CN1270151A - Luminous jade and preparing process thereof - Google Patents
Luminous jade and preparing process thereof Download PDFInfo
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Abstract
A luminous jade has a chemical formula: aM beta.bM'beta.cSiO2.dAl2O3.eEu2O3.fB2O3.gLn2O3.hZrO2, where M is one or more of Ca, Sr, Ba, Mg, Zn and Cd; M' is one or more of Be, Mg, Zn and Cd; beta is one or both of O and S; Ln is one or more of Ce, Pr, La, Dy, Ho, Nd, Er, Bi, Ga, Sb, Lu, Y, Mn, Mo, Cr, Sn, Cu and Tm; and a,b,c,d,e,f,g and h are mole ratios. It is prepared through mixing and high-temp sintering, and features compact mass, high toughness, and long luminous time after radiated by light.
Description
What the present invention relates to is artificial luminescent jade technology, particularly about artificial luminescent jade and the manufacture method thereof of holding light-luminescent properties arranged.
Jade is meant hardness below 3 degree above 7 are spent, quality densification, tough and tensile natural crystal, through being processed into various artworks, have very high view and admire, use and reserve value.But jade is natural goods, resource-constrained, and it costs an arm and a leg and embarrasses popular acceptance in addition.In fact this cup people have not seen real luminous beautiful cup in the good wine of grape described in the classic poetry luminous wine glass, and the beautiful made wineglass of the fine white tallow jade that NORTHWEST CHINA is produced, Jiuquan jade, Wushan is not luminous, be that beautiful wall of cup is thin, transparent, lamp has the noctilucence effect under shining.Imitative in recent years beautiful product constantly occurs on market, also constantly improves to some extent qualitatively.Mostly be to be that main raw material is made with macromolecular material.For make the technology for producing artificial jadeware product on weight and texture near natural jade, add stone flour therein.Zhejiang Province refreshing carving company adding embedded photoluminescent material is made the imitative jade carving arts with noctilucence effect, and (ZL 92105254.2, ZL 93110823.1, ZL 931009227.2 etc.) have much ornamental value, yet these imitative beautiful products are that macromolecular material is polymerized, on hardness, rigidity, feel, still have the vestige of plastics, not ideal enough on the emulation degree.Chinese patent (publication number) CN1186789A has described a kind of synthetic jewel and manufacture method thereof, and its raw material is general expression MNAl
2-xB
xO
4The sintered body of expression constitutes, M represents alkaline-earth metal in the formula, N represents rare earth element, 0.1≤x≤1. its synthesis temperature is 1550-1700 ℃, pressure is 2 above normal atmosphere, is two steps to burn till (the first step synthesis material), the material of its description is not fully aware of, the synthesis temperature height, and raw material variety is single, and the luminous gem of making can not reach the performance of its description.
The objective of the invention is to adopt Inorganic Chemicals,, synthesize performance at a lower temperature more near natural jade, and efficient luminous multiple artificial luminous jade can be arranged after illumination by practical and advanced sintering process.
Concrete scheme of the present invention is:
1. luminous jade of the present invention is to contain different kinds of ions activated silicate aluminate or sulfide luminescent material, and its main chemical constitution expression is:
aMβ·bM’β·cSiO
2·dAl
2O
3·eEu
2O
3·fB
2O
3·gLn
2O
3·hZrO
2
Wherein: M is one or more among Ca, Sr, Ba, Mg, Zn, the Cd
The combination of element;
M ' is the combination of one or more elements among Be, Mg, Zn, the Cd;
β is the combination of one or both elements among O, the S;
Ln be Ce, Pr, La, Dy, Ho, Nd, Er, Bi, Ga, Sb,
A kind of among Lu, Y, Mn, Mo, Cr, Sn, Cu, the Tm or
The combination of multiple element;
A, b, c, d, e, f, g, h are respectively mole coefficients,
0.6≤a≤6；0≤b≤4；0≤c≤3；0≤d≤8；0.00001≤e≤0.15；
0≤f≤0.4；0＜g≤0.2；0≤h≤0.3。
2. as 1 described artificial luminescent jade, can realize the orchid, blue green, green, Yellow luminous of jade, its main chemical constitution expression is:
AMObM ' OcSiO
2DAl
2O
3EEu
2O
3FB
2O
3GLn
2O
3HZrO
21.5≤a≤3.5 wherein; 0.5≤b≤1.5; 1.5≤c≤2.5; 0≤d≤0.4.
3. as 1 described artificial luminescent jade, can realize that yellow-green colour is luminous, its main chemical constitution expression is:
AMOcSiO
2DAl
2O
3EEu
2O
3FB
2O
3GLn
2O
3HZrO
20.6≤a≤1.4 wherein; B=0; 0≤c≤0.3; 0.7≤d≤1.3,
0≤f≤0.1。
4. as 1 described artificial luminescent jade, can realize blue green emitting, the expression of its main chemical constitution is:
AMOcSiO
2DAl
2O
3EEu
2O
3FB
2O
3GLn
2O
3HZrO
23.4≤a≤4.6 wherein; B=0; 0≤c≤0.4; 6.5≤d≤7.5.
