical material field.
Transparent spinel is present and following high speed seeker nose cone or the window material that uses, the physical strength height of this material, through performance and thermal conductivity are good, and Young's modulus and thermal expansivity are low, can stand high-speed flight pneumatic thermal shocking that causes and the erosion of resisting the environment rainwater, succeeding in developing of this material will speed up the update that China's missile armament is equipped, and shortens we and external gap.
Abroad to polycrystalline spinel (MgAl
2O
4) development of material is since the sixties.USpatent 3974249 in 1976 disclose the preparation method of transparent spinel.Zhi Bei spinel had only very low transmitance at ultraviolet, visible waveband at that time, was exposed to that transmitance also will descend under the ultraviolet light, and material is easily frayed and corrosion.Enter the nineties, US patent 4930731,4983555,5244849 discloses the preparation and the utilisation technology thereof of transparent polycrystalline spinel again in succession, and wherein the optical property of spinel and mechanical property all are greatly increased.EU patent 0334760 and US patent 5152940 also disclose the preparation method and the technology of spinel sintered body respectively.
But pass through the hip treatment two step method again after the related preparation method of above-mentioned these patents all adopts vacuum hotpressing or atmosphere sintering, and the hot isostatic apparatus investment is big, complex process causes material preparation cost costliness.In addition, prior art is to adopt magnesium oxide (MgO) and aluminum oxide (Al
2O
3) powdered mixture as compacting spinel multicrystal initial feed, and two kinds of powder in any case thorough mixing all be difficult to reach the homogenization of raw material, i.e. MgO, Al in the microcell scope
2O
3Mol ratio can not reach 1: 1, causes the heterogeneous phenomenon of the local appearance of the polycrystalline spinel that suppresses, and has influenced the optical property of material, and at the wave band greater than 4.5 μ m, transmitance is still on the low side.
The objective of the invention is to overcome the uneven shortcoming of raw material in the prior art, and seek a kind of easier drawing method, reduce the preparation cost of material.
For achieving the above object, the present invention at first adopts the bimetal alkoxide process directly to prepare the spinel powder, promptly obtains hydrolysate magnesium aluminate (MgAl by Virahol magnalium bimetal hydrolysis of alkoxide
2O
4), make hydrolysate carry out preparing the spinel powder after the vacuum-drying again, Zhi Bei spinel powder good uniformity like this, chemical ingredients not there are differences in the microcell scope, and foreign matter content is low.Because raw material of the present invention reached homogenization, so the present invention adopts one step of heat pressing process to finish the compacting of polycrystalline spinel material, and obtained with prior art in the suitable even more excellent transparent polycrystalline spinel product of material property.
Divide two portions to describe technical scheme of the present invention in detail below:
One, the preparation of spinel powder
In reactor, add high pure metal aluminium (99.99%), magnesium (99.99%), Virahol and micro-HgCl
2, reflux 48 hours, reaction after finishing is left standstill reaction solution to clarification, clear liquor is changed over to vacuum distillation apparatus again and carries out underpressure distillation, obtains colourless thick Virahol magnalium, and this reaction must be carried out under strict anhydrous condition.
Virahol magnalium adding water and organic solvents such as Virahol or ethanol are hydrolyzed, and hydrolysate can be prepared the spinel powder through vacuum-drying and 1000～1100 ℃ of high-temperature calcinations.
Synthetic spinel powder purity can reach more than 99.9%, and the non-ferrous metal foreign matter content is less than 30ppm (seeing Table 1).
Table 1 spinel powder foreign matter content
| Element | Fe | Cr | Zn | Na | Mn | Si | Ca | Ca | Zr | C | S | V |
| Content (ppm) | 11.0 | 0.1 | 5.0 | 129 | 3.0 | 200 | 5.0 | 1.4 | 300 | 10 | 3.0 |
Analysis means: neutron activation, plasma emission spectrum
Synthetic spinel powder particle size distribution is narrow, and 90% above powder diameter is less than 1.0 μ m, and mean particle size is 0.3～0.4 μ m (seeing Table 2).
