CN1108282C - Artificial synthetic luminous gem and its producing method - Google Patents
Artificial synthetic luminous gem and its producing method Download PDFInfo
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- CN1108282C CN1108282C CN96106373A CN96106373A CN1108282C CN 1108282 C CN1108282 C CN 1108282C CN 96106373 A CN96106373 A CN 96106373A CN 96106373 A CN96106373 A CN 96106373A CN 1108282 C CN1108282 C CN 1108282C
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Abstract
The present invention relates to an artificial synthesized gem and a preparing method thereof. A luminescent material with long afterglow and high brightness, which uses alkaline-earth aluminate containing boron as a substrate and uses a rare-earth element as an activator, is used as a raw material of the gem and is made into the artificial light-emitting gem of monoclinic crystal by high-temperature and high-pressure sintering under a protected environment. The Moh's hardness of the artificial synthesized gem is from 6 to 7, the specific gravity of the artificial synthesized gem is from 6 to 8, and the artificial synthesized gem has phosphorescent property.
Description
The present invention relates to the technical field of synthetic jewel, particularly a kind of the generation by High Temperature High Pressure agglomerating method has hard mass of luminescent properties and preparation method thereof.
Natural natural gemstone is of a great variety, for example: ruby, sapphire, emerald, jade ... or the like, have beautiful in colourly, quality is hard, preserves characteristics such as lasting, but its natural resources rareness can not satisfy people's needs.Therefore, the synthetic jewel has appearred, in patent documentation, put down in writing the technology of some newer synthetic jewels in recent years, for example, Chinese patent (notification number) CN1046726, denomination of invention " manufacture method of artificial cat's eye " adopts concentric crucible method, toning process etc. to prepare the cat's eye jewel of various colors; Chinese patent (notification number) CN1015651, denomination of invention " a kind of method for preparing asteria " relates to the directly wetting technology of touching of leading of the high admixture of preparation of star-light gem from melt; Disclose " artificial gem of high reflectance " among Chinese patent (notification number) CN1010971, this jewel is to mix people's rare earth element to make in containing the oxygen octahedra niobate.These hard masss have higher hardness and bigger proportion, and color and luster, outward appearance are all more true to nature, but, hard mass and most natural gemstone all are to produce beautiful color and glittering and translucent effect by reflection or refracted ray at present, and self do not have emitting characteristics, can not embody its existence at the dark place.Have only very rare a part of natural gemstone if any jade because its specific build environment makes it have faint fluorescent characteristic, and people more have a kind of distinctive mystique to this jewel, and quantity is very rare, thereby also just it is more treasured.
The contriver who has is in order to pursue the illumination effect of jewel, invented " Luminous precious stone jewelry ", be disclosed in the Chinese patent (application number) 90 2 20241, it is to coat luminescent powder in a side of jewel or the base of jewellery, the single-shot luminance brightness is not low, time of persistence short for this jewellery, and luminous not nature.In addition, also have the contriver to utilize the phosphor material of the steady persistence high brightness that occurs in recent years, use the mode of resin bonding the bonding one-tenth integral material of phosphor powder to be embedded on the jewelry such as jewellery.Though that but this material has the lax hardness of characteristics of luminescence quality is low, can't polish, ornamental poor, therefore some fundamental characteristics that do not have jewel can not be referred to as jewel.
In recent years succeeded in developing multiple steady persistence high brightness phosphor material, the application of morning is a Chinese patent 91 1 07337 in patent documentation, March 9 1991 applying date, open day on August 14th, 1991, the applicant: Fudan University, this invention is added the long after glow luminous material that the activated by rare earth elements agent constitutes for a kind of alkali earth metal aluminate.The inventor also studies for a long period of time to steady persistence high brightness phosphor material, particularly to carrying out a large amount of research with rare earth element as the alkali earth metal aluminate class luminescent material of activator and additional activation agent, has applied for multinomial patent of invention for this reason.This class luminescent material is compared with traditional zinc sulphide fluorescent material, has the original intensity height, and time of persistence is long, characteristics such as physics and steady chemical structure.
The inventor through experiment repeatedly, utilizes existing phosphor material through having machined the present invention further on to steady persistence high brightness phosphor material and synthetic jewel Study on Technology basis finally.
The purpose of this invention is to provide a kind of synthetic jewel and manufacture method thereof with characteristics of luminescence.