5. as 1 described artificial luminescent jade, described different kinds of ions activated silicate is main luminescent material, and its main chemical constitution expression is:
aMO·bM’O·cSiO
2·fB
2O
3：Eu
xLn
y
Wherein: M is the combination of one or more elements among Ca, Sr, the Ba;
M ' is the combination of one or more elements among Be, Mg, Zn, the Cd;
Ln be Ce, Pr, La, Dy, Ho, Nd, Bi, Sb, Mn, Sn,
The combination of one or more elements among the Tm;
A, b, c, f, x, y are respectively mole coefficients,
0.6≤a≤6；0≤b≤4；1≤c≤3；0＜f≤0.4；
0.00001≤x≤0.15；0＜y≤0.2。
6. as 1 described artificial luminescent jade, described different kinds of ions activated aluminate is main luminescent material, and its main chemical constitution expression is: aMOdAl
2O
3FB
2O
3: Eu
xLn
y
Wherein: M is the combination of one or more elements among Ca, Mg, Sr, Ba, the Zn;
A, d, f, x, y are respectively mole coefficients, 0.6≤a≤6;
0.5≤d≤8.0；0.001≤f＜0.1；00001≤y≤0.2。
7. as 1 described artificial luminescent jade, described polyion activated sulfide is main luminescent material, and its main chemical constitution expression is: (Ca
1-zSr
z) S:Eu
xLn
y
Wherein: Ln is one or more elements among Pr, Tm, Y, the Mn
Combination;
X, y, z are respectively mole coefficients,
0≤z≤1.0；0.00001≤x≤0.15；0＜y≤0.2。
8. as the luminescent material of 5 described different kinds of ions activated based on silicate, main chemical constitution expression is:
M
2MgSi
2O
7：Eu
xLn
y
Wherein: M is the combination of one or more elements among Ca, Sr, the Ba;
Ln is one or more elements among La, Dy, Ho, Nd, Bi, the Sn
Combination;
0.00001≤x≤0.15；0＜y≤0.2。
9. as the luminescent material of 5 described different kinds of ions activated based on silicate, main chemical constitution expression is:
M
3MgSi
2O
8：Eu
xLn
y
Wherein: M be among Ca, Sr, the Ba one or more elements
Combination;
Ln is one or more elements among La, Dy, Ho, Nd, Bi, the Sn
Combination;
0.00001≤x≤0.15；0＜y≤0.2。
10. as the luminescent material of 6 described different kinds of ions activated based on aluminate, its main chemical constitution expression is: MAl
2O
4: Eu
xLn
yWherein: M is the group of one or more elements among Ca, Mg, Sr, Ba, the Zn
Close.
11. as the luminescent material of 6 described different kinds of ions activated based on aluminate, its main chemical structure expression is: M
4Al
14O
25: Eu
xLn
yWherein: M is one or more element combinations among Ca, Mg, Sr, Ba, the Zn.
In the above-mentioned chemical constitution expression formula, when a, b, c, the variation of d value, M, M ', the element of β representative and the difference of element combinations, it is luminous to make jade produce different colours.If: 1.5≤a≤3.5,0.5≤b≤1.5,1.5≤c≤2.5,0≤d≤0.4, β is an oxygen element, it is blue, blue green, green, Yellow luminous that jade is produced; At this moment, if M is Sr, M ' is Mg, and the main chemical constitution composition that changes jewel according to a value is Sr
2MgSi
2O
7Or Sr
3MgSi
2O
8If M is Sr, the Ca element of different ratios, can realize that then orchid is green, green, Yellow luminous, the main chemical constitution composition of jade is (SrCa)
2MgSi
2O
7Or (SrCa)
3MgSi
2O
8If 0.6≤a≤1.4,0≤b≤0.1,0≤c≤0.3,0.7≤d≤1.3, β is an oxygen element, and M is the Sr element, and it is luminous to make jade produce yellow-green colour, and the main chemical constitution composition of jade is SrAl
2O
4If M is the Ca element, also can realize blue violet light, the main chemical constitution composition of jade is CaAl
2O
4If 3.4≤a≤4.6,0≤b≤0.1,0≤c≤0.4,6.5≤d≤7.5, β is an oxygen element, and M is the Sr element, can make jade produce blue green emitting, the main chemical constitution composition of jade Sr
4Al
14O
25If 0.5≤a≤1.5,0≤b≤0.2,0≤c≤0.1,0≤d≤0.1, β is an element sulphur, and M is that Ca can realize emitting red light, and main chemical constitution composition is CaS.
Experiment showed, that the adding of Zr element can increase the hardness of jade, the variation of Al, Si amount of element has tangible influence to density, chemical stability, the machining property (as intensity etc.) of jade.
Raw materials used during products production of the present invention is the oxide compound, oxyhydroxide, carbonate, sulfide etc. of above-mentioned element; Luminescent materials such as also available different kinds of ions activated aluminate, silicate, sulfide.Calculate the raw material consumption by required element proportioning, mix, moulding, high-temperature pressure or pressurization, the one or many sintering forms.Its concrete steps are:
If adopt disposable burning till, the ratio weighing contains the raw material of above-mentioned element on request, and after mixing, water or binding agent are piled up or compression moulding, after the oven dry, adopts gradually and heats up, and under reducing atmosphere, generally adopts H
2, H
2+ N
2Or CO was in 1100-1550 ℃ of sintering 0.5-24 hour; Maybe will contain the raw material weighing in proportion of above-mentioned element, mix, in hot pressing furnace or under the hot isostatic pressing furnace reduction atmosphere, generally adopt H
2, H
2+ N
2Or CO is under 600-1450 ℃, hot pressing 0.5-4 hour, and pressure 5-300MPa.
If adopt twice firing, after will containing the raw material of above-mentioned element weighing mixing in proportion, in stove 800-1550 ℃, elder generation's pre-burning 1-20 hour with burned material grinding, sieve back water or binding agent accumulation or compression moulding, heats up gradually, under 1000-1550 ℃, in reducing atmosphere, as H
2, H
2+ N
2Or CO sintering 0.5-10 hour; Maybe will contain above-mentioned element raw material weighing in proportion, mix after, in stove 800-1550 ℃, first pre-burning 1-20 hour, with burned material grind, sieve the back in heat (waiting quiet) is pressed stove in reducing atmosphere, as H
2, H
2+ N
2Or CO pressed sintering 0.5-4 hour in 600-1450 ℃ of heat (waiting quiet), pressure 5-300MPa.
Certainly, can also be with the raw material that contains above-mentioned element after weighing mixes in proportion, in stove 800-1300 ℃, first pre-burning 10-40 hour, in reducing atmosphere, produce monocrystalline with conventional crystal pulling method or zone melting method again, produce jewel truly.
The manufacture method of this luminous jade can be by following scheme implementation: 1. the manufacture method of the described artificial luminescent jade of above-mentioned 1-11, be that ratio by the requirement of chemical constitution expression formula will contain the raw materials of compound of required element after grinding, mixing, moulding, under reducing atmosphere, through 600-1550 ℃, under the 0-400MPa pressure, carry out once or double sintering 0.5-30h forms; The oxide compound that the described raw materials of compound that contains required element is this element, oxyhydroxide, carbonate, sulfide etc.2. as the manufacture method of artificial luminescent jade as described in 1, the described raw materials of compound that contains required element can be different kinds of ions activated aluminate, silicate or sulfide luminescent material and Al
2O
3, SiO
2, ZrO
2Or contain the compound of this oxide compound; Three kinds of oxide compounds can use wherein one or more; The weight percent that its usage quantity accounts for luminescent material is: Al
2O
30-10%
SiO
2????0-8％
ZrO
2????0-5％
And its consumption sum is not more than 10%3. manufacture method as 1 described artificial luminescent jade, is the raw material that ratio weighing on request contains above-mentioned element, after mixing, water or binding agent are piled up or compression moulding, after the oven dry, adopt gradually and heat up, under reducing atmosphere, generally adopt H
2, H
2+ N
2Or CO was in 1100-1550 ℃ of sintering 0.5-24 hour.4. as the manufacture method of artificial luminescent jade as described in 1, be to contain the raw material weighing in proportion of above-mentioned element, to mix, under hot pressing or hot isostatic pressing furnace reduction atmosphere, generally adopt H
2, H
2+ N
2Or CO is under 600-1450 ℃, hot pressing or HIP sintering 0.5-4 hour, and pressure 5-300MPa.5. as the manufacture method of artificial luminescent jade as described in 1, be the raw material weighing in proportion that will contain above-mentioned element, mix after, in stove 800-1550 ℃, elder generation's pre-burning 1-20 hour, with burned material grinding, sieve back water or binding agent accumulation or compression moulding, heat up gradually, under 1000-1550 ℃, in reducing atmosphere, as H
2, H
2+ N
2Or CO sintering 0.5-10 hour.6. as the manufacture method of artificial luminescent jade as described in 1, be the raw material weighing in proportion that will contain above-mentioned element, mix after, in stove 800-1550 ℃, first pre-burning 1-20 hour, with burned material grind, sieve the back hot pressing or etc. in the static pressure stove in reducing atmosphere, as H
2, H
2+ N
2, CO is in 600-1450 ℃ of hot pressing or HIP sintering 0.1-4 hour, pressure 5-300MPa.7. as the manufacture method of artificial luminescent jade as described in 1, be the raw material weighing in proportion that will contain above-mentioned element, mix after, in stove 800-1200 ℃, first pre-burning 10-40 hour, under reducing atmosphere, produce monocrystalline with conventional crystal pulling method or zone melting method again.
This jade of making, hardness are between the 3-7 degree, and density is 2.5-4.6g/cm
3, its quality densification, exquisiteness, tough and tensile are as then gentle more smooth, bright and clean through polishing.In the dark can be luminous after illumination, according to the difference of combination of materials, can present 1-100 hour afterglow.Luminous afterglow intensity testing method is the thin slice that the luminous jade that will make is polished into 10mm, in the darkroom, deposit more than 10 hours, taking-up places standard D65 light source under 1000LX illumination, and irradiation 10min tries its time dependent luminous intensity with the glorious degrees instrumentation.
The present invention compared with prior art because jade of the present invention is to form with the inorganic raw material sintering, more near natural jade, the while has more luminous after illumination on its quality and the sense organ, makes the luminous jade of multiple color.
Example 1. Yellow luminous jades
Choose a=2.0, b=1.1, c=1.8, d=0.01, e=0.03, f=0.1, g=0.05, h=0,
M＝Sr
0.05Ca
0.95，M’＝Mg
0.95Zn
0.05，β＝0
Ln＝Dy
0.95Sb
0.05
| Raw material | Molecular weight | Mol ratio | Weight (g) |
| SrCO 3 | 147.62 | ?2.0×0.05 | ?14.76 |
| CaCO 3 | 100.0 | ?2.0×0.95 | ?190.00 |
| MgO | 40.31 | ?1.1×0.95 | ?42.12 |
| ZnO | 81.31 | ?1.1×0.05 | ?4.47 |
| SiO 2 | 60.09 | ?1.8×1.0 | ?108.16 |
| Al 2O 3 | 102.0 | ?0.01×1.0 | ?1.02 |
| ?Eu 2O 3 | ?352 | ?0.03×1.0 | ?10.56 |
| ?B 2O 3 | ?69.62 | ?0.1×1.0 | ?6.96 |
| ?Dy 2O 3 | ?374 | ?0.05×0.95 | ?17.77 |
| ?Sb 2O 3 | ?291.6 | ?0.05×0.05 | ?0.73 |
Above-mentioned raw materials being weighed by weight, behind the porphyrize mixing, under 10MPa pressure, be pressed into right cylinder, be encased in the plasticity-mould, through the further compacting of 200MPa isostatic cool pressing, is 90%N in atmosphere
2+ 10%H
2The reducing atmosphere stove in, be warming up to 1150 ℃ gradually, constant temperature was reduced to room temperature gradually and is promptly got Yellow luminous artificial luminescent jade after 5 hour.Example 2. blue look luminous jades
Choose a=2.2, b=1.0, c=2.0, d=0.04, e=0.03, f=0.05, g=0.03, h=0.01, M=Sr
0.95Ca
0.05, M '=Mg, Ln=Dy
0.90Bi
0.10, β=0
Above-mentioned raw materials is weighed by weight, behind the porphyrize mixing, be encased in the hot pressing furnace mould, the ventilation atmosphere is 95%N
2+ 5%H
2Reducing atmosphere, heat up gradually and be forced into 1000 ℃, under the 30MPa, sintering 1 hour is reduced to the artificial luminescent jade that room temperature promptly gets luminous blue look gradually.Example 3. avy blue luminous jades
| Raw material | Molecular weight | Mol ratio | Weight (g) |
| SrO | ?103.62 | ??2.2×0.95 | ?216.57 |
| CaO | ?56.08 | ??2.2×0.05 | ?6.17 |
| MgO | ?40.31 | ??1.0×1.0 | ?40.31 |
| SiO 2 | ??60 | ??2.0×1.0 | ??120 |
| Al 2O 3 | ??102.0 | ??0.04×1.0 | ??4.08 |
| Eu 2O 3 | ??352 | ??0.03×1.0 | ??10.56 |
| B 2O 3 | ??69.62 | ??0.05×1.0 | ??3.48 |
| Dy 2O 3 | ??374 | ??0.03×0.9 | ??10.10 |
| Bi 2O 3 | ??466 | ??0.03×0.1 | ??1.4 |
| ZrO 2 | ??123.22 | ??0.01×1.0 | ??1.23 |
Choose a=3.2, b=0.8, c=2.0, d=0, e=0.01, f=0.05, g=0.03, h=0,
M＝Sr，M’＝Mg，Ln＝Nd
0.95La
0.05，β＝0
| Raw material | Molecular weight | Mol ratio | Weight (g) |
| SrO | ?103.62 | ?3.2×1.0 | ?331.58 |
| MgO | ?40.31 | ?0.8×1.0 | ?32.25 |
| SiO 2 | ?60 | ?2.0×1.0 | ?120 |
| Eu 2O 3 | ?352 | ?0.01×1.0 | ?3.52 |
| B 2O 3 | ?69.62 | ?0.05×1.0 | ?3.48 |
| Nd 2O 3 | ?336.4 | ?0.03×0.95 | ?9.59 |
| La 2O 3 | ?325.8 | ?0.03×0.05 | ?0.49 |
Above-mentioned raw materials is weighed by weight, behind the porphyrize mixing, at logical H
2High Temperature Furnaces Heating Apparatus in 1300 ℃ of first sintering 4 hours, after the cooling with block sintered compact porphyrize, cross 400 eye mesh screens after, with the aqueous solution that adds CMC the powder that sieves is compacted into definite shape, after the oven dry, at logical N
2High Temperature Furnaces Heating Apparatus in, be warming up to 1420 ℃ gradually, constant temperature is reduced to the artificial luminescent jade that room temperature promptly gets luminous avy blue after 5 hours gradually.Example 4. blue green emitting jades
Choose a=4.0, b=0.05, c=0, d=7.0, e=0.01, f=0.03, g=0.01, h=0.05, M=Sr
0.85Ca
0.15, M '=Zn, Ln=Dy
0.9La
0.1, β=0
| Raw material | Molecular weight | Mol ratio | Weight (g) |
| ?SrO | ?103.62 | ?4.0×0.85 | ?352.31 |
| ?CaO | ?56.08 | ?4.0×0.15 | ?33.65 |
| ?ZnO | ?81.31 | ?0.05×1.0 | ?4.07 |
| ?Al 2O 3 | ?102 | ?7.0×1.0 | ?714 |
| ?Eu 2O 3 | ?352 | ?0.01×1.0 | ?3.52 |
| ?B 2O 3 | ?69.62 | ?0.03×1.0 | ?2.09 |
| ?Dy 2O 3 | ?374 | ?0.01×0.9 | ?3.37 |
| ?La 2O 3 | ?325.8 | ?0.01×0.1 | ?0.33 |
| ?ZrO 2 | 123.22 | ?0.05×1.0 | ?6.16 |
Above-mentioned raw materials is weighed by weight, behind the porphyrize mixing, at logical N
2In the High Temperature Furnaces Heating Apparatus of+CO in 1450 ℃ of sintering 4 hours, after the cooling with block sintered compact porphyrize, cross 300 eye mesh screens after, screen underflow is put into the hot pressing furnace mould, at N
2Heat up gradually under the atmosphere and be forced into 1200 ℃, be incubated 2 hours, pressure is 30MPa, reduces to room temperature gradually and promptly gets luminous blue green artificial luminescent jade.Example 5. blue violet light jades
Choose a=1.0, b=0, c=0, d=1.0, e=0.01, f=0.01, g=0.02, h=0,
M＝Ca，Ln＝Nd
0.5Tm
0.5，β＝0
| Raw material | Molecular weight | Mol ratio | Weight (g) |
| ?CaCO 3 | ?100.0 | ?1.0×1.0 | ?100.00 |
| ?Al 2O 3 | ?102.0 | ?1.0×1.0 | ?102 |
| ?Eu 2O 3 | ?352 | ?0.01×1.0 | ?3.52 |
| ?B 2O 3 | ?69.62 | ?0.01×1.0 | ?0.7 |
| ?Nd 2O 3 | ?336.4 | ?0.02×0.5 | ?3.36 |
| ?Tm 2O 3 | ?385.8 | ?0.02×0.5 | ?3.86 |
Above-mentioned raw materials is weighed by weight, behind the porphyrize mixing, in air,, behind the porphyrize, adopt zone melting method, at 96%Ar+4%H in 1100 ℃ of calcinings 30 hours
2Generate the long monocrystalline of about 10mm under the atmosphere.Example 6. yellow-green colour luminous jades
Choose a=1.0, b=0, c=0.037, d=1.01, e=0.01, f=0.03, g=0.01, h=0.008, M=Sr, Ln=Dy
0.95Y
0.05, β=0
| Raw material | Molecular weight | Mol ratio | Weight (g) | |
| ????A | ?SrO | ?103.62 | ?1.0×1.0 | ?103.62 |
| ?Al 2O 3 | ?102.0 | ?1.0×1.0 | ?102 | |
| ?Eu 2O 3 | ?352 | ?0.01×1.0 | ?3.52 | |
| ?B 2O 3 | ?69.62 | ?0.03×1.0 | ?2.09 | |
| ?Dy 2O 3 | ?374 | ?0.01×0.95 | ?3.55 | |
| ?Y 2O 3 | ?225.82 | ?0.01×0.05 | ?0.11 | |
| ????B | Kaolin | ??????????????????????????????????2.0 | ||
| ?ZrO 2 | ??????????????????????????????????1.0 | |||
| Feldspar | ??????????????????????????????????2.0 | |||
Accurately take by weighing the category-A raw material by weight, behind the porphyrize mixing, at logical 90%N
2+ 10%H
2High Temperature Furnaces Heating Apparatus in, in 1350 ℃ of sintering 4 hours, after the cooling,, cross 300 mesh sieves with block sintered compact porphyrize, add less water mixing porphyrize with the category-B material that accurately takes by weighing, be molded into definite shape, dry back is at reducing atmosphere (90%N
2+ 10%H
2) in the stove, slowly be warming up to 1400 ℃, be incubated 4 hours, reduce to room temperature gradually and promptly get luminous yellowish green artificial luminescent jade.Example 7: emitting red light jade
Took by weighing red long-afterglow powder 300 grams (RO-7, Luming technology Group Co., Ltd., Dalian city produces) of 400 mesh sieves, the chemical constitution expression formula is claims 7 described CaS:Eu, Tm, Pr.Put into the hot isostatic pressing stove, at 750 ℃, 300MPa pressure kept 0.5 hour down, promptly got the emitting red light jade after the cooling.