Table 2 spinel powder size-grade distribution
| Sample distribution | ＞2μ | 2～1.5 | 1.5～1.0 | 1.0～0.8 | 0.8～0.6 | 0.6～0.4 | 0.4～0.3 | 0.3～0.2 | 0.2～0.1 |
| 1 | 1.3 | 1.1 | 1.3 | 1.9 | 4.3 | 13.2 | 15.0 | 29.4 | 32.5 |
| 2 | 1.8 | 1.5 | 1.8 | 2.7 | 5.6 | 16.1 | 17.3 | 27.1 | 26 |
Mensuration means: Britain MK-3 type particle-size analyzer
Two, the preparation of transparent polycrystalline spinel
Select for use high-strength, high-purity, high fine and close graphite as hot pressing die, this mould requirement of withstand voltage is at 500～700Kg/cm
2And at graphite surface plating one deck pyrolytic graphite or at the graphite surface pad last layer carbon-to-carbon fiber that contacts the spinel powder, prevent the pollution of graphite jig,, adopt the intermediate frequency power supply induction heating by the up and down pressure head pressurization of hydraulic pressure or pressure testing machine to vacuum hotpressing stove to the spinel raw material.
Before heat pressing process begins, the levigate LiF of weight 1～2% is added the spinel powder as sintering agent, thorough mixing, then this powder is put into hot pressing die and carry out coldmoulding, the forming pressure scope is at 5～10MPa, give being evacuated to about 5Pa after the moulding, power supply low-temperature heat, moisture in baking raw material and the stove.When temperature rises to 1000～1100 ℃ of scopes, be incubated 30 minutes, get rid of raw material impurity, open the pressure testing machine pressurization simultaneously, in case powder is contracted in the mould middle part, cause spinel edge devitrification.Along with the rising of temperature, pressure rises simultaneously, and when temperature reached 1500～1700 ℃, pressure is also corresponding to be risen to and be incubated 2～5 hours 40～55 tons (φ 100mm mould) this moment, carry out cooling process then, and rate of temperature fall is controlled in 5 ℃/minute.The multicrystal Main physical performance of transparent spinel that makes of heat pressing process sees Table 3 thus.
The multicrystal Main physical performance of table 3 hot pressing spinel
The performance unit data
Density g/cc 3.58
Fusing point ℃ 2135
Knoop hardness Kg/mm
21200
Bending strength Mpa 1220
Young's modulus Gpa 190
Poisson's ratio 0.2608
Thermal linear expansion coefficient 10
-6/ ℃
40～200℃ 5.7
40～800℃ 7.0
Thermal conductivity (30 ℃) W/M.K 15
Specific inductivity 10
3Hz 8.2
10
6Hz 8.2
9.3×10
9Hz 8.3
Because the present invention optimizes raw material, only adopt heat pressing process once going on foot the compacting of having finished the transparent polycrystalline spinel material, saved and invested huge hot isostatic apparatus, simplified technological process, reduced the material preparation cost, and obtained equally with prior art in the suitable even more excellent transparent polycrystalline spinel product of material property.
Embodiment 1 (feedstock production)
Claim pure magnesium 70 grams with table balance, aluminum isopropylate 1160 grams in the 5000ml three-necked bottle of packing into, add the 1000ml Virahol, and slowly heating to little boiling, adds micro-HgCl
2, refluxing 48 hours, controlled temperature is at 80～90 ℃, and question response finishes, and product is left standstill clarification, and the elimination throw out changes clear liquid over to vacuum distillation apparatus and steams excessive Virahol earlier, and redistillation goes out the Virahol magnalium.The water of 8～24 moles of 1 product of moles addings and the Virahol of 1000～1500ml are hydrolyzed.Hydrolysate is through the vacuum drying oven drying, and drying temperature is controlled at 90～120 ℃, and dried powder is put into High Temperature Furnaces Heating Apparatus calcining again, 500～600 ℃ of dryings 2 hours, rises to 1000～1100 ℃ of calcinings 1.5～2 hours more earlier.
Embodiment 2 (feedstock production)
Take by weighing pure magnesium 70 grams, aluminium 154 grams add the 3000ml Virahol, slowly are heated to little boiling, and add micro-HgCl
2Cause, produce a large amount of bubbles, after question response is steady, reflux 48 hours, reaction finishes, and product is left standstill underpressure distillation.Process is the same later on.