The object of the present invention is achieved like this:
1. one kind from worker's synthetic luminous gem; it is characterized in that with the boracic alkaline earth aluminate be matrix; rare earth element is that the long Persistence and high brightness fluorescent materials of activator is a raw material; the monoclinic system crystal body of under the protection environment, making through the High Temperature High Pressure sintering; its Mohs' hardness is 6～7; proportion is 6～8, has phosphorescent characteristics.
2. preceding paragraph 1 described luminous gem is characterized in that described raw material is general expression MNAL
2-xB
xO
4The sintered body of expression constitutes, and in the formula, M represents alkaline-earth metal, and N represents rare earth element, 0.1≤x≤1.
3. preceding paragraph 2 described luminous gems is characterized in that M is a strontium in the general expression, and N is an europium.
4. the manufacture method of the luminous gem of preceding paragraph 1 described synthetic is characterized in that this method comprises following operation:
(1) getting described raw material is positioned in the crucible;
(2) described crucible is put people's pressure electric furnace, in reducing atmosphere, furnace temperature was warmed up to 1550 ℃～1700 ℃ by room temperature gradually through 5～8 hours, kept 2～3 hours, naturally cooled to 200 ℃ then in stove;
(3) sintered body is taken out from electric furnace be cooled to room temperature;
(4) the sintered compact sanding and polishing is made diamond material.
5. the manufacture method of the luminous gem of preceding paragraph 4 described synthetic is characterized in that reducing atmosphere described in the described operation (2) is with the direct method of reducing of powdered carbon, buries crucible in people's powdered carbon.
6. the manufacture method of the luminous gem of preceding paragraph 4 described synthetic is characterized in that the raw material in the described operation (1) is pulverous luminescent material.
7. the manufacture method of the luminous gem of preceding paragraph 4 described synthetic is characterized in that the raw material in the described operation (1) is the luminescent material sintered body without crushing screening.
8. the preparation method of the luminous gem of preceding paragraph 4 described synthetic is characterized in that in the operation (2), and the electric furnace internal pressure is 2 above normal atmosphere.
The present invention is described in detail below in conjunction with embodiment.
The raw material of synthetic jewel of the present invention is the phosphor material that utilizes the steady persistence high brightness that occurs in recent years, it mainly by rare earth elements europium as activator or/and the sintered body that other rare earth elements constitute as the alkali earth metal aluminate of additional activation agent, it is long that this class phosphor material has a time of persistence than traditional zinc sulphide phosphor material, the original intensity height, characteristics such as steady chemical structure.The visual time of persistence of general this class material, original intensity was 2000～5500 (mcd/m more than 20～30 hours
2) about, characteristics such as acid-alkali-corrosive-resisting are also very good.
The patent application in recent years of steady persistence high brightness phosphor material is more, wherein, and Chinese patent 91 1 07337, open day on August 14th, 1991, applicant Fudan University, the long after glow luminous material of this invention, contain components such as strontium, europium, aluminium, and the boron oxide component, its chemical constitution formula is: m (Sr
1-xEu
x) O.nAl
2O
3.yB
2O
31≤m≤5,1≤n≤8,0.001≤y≤0.35. wherein
The Chinese patent (application number) 96 1 00981.0 of inventor application, priority date on July 17th, 95, name is called " long Persistence and high brightness fluorescent materials and preparation method thereof ", and the chemical expression of its luminescent material is: MNAL
2-xB
xO
4, in the formula, M represents alkaline-earth metal, and N represents rare earth element, and 0.1≤x≤1. particularly M is a strontium, and N is an europium.The part of strontium can be by Mg in addition, Ca, and at least a alkaline-earth metal is replaced among the Ba; The part of europium can be by La, Ce, and Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, at least a metal is replaced among Mn or the Bi.In the preparation with described raw material pulverizing, mix after sintering at high temperature, in reducing atmosphere, reduce then, make the monoclinic system crystal body.Luminescent material according to the method preparation of above-mentioned application record has the good characteristics of luminescence and persistence characteristic, therefore, is raw material with the luminescent material of above-mentioned application all in embodiments of the present invention.Obviously, the present invention is not limited to a certain luminescent material, and the luminescent material with above-mentioned characteristic all is suitable for doing raw material of the present invention.
The embodiment of the invention is simple in order to explain, and the luminescent material that all adopts following composition proportion and preparation method is a raw material:
SrCO
3?71.6g；Al
2O
3?50.5g；H
3BO
3?0.3g；
Activator and additional activation agent: Eu
2O
30.88g; Nd
2O
30.84g; Dy
2O
30.93g;
After these raw material pulverizing, thorough mixing is placed in the crucible then.This crucible is placed electric furnace, and 800 ℃～1400 ℃ kept 3 hours under reductive condition, kept 2 hours at 1300 ℃ again, took out from electric furnace after being cooled to 200 ℃ thereafter, as the raw material of artificial synthetic luminous gem.
Embodiment 1:
Get described luminescent material after crushed, cross 300 mesh sieves and obtain luminescent material powder, get this powder 200g and put into crucible.This crucible is put into electric furnace, under reducing atmosphere, being about to crucible buries in people's powdered carbon, heat for electric furnace gradually, make furnace temperature be heated to 1550 ℃ through 6 hours, and kept 3 hours from room temperature, electric furnace is lowered the temperature naturally then, from electric furnace, take out crucible after cooling to 200 ℃, continue cool to room temperature and in crucible, take out sintered body, make luminous gem sample of the present invention [1] through sanding and polishing.
Embodiment 2
Get described luminescent material after crushed, cross 400 mesh sieves and obtain luminescent material powder, get this powder 200g and put into crucible.This crucible is put into electric furnace, under reducing atmosphere, make furnace temperature be heated to 1650 ℃ gradually through 7 hours from room temperature, and kept 3 hours, electric furnace is lowered the temperature naturally then, from electric furnace, take out crucible after cooling to 200 ℃, continue cool to room temperature and in crucible, take out sintered body, make luminous gem sample of the present invention [2] through sanding and polishing.
Embodiment 3
Get described luminescent material after crushed, cross 400 mesh sieves and obtain luminescent material powder, get this powder 200g and put into crucible.This crucible is put into electric furnace, under reducing atmosphere, make furnace temperature be heated to 1700 ℃ gradually through 8 hours from room temperature, and kept 3 hours, electric furnace is lowered the temperature naturally then, from electric furnace, take out crucible after cooling to 200 ℃, continue cool to room temperature and in crucible, take out sintered body, make luminous gem sample of the present invention [3] through sanding and polishing.
Embodiment 4
Get described luminescent material sintered compact, promptly luminescent material burns till the back without the block of pulverizing, and gets this block 200g and puts into crucible.This crucible is put into electric furnace, under reducing atmosphere, make furnace temperature be heated to 1700 ℃ gradually through 8 hours from room temperature, and kept 3 hours, electric furnace is lowered the temperature naturally then, from electric furnace, take out crucible after reducing to 200 ℃, continue in crucible, to take out sintered body behind the cool to room temperature, make luminous gem sample of the present invention [4] through sanding and polishing.
Embodiment 5
Get described luminescent material sintered compact block 200g and put into crucible, this crucible is put into electric furnace, under reducing atmosphere, make furnace temperature be heated to 1700 ℃ gradually through 8 hours from room temperature, pressurization in the electric furnace simultaneously, pressure increases to 2 normal atmosphere gradually from standard atmospheric pressure, and kept 3 hours, electric furnace is lowered the temperature naturally then, the stove internal gas pressure reduces gradually, and furnace temperature is reduced to 200 ℃, and the stove internal gas pressure recovers to take out crucible behind the normal pressure from electric furnace, continue in crucible, to take out sintered body behind the cool to room temperature, make luminous gem sample of the present invention [5] through sanding and polishing.
Physical propertys such as the hardness of luminous gem [1]～[5] that generate under different condition in the foregoing description, density are tested, and test result is seen " table 1 ".The experiment repeatedly the invention process from the test result and the inventor, think:
The luminous gem of making according to present method does not change the crystalline structure of luminescent material, so its characteristics of luminescence is identical with luminescent material;
Sintering temperature, pressure are high more in preparation luminous gem of the present invention, and the jewel hardness of formation, proportion (density) are also big more, but after temperature surpassed 1700 ℃, the product of generation can become fragile, and influences the quality of jewel.
The size of raw material granularity also influences the quality of jewel, granularity density, the hardness of miscellaneous goods more is big more, but undersized can obviously influence the luminescent properties of product, and block raw material utilizes this raw material to make that the quality of product is higher owing to self have certain density, hardness;
The intensification of furnace temperature, temperature lowering curve can have influence on bubble and other physical propertys in the jewel, so temperature variation slowly is very important, and the conversion of air pressure also has same requirement.
Luminous gem quality of the present invention is hard, and body colour is gorgeous various, can be processed into various jewelrys, again can be luminous for a long time at night or dark place, and therefore, it will be subjected to liking of people, becomes a kind of new hard mass kind.
Change some composition and proportioning in the luminescent material, can generate the luminescent material of different colours, use these materials can produce synthetic jewel of all kinds, its preparation method is identical, does not repeat them here.
Advantage of the present invention is: the synthetic jewel has the general characteristic of natural gemstone, the high steady chemical structure of hardness; The simple control easily of production technique, less demanding to production unit, the yield rate height; Particularly this product has unique characteristics of luminescence, and luminosity is that other natural gemstones and hard mass are incomparable time of persistence.
Above-described embodiment is a kind of specific implementation in the technical solutions of the utility model, rather than to qualification of the present utility model, those of ordinary skill can be made various changes according to the scope of the technical scheme that claim limited." table 1 "
Claims (8)
1. the luminous gem of a synthetic is characterized in that with the boracic alkali earth metal aluminate be matrix, and rare earth element is that the long Persistence and high brightness fluorescent materials of activator is a raw material, described luminous gem is the monoclinic system crystal body, Mohs' hardness is 6-7, and proportion is 6-8, has phosphorescent.
2. luminous gem as claimed in claim 1 is characterized in that described raw material is general expression MNAl
2-xB
xO
4The sintered compact of expression constitutes, and in the formula, M represents alkaline-earth metal, and N represents rare earth element, 0.1≤X≤1.
3. the luminous gem of synthetic as claimed in claim 2 is characterized in that the M in the general expression is a strontium, and N is an europium.
4. the manufacture method of the luminous gem of the synthetic described in the claim 1 is characterized in that this method comprises following operation:
(1) getting described raw material is positioned in the crucible;
(2) described crucible is put into the pressure electric furnace, in reducing atmosphere, furnace temperature heated up 1550-1700 ℃ by room temperature gradually through 5-8 hour, kept 2-3 hour, naturally cooled to 200 ℃ then in stove;
(3) sintered body is taken out from electric furnace be cooled to room temperature;
(4) the sintered body sanding and polishing is made diamond material.
5. the manufacture method of the luminous gem of synthetic as claimed in claim 4 is characterized in that the reducing atmosphere described in the operation (2) is with the direct method of reducing of powdered carbon, imbeds crucible in the powdered carbon.
6. the manufacture method of the luminous gem of synthetic as claimed in claim 4 is characterized in that the described raw material in the described operation (1) is pulverous luminescent material.
7. the manufacture method of the luminous gem of synthetic as claimed in claim 4 is characterized in that the raw material described in the operation is the luminescent material sintered body without crushing screening.
8. the manufacture method of the luminous gem of synthetic as claimed in claim 4 is characterized in that in the described operation (2), and the electric furnace internal pressure is 2 above normal atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106373A CN1108282C (en) | 1996-06-07 | 1996-06-07 | Artificial synthetic luminous gem and its producing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106373A CN1108282C (en) | 1996-06-07 | 1996-06-07 | Artificial synthetic luminous gem and its producing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1186789A CN1186789A (en) | 1998-07-08 |
| CN1108282C true CN1108282C (en) | 2003-05-14 |
Family
ID=5119112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96106373A Expired - Fee Related CN1108282C (en) | 1996-06-07 | 1996-06-07 | Artificial synthetic luminous gem and its producing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1108282C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442816B (en) * | 2011-10-17 | 2013-12-18 | 王蕴渔 | Synthetic grey-white jade and manufacturing method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3294699A (en) * | 1962-02-08 | 1966-12-27 | Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh | Luminescent europium activated strontium aluminate |
| CN1053807A (en) * | 1991-03-09 | 1991-08-14 | 复旦大学 | Long-lasting phosphorescent materials and their preparation |
-
1996
- 1996-06-07 CN CN96106373A patent/CN1108282C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3294699A (en) * | 1962-02-08 | 1966-12-27 | Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh | Luminescent europium activated strontium aluminate |
| CN1053807A (en) * | 1991-03-09 | 1991-08-14 | 复旦大学 | Long-lasting phosphorescent materials and their preparation |
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| Publication number | Publication date |
|---|---|
| CN1186789A (en) | 1998-07-08 |
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Granted publication date: 20030514 Termination date: 20100607 |