The performance of above-mentioned example is listed in table 1.
Table 1
Annotate: fluorescent lifetime is the minimum visible diopter 0.32mcd/m of specimen intelligent eye
2Time
| Main chemical composition | Hardness | Proportion | Luminous afterglow intensity (mcd/m 2) ?10???30???60????90(min) | Fluorescent lifetime (min) | |
| Example 1 | ?Ca 2MgSi 2O 7 | ?6.5 | ?3.2 | ?200??66???30????16 | ?630 |
| Example 2 | ?Sr 2MgSi 2O 7 | ?6.2 | ?30.1 | ?210??77???40????25 | ?1875 |
| Example 3 | ?Sr 3MgSi 2O 7 | ?6.3 | ?3.1 | ?100??35???18????10 | ?1230 |
| Example 4 | ?Sr 4Al 14O 25 | ?6.2 | ?3.6 | ?598??222??117???77 | ?5940 |
| Example 5 | ?CaAl 2O 4 | ?7.1 | ?3.6 | ?46???16???8?????5 | ?362 |
| Example 6 | ?SrAl 2O 4 | ?6.9 | ?3.5 | ?625??239??123???84 | ?4756 |
Claims (18)
1. an artificial luminescent jade is characterized in that containing different kinds of ions activated silicate, aluminate or sulfide luminescent material, and its main chemical constitution expression formula is:
AM β bM ' β cSiO
2DAl
2O
3EEu
2O
3FB
2O
3GLn
2O
3HZrO
2Wherein: M is one or more among Ca, Sr, Ba, Mg, Zn, the Cd
The combination of element;
M ' is the combination of one or more elements among Be, Mg, Zn, the Cd;
β is the combination of one or both elements among O, the S;
Ln be Ce, Pr, La, Dy, Ho, Nd, Er, Bi, Ga, Sb,
A kind of among Lu, Y, Mn, Mo, Cr, Sn, Cu, the Tm or
The combination of multiple element;
A, b, c, d, e, f, g, h are respectively mole coefficients,
0.6≤a≤6；0≤b≤4；0≤c≤3；
0≤d≤8；0.00001≤e≤0.15；
0≤f≤0.4；0＜g≤0.2；0≤h≤0.3。
2. as claim 1 described artificial luminescent jade, it is characterized in that realizing the orchid, blue green, green, Yellow luminous of jade, its main chemical constitution expression is:
AMObM ' OcSiO
2DAl
2O
3EEu
2O
3FB
2O
3GLn
2O
3HZrO
21.5≤a≤3.5 wherein; 0.5≤b≤1.5; 1.5≤c≤2.5; 0≤d≤0.4.
3. as claim 1 described artificial luminescent jade, it is characterized in that realizing that yellow-green colour is luminous, its main chemical constitution expression is:
AMOcSiO
2DAl
2O
3EEu
2O
3FB
2O
3GLn
2O
3HZrO
20.6≤a≤1.4 wherein; B=0; 0≤c≤0.3; 0.7≤d≤1.3,0≤f≤0.1.
4. as claim 1 described artificial luminescent jade, it is characterized in that realizing blue green emitting that the expression of its main chemical constitution is:
AMOcSiO
2DAl
2O
3EEu
2O
3FB
2O
3GLn
2O
3HZrO
23.4≤a≤4.6 wherein; B=0; 0≤c≤0.4; 6.5≤d≤7.5.
5. as claim 1 described artificial luminescent jade, it is characterized in that described different kinds of ions activated silicate is main luminescent material, its main chemical constitution expression is:
aMO·bM’O·cSiO
2·fB
2O
3：Eu
xLn
y
Wherein: M is the combination of one or more elements among Ca, Sr, the Ba;
M ' is the combination of one or more elements among Be, Mg, Zn, the Cd;
Ln is Ce, Pr, La, Dy, Ho, Nd, Bi, Sb, Mn, Sn, Tm
In the combination of one or more elements;
A, b, c, f, x, y are respectively mole coefficients,
0.6≤a≤6；0≤b≤4；1≤c≤3；0＜f≤0.4；
0.00001≤x≤0.15；0＜y≤0.2。
6. as claim 1 described artificial luminescent jade, it is characterized in that described different kinds of ions activated aluminate is main luminescent material, its main chemical constitution expression is:
AMOdAl
2O
3FB
2O
3: Eu
xLn
yWherein, M is the combination of one or more elements among Ca, Mg, Sr, Ba, the Zn;
A, d, f, x, y are respectively mole coefficients,
0.6≤a≤6；0.5≤d≤8.0；0.001≤f＜0.1；
0.00001≤x≤0.15；0.0001≤y≤0.2。
7. artificial luminescent jade as claimed in claim 1 is characterized in that described different kinds of ions activated sulfide is main luminescent material, and its main chemical constitution expression is:
(Ca
1-zSr
z)S：Eu
xLn
y
Wherein: Ln is the combination of one or more elements among Pr, Tm, Y, the Mn;
X, y, z are respectively mole coefficients,
0≤z≤1.0；0.00001≤x≤0.15；0＜y≤0.2。
8. different kinds of ions activated as claimed in claim 5 is characterized in that based on the luminescent material of silicate main chemical constitution expression is:
M
2MgSi
2O
7：Eu
xLn
y
Wherein: M is the combination of one or more elements among Ca, Sr, the Ba;
Ln is one or more elements among La, Dy, Ho, Nd, Bi, the Sn
Combination;
0.00001≤x≤0.15；0＜y≤0.2。
9. as the luminescent material of claim 5 described different kinds of ions activated, it is characterized in that main chemical constitution expression is based on silicate:
M
3MgSi
2O
8：Eu
xLn
y
Wherein: M is the combination of one or more elements among Ca, Sr, the Ba;
Ln is one or more elements among La, Dy, Ho, Nd, Bi, the Sn
Combination;
0.00001≤x≤0.15；0＜y≤0.2。
10. as the luminescent material of claim 6 described different kinds of ions activated, it is characterized in that main chemical constitution expression is based on aluminate:
MAl
2O
4：Eu
xLn
y
Wherein: M is one or more elements among Ca, Mg, Sr, Ba, the Zn
Combination;
11. different kinds of ions activated as claimed in claim 6, is characterized by main chemical constitution expression based on the luminescent material of aluminate:
M
4Al
14O
25：Eu
xLn
y
Wherein: M is one or more elements among Ca, Mg, Sr, Ba, the Zn
Combination;
12. the manufacture method of an artificial luminescent jade, it is characterized in that to contain the raw materials of compound of required element after grinding, mixing, moulding by the ratio of chemical constitution expression formula requirement, under reducing atmosphere, through 600-1550 ℃, under the 0-400MPa pressure, carry out once or double sintering 0.5-30h forms; Described oxide compound, oxyhydroxide, carbonate, the sulfide that contains the raw materials of compound of required element for this element.
13. the manufacture method as artificial luminescent jade as described in the claim 12 is characterized in that the described raw materials of compound of required element that contains is for having different kinds of ions activated aluminate, silicate or sulfide luminescent material and Al
2O
3, SiO
2, ZrO
2Or contain the compound of this oxide compound; Three kinds of oxide compounds can use wherein one or more; Its usage quantity is that the weight percent that accounts for luminescent material is:
Al
2O
3??0-10％
SiO
2????0-8％
ZrO
20-5% and its consumption sum are not more than 10%
14. the manufacture method of artificial luminescent jade as claimed in claim 12 is characterized in that ratio weighing on request contains the raw material of above-mentioned element, after mixing, water or binding agent are piled up or compression moulding, after the oven dry, adopt gradually and heat up, under reducing atmosphere, generally adopt H
2, H
2+ N
2Or CO was in 1100-1550 ℃ of sintering 0.5-24 hour.
15. the manufacture method as artificial luminescent jade as described in the claim 12 is characterized in that mixing containing the raw material weighing in proportion of above-mentioned element, in hot pressing or hot isostatic pressing stove, under reducing atmosphere, generally adopts H
2, H
2+ N
2Or CO is under 600-1450 ℃, hot pressing or HIP sintering 0.5-4 hour, and pressure 5-300MPa.
16. manufacture method as artificial luminescent jade as described in the claim 12, it is characterized in that containing above-mentioned element raw material weighing in proportion, mix after, in stove 800-1550 ℃ first pre-burning 1-20 hour, with burned material grinding, sieve back water or binding agent accumulation or compression moulding, heat up gradually, under 1000-1550 ℃, in reducing atmosphere, as H
2, H
2+ N
2Or CO sintering 0.5-10 hour.
17. manufacture method as artificial luminescent jade as described in the claim 12, it is characterized in that containing above-mentioned element raw material weighing in proportion, mix after, in stove 800-1550 ℃, first pre-burning 1-20 hour, with burned material grind, sieve the back hot pressing or etc. in the static pressure stove in reducing atmosphere, as H
2, H
2+ N
2Or CO is in 600-1450 ℃ of hot pressing or isostatic sintering 0.1-4 hour, pressure 5-300MPa.
18. manufacture method as artificial luminescent jade as described in the claim 12, it is characterized in that containing above-mentioned element raw material weighing in proportion, mix after, in stove 800-1300 ℃, first pre-burning 10-40 hour, under reducing atmosphere, produce monocrystalline with conventional crystal pulling method or zone melting method again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB99126777XA CN1192077C (en) | 1999-04-09 | 1999-11-13 | Luminous jade and preparing process thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99105055.X | 1999-04-09 | ||
| CN99105055 | 1999-04-09 | ||
| CNB99126777XA CN1192077C (en) | 1999-04-09 | 1999-11-13 | Luminous jade and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1270151A true CN1270151A (en) | 2000-10-18 |
| CN1192077C CN1192077C (en) | 2005-03-09 |
Family
ID=25745009
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB99126777XA Expired - Fee Related CN1192077C (en) | 1999-04-09 | 1999-11-13 | Luminous jade and preparing process thereof |
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| Country | Link |
|---|---|
| CN (1) | CN1192077C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325603C (en) * | 2003-11-27 | 2007-07-11 | 上海交通大学 | Long-time afterglow luminescent silicate material and its producing method |
| CN102442816A (en) * | 2011-10-17 | 2012-05-09 | 王蕴渔 | Synthetic grey-white jade and manufacturing method thereof |
| CN104086155A (en) * | 2013-07-05 | 2014-10-08 | 孟庆洪 | Artificial colorful jade as well as production method and application thereof |
| CN104802278A (en) * | 2015-04-07 | 2015-07-29 | 浙江省地质矿产研究所 | Method for preparing jade article by adopting 3D printing technology |
| CN106010522A (en) * | 2016-06-28 | 2016-10-12 | 东台市天源荧光材料有限公司 | Dysprosium ion-doped borosilicate red nano fluorescent powder and preparation method thereof |
| CN106116537A (en) * | 2016-06-24 | 2016-11-16 | 保磁（广州）磁性材料有限公司 | Pottery lazurite, for preparing the pottery powder of lazurite and preparation thereof and application |
-
1999
- 1999-11-13 CN CNB99126777XA patent/CN1192077C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325603C (en) * | 2003-11-27 | 2007-07-11 | 上海交通大学 | Long-time afterglow luminescent silicate material and its producing method |
| CN102442816A (en) * | 2011-10-17 | 2012-05-09 | 王蕴渔 | Synthetic grey-white jade and manufacturing method thereof |
| CN102442816B (en) * | 2011-10-17 | 2013-12-18 | 王蕴渔 | Synthetic grey-white jade and manufacturing method thereof |
| CN104086155A (en) * | 2013-07-05 | 2014-10-08 | 孟庆洪 | Artificial colorful jade as well as production method and application thereof |
| CN104086155B (en) * | 2013-07-05 | 2016-08-24 | 孟庆洪 | Artificial colour jade material, its production method and application |
| CN104802278A (en) * | 2015-04-07 | 2015-07-29 | 浙江省地质矿产研究所 | Method for preparing jade article by adopting 3D printing technology |
| CN104802278B (en) * | 2015-04-07 | 2018-01-12 | 浙江省地质矿产研究所 | Method for preparing jade article by adopting 3D printing technology |
| CN106116537A (en) * | 2016-06-24 | 2016-11-16 | 保磁（广州）磁性材料有限公司 | Pottery lazurite, for preparing the pottery powder of lazurite and preparation thereof and application |
| CN106116537B (en) * | 2016-06-24 | 2019-01-11 | 保磁（广州）磁性材料有限公司 | Ceramic lapis lazuli, the powder for being used to prepare ceramic lapis lazuli and its preparation and application |
| CN106010522A (en) * | 2016-06-28 | 2016-10-12 | 东台市天源荧光材料有限公司 | Dysprosium ion-doped borosilicate red nano fluorescent powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1192077C (en) | 2005-03-09 |
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