Embodiment 3 (the multicrystal preparation of spinel)
Take by weighing 90 gram spinel powders, add 1.4～1.8 gram LiF, after the mixing fine grinding, in the 100mm graphite jig, graphite jig gives earlier and handling through pyrolytic graphite, again at graphite jig upper and lower surface pad one deck carbon-to-carbon fiber in the internal diameter of packing into.Raw material is packed into behind the mould, first coldmoulding, and low-temperature heat, when temperature rose to 1600 ℃, pressure also rose to 50 tons, and heat-insulation pressure keeping is 3～4 hours under this temperature, after the soaking time, carries out cooling process, and rate of temperature fall is controlled in 5 ℃/minute.After cooling, take out crystal, crystal is through corase grind, fine grinding and polishing.The transmitance of spinel (2mm is thick) is not less than 80% (Fig. 1) at 0.3～0.5 μ m, reaches 87% (Fig. 2) in 3～5 μ m transmitances.
Fig. 1 ultraviolet, visible light transmissivity curve synoptic diagram
Fig. 2 infrared transmittivity curve synoptic diagram
Claims (1)
1. the preparation method of a transparent polycrystalline spinel, it is characterized in that: Virahol magnalium bimetal alkoxide is hydrolyzed, make hydrolysate carry out vacuum-drying and calcining under 1000～1100 ℃, make the spinel powder, levigate LiF with 1～2% weight joins in the above-mentioned spinel powder as sintering agent then, thorough mixing, at 5～10MPa compacted under, being heated to temperature is 1000～1100 ℃, be incubated 30 minutes, continue to be warming up to 1500～1700 ℃, be incubated 2～5 hours, with 5 ℃/minute speed cooling, make transparent polycrystalline spinel then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117836A CN1049881C (en) | 1995-12-15 | 1995-12-15 | Method for preparing transparent polycrystalline spinel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117836A CN1049881C (en) | 1995-12-15 | 1995-12-15 | Method for preparing transparent polycrystalline spinel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1127734A CN1127734A (en) | 1996-07-31 |
| CN1049881C true CN1049881C (en) | 2000-03-01 |
Family
ID=5081383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95117836A Expired - Fee Related CN1049881C (en) | 1995-12-15 | 1995-12-15 | Method for preparing transparent polycrystalline spinel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049881C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919762B (en) * | 2006-09-20 | 2012-02-08 | 郑州大学 | Transparent magnesium aluminum spinel fibre and manufacture method thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398488C (en) * | 2006-11-24 | 2008-07-02 | 四川大学 | Process for preparing magnesium aluminate spinel nano transparent ceramic |
| JP2010514173A (en) * | 2006-12-21 | 2010-04-30 | カール・ツァイス・エスエムティー・アーゲー | Transmissive optical element |
| US8440584B1 (en) * | 2010-12-23 | 2013-05-14 | Lehigh University | Methods for decontamination of powders |
| KR20150097714A (en) * | 2012-12-19 | 2015-08-26 | 세람텍-에텍 게엠베하 | Ceramic material |
| CN104556166A (en) * | 2014-12-09 | 2015-04-29 | 东北大学 | Method for preparing MgO.Al2O3 superfine powder by sol-gel process |
| KR102510257B1 (en) * | 2016-10-05 | 2023-03-16 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Transparent spinel sintered body, optical member and transparent spinel sintered body manufacturing method |
| JP6975863B2 (en) * | 2018-08-07 | 2021-12-01 | 三井金属鉱業株式会社 | Light diffusion member, and light diffusion structure and light emission structure using this |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1039792A (en) * | 1911-11-15 | 1912-10-01 | William S Payne | Egg marker and dater. |
| US1047271A (en) * | 1911-11-13 | 1912-12-17 | Hartley A Mitchell | Convertible motor-boat and automobile combined. |
| US3974249A (en) * | 1970-09-16 | 1976-08-10 | Coors Porcelain Company | Method for manufacturing a transparent ceramic body |
| US4930731A (en) * | 1987-05-06 | 1990-06-05 | Coors Porcelain Company | Dome and window for missiles and launch tubes with high ultraviolet transmittance |
| US4983555A (en) * | 1987-05-06 | 1991-01-08 | Coors Porcelain Company | Application of transparent polycrystalline body with high ultraviolet transmittance |
| US5244849A (en) * | 1987-05-06 | 1993-09-14 | Coors Porcelain Company | Method for producing transparent polycrystalline body with high ultraviolet transmittance |
| CN1086799A (en) * | 1992-11-10 | 1994-05-18 | 冶金工业部洛阳耐火材料研究院 | A kind of method of synthetic MgAl spinal |
-
1995
- 1995-12-15 CN CN95117836A patent/CN1049881C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1047271A (en) * | 1911-11-13 | 1912-12-17 | Hartley A Mitchell | Convertible motor-boat and automobile combined. |
| US1039792A (en) * | 1911-11-15 | 1912-10-01 | William S Payne | Egg marker and dater. |
| US3974249A (en) * | 1970-09-16 | 1976-08-10 | Coors Porcelain Company | Method for manufacturing a transparent ceramic body |
| US4930731A (en) * | 1987-05-06 | 1990-06-05 | Coors Porcelain Company | Dome and window for missiles and launch tubes with high ultraviolet transmittance |
| US4983555A (en) * | 1987-05-06 | 1991-01-08 | Coors Porcelain Company | Application of transparent polycrystalline body with high ultraviolet transmittance |
| US5244849A (en) * | 1987-05-06 | 1993-09-14 | Coors Porcelain Company | Method for producing transparent polycrystalline body with high ultraviolet transmittance |
| CN1086799A (en) * | 1992-11-10 | 1994-05-18 | 冶金工业部洛阳耐火材料研究院 | A kind of method of synthetic MgAl spinal |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919762B (en) * | 2006-09-20 | 2012-02-08 | 郑州大学 | Transparent magnesium aluminum spinel fibre and manufacture method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1127734A (en) | 1996-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1049881C (en) | Method for preparing transparent polycrystalline spinel | |
| CN110128146B (en) | Multifunctional boron carbide-based multiphase ceramic and reactive hot-pressing sintering preparation method thereof | |
| CN101734918B (en) | Compact 10 B boron carbide-rich ceramics and preparation thereof | |
| CN113149652B (en) | High-light-transmittance transparent ceramic prepared based on cold sintering technology and preparation method thereof | |
| CN106747399A (en) | A kind of preparation method of fine grain wideband light-weight magnesite-alumina spinel refractories | |
| CN108546109B (en) | Preparation method of large-size AZO magnetron sputtering target with controllable oxygen vacancy | |
| CN1974403A (en) | Mechanical activation-reaction heat treating preparation process of nanometer titanium carbonitride | |
| CN114455952B (en) | AlON powder, direct nitridation method high-pressure synthesis method and application thereof | |
| CN112299861B (en) | AlON transparent ceramic pseudo-sintering agent and application thereof, and preparation method of transparent ceramic | |
| CN1974477A (en) | Prepn process of transparent toughened magnesia alumina spinel ceramic | |
| CN110981484B (en) | Method for preparing nanoscale magnesium fluoride transparent ceramic by hot-pressing method | |
| CN114315351B (en) | High-entropy near-zero-expansion vanadate ceramic material and sintering synthesis method thereof | |
| CN1259281C (en) | Silicon nitride - boron nitride- silicon dioxide ceramic wave-transparent material and preparation process thereof | |
| CN100422109C (en) | Aluminium oxide silicon titanium carbonate/aluminium oxide lamina composite material and preparing method | |
| CN1182069C (en) | Prepn. of submicron high-purity transparent alumina ceramic material | |
| CN1699159A (en) | Titanium aluminium carbide powder and synthesis method using tin as reactive adjuvant therefor | |
| CN1821175A (en) | Method for preparing silicon carbide whisker/aluminium oxide composite ceramic powder using natural kaolin | |
| CN112111663A (en) | High-strength MAB ceramic compact block and preparation method thereof | |
| CN101885608A (en) | Boron nitride nanotube strengthened silicon nitride ceramic material and preparation method thereof | |
| CN116178019B (en) | Method for preparing porous MAX phase ceramic material by pressureless wrapping calcination | |
| CN108821773A (en) | A kind of method that the sintering of wet forming reaction in-situ prepares boron carbide ceramics | |
| CN113045310B (en) | Method for preparing lanthanum gadolinium zirconate transparent ceramic by AM gel casting process | |
| CN1944337A (en) | Atmospheric synthetic method for high purity titamum aluminum carbide ceramic powder | |
| CN112225564B (en) | Aluminum oxynitride transparent ceramic and preparation method thereof | |
| CN114988881A (en) | Boride high-entropy ceramic precursor, high-entropy ceramic and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |