CN1105765C - Luminous silicate-borate substance - Google Patents

Luminous silicate-borate substance Download PDF

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CN1105765C
CN1105765C CN98115943A CN98115943A CN1105765C CN 1105765 C CN1105765 C CN 1105765C CN 98115943 A CN98115943 A CN 98115943A CN 98115943 A CN98115943 A CN 98115943A CN 1105765 C CN1105765 C CN 1105765C
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metaborate
luminous
luminophore
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CN1206734A (en
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W·图斯
G·罗思
I·菲思克
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/778—Borates
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7775—Germanates
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7777—Phosphates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention relates to a plurality of activated luminescent silicate-borate compounds, which has improved luminescent properties compared with the conventional luminescence material, and has excellent stability in the impact of ultraviolet short wave radiation, so the activated luminescent silicate-borate compounds is suitable for fluorescent screen, especially low pressure vapor mercury lamp. The luminescence material of the invention is based on metaborate of rare earth metal and has a formula of: (Y,La)(1-x-y-z)Ce(x)Gd(y)Tb(z)(Mg,Zn,Cd)(1-p)Mn(p)B(5-q-s)(Al,Ga)(q)X(s)O(10), which could be used for emitting layer of fluorescent screen and low pressure vapor mercury lamp.

Description

Luminous metaborate material
The present invention relates to the luminous metaborate material after the various activation, its luminosity has improvement than traditional luminophore, and under UV shortwave irradiation, remarkable stability is arranged, so they preferably are applicable to fluorescent screen, are particularly useful for the low-voltage mercury arc lamp of all types and design.
Because the maximum wavelength of their typical terbium emissions is at about 541-543nm, the narrow compound of those emission bands preferably is used as the screen component in the luminescent lamp, especially for compact fluorescent lamp and three phosphorus pipe luminescent lamps.These compounds comprise following luminophore: according to the cerium-zirconium aluminic of AT 351635: Tb (CAT), lanthanum orthophosphate according to DE 33 26 921 and US 4,891,550: Ce, Tb (LAP) and according to the phosphoric acid lanthanum silicate of DE 32 48 809: Ce, Tb (LAPS) and according to the Y of EP 037 688 2SiO 5: Ce, Tb, they are its most important materials.All these luminophores are characteristics with its thermostability height and luminous efficiency height all.But, be its shortcoming owing to preparation requires temperature to make the production cost height at 1300-1600 ℃.
Also having a kind of is five boric acid gadolinium magnesium at the maximum luminophore of 542nm emission: Ce, Tb, describe in EP 023 068 to some extent.The feature of luminophore CBT is that the production temperature is relatively low, only is slightly higher than 1000 ℃.Because its stability is high and emissivity is good, is used for luminophore CAT, LAP, LAPS and Y 2SiO 5: Ce, Tb are of equal value, but its shortcoming to be the particle of most of fluorescence borate substance more coarse relatively, irregular and be difficult to processing.
The object of the invention is to develop a kind of luminophore, and its emissivity and processing characteristics are further improved, and can be used for standard fluorescent lamp, miniature energy-saving lamp and modern luminescent lamp.
For reaching this purpose, adopted luminophore based on the rare earth metal metaborate of following general formula according to the present invention:
(Y，La) 1-x-y-zCe xGd yTb z(Mg，Zn，Cd) 1-pMn pB 5-q-s(Al，Ga) q(X) sO 10，
Wherein X is the perhaps summation of how above-mentioned element of Si, Ge, P, Zr, V, Nb, Ta, W, y=z=p=0 0.01≤x≤1.0 in addition
0 ≤q≤ 1.0
0＜s≤1.0z=p=0 and y ≠ 0 0.01≤x≤1-y
0.02 ≤y≤ 0.80
0 ≤q≤ 1.0
0＜s≤1.0p=0 and z ≠ 0 0.01≤x≤1-y-z
0 ≤y≤ 0.98
y+z ≤ 0.99
0.01 ≤z≤ 0.75
0 ≤q≤ 1.0
0＜s≤1.0z=0 and p ≠ 0 0.01≤x≤1-y
0 ≤y≤ 0.99
0.01 ≤p≤ 0.30
0 ≤q≤ 1.0
0＜s≤1.0 p ≠ 0 and z ≠ 0 0.01≤x＜1-y-z
0 ≤y≤ 0.98
0.01 ≤z≤ 0.75
x+z ≤ 0.99
0.01 ≤p≤ 0.30
0 ≤q≤ 1.0
0 ＜s≤ 1.0
According to B.Saubat, M.Vlasse and the C.Fouassier article on solid state chemistry magazine 34 (1980) 3,271-277 pages or leaves, the complete provable space group P2 that has of these luminophors 1The monoclinic structure of/c, can with LnMgB 5O 10Quite.
According to luminophore of the present invention, emission maximum is arranged and/or wide emission band is arranged at 630nm at 542nm.Quantity and the type of peaked drift of emission band and added element X are closely related.
In more particular embodiment of the present invention, provide a kind of as above-mentioned luminous metaborate material, wherein y=z=p=0 and 0.01≤x≤0.50.
In another more particular embodiment of the present invention, provide a kind of as above-mentioned luminous metaborate material, wherein z=p=0 and 0.01≤x≤0.50 and 0.05≤y≤0.75 and x+y≤1.
In addition, the present invention also provide a kind of its diameter greater than the Radiant UV Power of 5mm, discharge greater than 200W/m 2Low-voltage mercury arc lamp, comprise one or more above-mentioned luminous metaborate materials that are arranged in this lamp discharge vessel inboard.
With reference to following each embodiment test-results, will more at large be illustrated the present invention.
List in again among table 1-table 5 and Fig. 1-Fig. 3 according to the test-results of luminophore of the present invention and each embodiment.
In table 1-table 4, " Rel.int. " is illustrated in the relative emissive porwer at emission maximum place, and " Rel.integr. " expression is the accumulation emissive porwer relatively, " q " expression relative quantum yield.The nothing of luminophore replace sample (X=0) be used as with Welker at fluorescence magazine 48/49 (1991), 53 pages and the Smets data in 16 (1987) 292 pages of chemistry and physics materials (Mater.Chem.and Phys.) are carried out the quantum yield comparative standard.
Embodiment is:
1). the luminophore according to table 2 embodiment 2 has general formula:
Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Si 0.05B 4.85O 10，
Parent material is:
H 3BO 3 5.176g
CeO 2 0.431g
Gd 2O 3 1.360g
MgCO 3(1.230g 0.05 molar excess)
SiO 2 0.038g
Tb 4O 7 0.467g
Al 2O 3 0.064g
The preparation: with oxidized form or comprise that the parent material that can be converted into oxide compound mixes with the magnesium of 0.05 molar excess and according to the excessive boric acid between 5-50% of reaction conditions according to aforementioned ratio, again in 600 ℃ down at the beginning of calcination 30 minutes, after intermediate product is ground, powder further is heated to 1035 ℃ in corundum crucible, calcination under the reductive condition of nitrogen/hydrogen mixture and under this temperature of reaction 3 hours.Wash the gained final product with water, again dried and screened in addition.The gained compound has emission maximum at the 542nm place, as shown in Figure 1.
2). the luminophore according to table 2 embodiment 5 has general formula:
Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Si 0.05B 4.80O 10，
Initial substance is:
H 3BO 3 5.176g
CeO 2 0.431g
Gd 2O 3 1.360g
MgCO 3(1.230g 0.05 molar excess)
SiO 2 0.075g
Tb 4O 3 0.467g
Al 2O 3 0.064g
Preparation: this preparation is according to the carrying out that is analogous to embodiment 2 in the table 1.The luminophor of gained has emission maximum at the 542nm place.
3). the luminophore according to table 2 embodiment 9 has general formula:
Gd 0.8Ce 0.2Mg 0.9Mn 0.1Al 0.1Si 0.05B 4.85O 10，
Initial substance is:
H 3BO 3 12.748g
CeO 2 1.291g
Gd 2O 3 5.439g
MgCO 3(3.342g 0.05 molar excess)
MnCO 3 0.4311g
Al 2O 3 0.1911g
SiO 2 0.113g
Preparation: this parent material is mixed fully, be introduced in the stove under the room temperature, in nitrogen atmosphere, be heated to 560 ℃ again.Keep taking out intermediate product afterwards in 30 minutes, ground.Again this intermediate product through fine grinding is sent in the stove, in reductive condition and 1015 ℃ of following calcinations 4 hours.After being cooled to 500 ℃ again, with the final product of this grain of 80 ℃ of water agitator treatings, and then in addition dry.The product that obtains thus has peaked emission band at the 628nm place.The puberty spectrogram is shown in Fig. 2.
4). the luminophore according to embodiment in the table 2 11 has general formula:
Gd 0.8Ce 0.2Mg 0.9Mn 0.1Si 0.1B 4.9O 10，
Initial substance is:
H 3BO 3 12.748g
CeO 2 1.291g
Gd 2O 3 5.439g
MgCO 3(3.342g 0.05 molar excess)
MnCO 3 0.431g
SiO 2 0.226g
Preparation: with all parent materials all by handling in table 2 embodiment 9 methods, but calcination 6 hours under described temperature of reaction.The luminophor that forms has peaked emission band at the 629nm place.
5). the luminophore according to embodiment in the table 314 has general formula:
Gd 0.6Ce 0.2Tb 0.2Mg 0.9Mn 0.1Al 0.1Si 0.05B 4.85O 10，
Initial substance is:
H 3BO 3 4.801g
CeO 2 0.431g
Gd 2O 3 1.360g
MgCO 3(1.113g 0.05 molar excess)
MnCO 3 0.144g
SiO 2 0.075g
Tb 4O 3 0.467g
Al 2O 3 0.064g
Preparation: this parent material is heated to 580 ℃ in nitrogen atmosphere, after keeping 30 minutes, from stove, takes out, ground.Then with the further calcination 2 hours under 1025 ℃ of reductive conditions of this intermediate product.After taking out and grinding, under same condition, carry out the calcination second time.Product after cooling and the washing has the feature line of departure of terbium and the emission band of manganese is arranged at the 628nm place at the 542nm place, as shown in Figure 3.
Table 1
Embodiment number General formula Explanation Relative intensity (%) Relative integral intensity (%) q
1 Gd 0.6Ce 0.2Tb 0.2MgAl 0.1B 4.9O 10 Heat is washed 100 100 0.93
2 Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Si 0.05B 4.85O 10 Heat is washed 103 102 0.95
3 Gd 0.6Ce 0.2Tb 0.2MgAl 0.05Si 0.05B 4.9O 10 EDTA 101 100 0.94
4 Gd 0.6Ce 0.2Tb 0.2MgSi 0.1B 4.9O 10 EDTA 99 99 0.91
5 Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Si 0.1B 4.8O 10 Heat is washed 101 100 0.93
6 Gd 0.6Ce 0.2Tb 0.2ZnAl 0.05Si 0.05B 4.9O 10 Be untreated 102 101 0.94
7 Gd 0.6Ce 0.2Tb 0.2Mg 0.75Cd 0.25Al 0.1Si 0.05B 4.85O 10 Be untreated 102 101 0.94
Table 2
Embodiment number General formula Explanation Relative intensity (%) Relative integral intensity (%) q
8 Gd 0.8Ce 0.2Mg 0.9Mn 0.1Al 0.1B 4.9O 10 Heat is washed 100 100 0.90
9 Gd 0.8Ce 0.2Mg 0.9Mn 0.1Al 0.1Si 0.05B 4.85O 10 Heat is washed 104 105 0.94
10 Gd 0.8Ce 0.2Mg 0.9Mn 0.1Al 0.05Si 0.05B 4.9O 10 Be untreated 102 104 0.93
11 Gd 0.8Ce 0.2Mg 0.9Mn 0.1Si 0.1B 4.9O 10 EDTA 99 101 0.91
12 Gd 0.8Ce 0.2Mg 0.9Mn 0.1Al 0.25Si 0.75B 4.9O 10 Heat is washed 100 101 0.91
Table 3
Embodiment number General formula Explanation Relative intensity (%) Relative integral intensity (%) q
13 Gd 0.6Ce 0.2Tb 0.2Mg 0.9Mn 0.1Al 0.1B 4.9O 10 Heat is washed 100 100 0.90
14 Gd 0.6Ce 0.2Tb 0.2Mg 0.9Mn 0.1Al 0.1Si 0.05B 4.85O 10 Heat is washed 102 103 0.92
15 Gd 0.6Ce 0.2Tb 0.2Mg 0.9Mn 0.1Si 0.1B 4.9O 10 Heat is washed 99 100 0.90
Table 4
Embodiment number General formula Explanation Relative intensity (%) Relative integral intensity (%) q
16 Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Ge 0.05B 4.85O 10 Heat is washed 101 101 0.91
17 Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Zr 0.05B 4.85O 10 Heat is washed 100 100 0.9
18 Gd 0.8Ce 0.2Mg 0.9Mn 0.1Al 0.1P 0.05B 4.85O 10 Heat is washed 102 101 0.91
19 Gd 0.8Ce 0.2Mg 0.9Mn 0.1Al 0.1V 0.05B 4.85O 10 Heat is washed 99 99 0.89
20 Gd 0.6Ce 0.2Tb 0.2MgAl 0.1Nb 0.05B 4.85O 10 Heat is washed 95 94 0.84
21 Gd 0.8Ce 0.2Mg 0.9Mn 0.1Al 0.1Ta 0.05B 4.85O 10 Heat is washed 96 96 0.85
Owing to be used to prepare the excessive of required boric acid and two valency positively charged ions are excessive, in the neutralization of table 1-table 4 in the above-described embodiments,, therefore, simply be written as O to because the charge compensation that Sauerstoffatom caused that substituent produced of selection does not give consideration 10To replace O 10+s
According to table 1 couple luminophore BSCT, according to table 2 couple luminophore BSCM, all prove according to table 3 couple luminophore BSCTM with according to the result of table 4 couple luminophore BSCX, they have surpassed the characteristics of luminescence of known so far simple pentaborate luminophore significantly in some cases, particularly by mixing silicon in addition and forming based on the example of only using magnesium activatory metaborate luminophore according to table 5, its structure obviously is different from the structure of known simple pentaborate so far, contraction has generally all taken place in lattice, increases as the θ value size as shown in the diffractometer image.
In table 5, the Si=0 of embodiment 8 represents CBM, and Si=0.05 represents BSCM among the embodiment 10, among the embodiment 11 Si=0.1 represent BSCM and in addition in embodiment 9 Si=0.05 represent BCSM.In the embodiment that all have been studied, similar structural changes all takes place, the central ion size reduces to have caused the lattice contraction, but size increases and then causes lattice dilatation.For first kind of situation, mainly observe the characteristics of luminescence and improve; For second kind of situation, compare with the luminous pentaborate of routine, but do not observe variation, or slightly destroy.
Embodiment shown in the table 1-5 all shows, not only particularly metaborate but also germanic acid borate and borophosphoric acid hydrochlorate all have outstanding basic lattice because of activating with cerium, terbium, gadolinium and magnesium, and, can be used for fluorescent screen individually or as mixture because they have the extraordinary characteristics of luminescence.Particularly, they can be used for as the luminescent layer at low-voltage mercury arc lamp, and then cause several percentage points of optical throughput gains.
Table 5
A B C D E B-C B-D B-E
Si＝0 Si＝0.05 Si=0.05 in addition Si＝0.1
CBM embodiment 8 BSCM embodiment 10 BSCM embodiment 9 BSCM embodiment 11
hkl Θ Θ Θ Θ ΔΘ ΔΘ ΔΘ
100 13.5 13.52 13.52 13.54 -0.02 -0.02 -0.04
10-2 14.24 14.24 14.24 14.26 0 0 -0.02
11-1 15.48 15.46 15.5 15.54 0.02 -0.02 -0.06
11-2 18.42 18.42 18.44 18.44 0 -0.02 -0.02
002 18.84 18.86 18.88 18.9 -0.02 -0.04 -0.06
20-2 20.5 20.52 20.5 20.5 -0.02 0 0
020 23.34 23.36 23.36 23.4 -0.02 -0.02 -0.06
21-1 23.64 23.64 23.66 23.68 0 -0.02 -0.04
021 25.24 25.22 25.24 25.26 0.02 0 -0.02
12-1 25.56 25.58 25.56 25.58 -0.02 0 -0.02
21-3 25.92 25.92 25.94 25.92 0 -0.02 0
120 27.1 27.1 27.1 27.12 0 0 -0.02
12-2 27.48 27.48 27.48 27.5 0 0 -0.02
102 29.78 29.8 29.78 29.84 -0.02 0 -0.06
022 30.2 30.22 30.22 20.24 -0.02 -0.02 -0.04
10-4 30.86 30.86 30.86 30.88 0 0 -0.02
21-4 31.14 31.14 31.14 31.16 0 0 -0.02
121 31.64 31.64 31.64 31.68 0 0 -0.04
30-2 31.98 32 32.02 32.06 -0.02 -0.04 -0.08
12-3 32.3 32.32 32.32 32.32 -0.02 -0.02 -0.02
22-3 33.1 33.1 33.08 33.1 0 0.02 0
31-2 34.12 34.14 34.16 34.16 -0.02 -0.04 -0.04
31-4 35.04 35.08 35.1 35.08 -0.04 -0.06 -0.04
220 36.22 36.22 36.22 36.26 0 0 -0.04
211 36.46 36.48 36.48 36.5 -0.02 -0.02 -0.04
023 37.16 37.18 37.18 37.2 -0.02 -0.02 -0.04
31-1 37.6 37.62 37.66 37.68 -0.02 -0.06 -0.08
Average drift -0.010 -0.016 -0.035

Claims (9)

1. luminous metaborate material, it is based on the metaboric acid rare earth metal salt, and its general formula is:
(Y，La) 1-x-y-zCe xGd yTb z(Mg，Zn，Cd) 1-pMn pB 5-q-s(Al，Ga) q(X) sO 10，
Wherein X is the perhaps summation of how above-mentioned element of Si, Ge, P, Zr, V, Nb, Ta, W, y=z=p=0 0.01≤x≤1.0 in addition
0 ≤q≤ 1.0
0＜s≤1.0z=p=0 and y ≠ 0 0.01≤x≤1-y
0.02 ≤y≤ 0.80
0 ≤q≤ 1.0
0＜s≤1.0p=0 and z ≠ 0 0.01≤x≤1-y-z
0 ≤y≤ 0.98
y+z ≤ 0.99
0.01 ≤z≤ 0.75
0 ≤q≤ 1.0
0＜s≤1.0z=0 and p ≠ 0 0.01≤x≤1-y
0 ≤y≤ 0.99
0.01 ≤p≤ 0.30
0 ≤q≤ 1.0
0＜s＜1.0p ≠ 0 and z ≠ 0 0.01≤x＜1-y-z
0 ≤y≤ 0.98
0.01 ≤z≤ 0.75
x+z ≤ 0.99
0.01 ≤p≤ 0.30
0 ≤q≤ 1.0
0 ＜s≤ 1.0。
2. according to the luminous metaborate material described in the claim 1, wherein y=z=p=0 and 0.01≤x≤0.50.
3. according to the luminous metaborate material described in the claim 1, wherein z=p=0 and 0.01≤x≤0.50 and 0.05≤y≤0.75 and x+y≤1.
4. according to the luminous metaborate material described in the claim 1, wherein p=0 and 0.01≤z≤0.75 and x+y+z=1.
5. according to the luminous metaborate material described in the claim 1, wherein z=0 and 0.01≤p≤0.30 and x+y=1.
6. according to the luminous metaborate material described in the claim 1, wherein 0.01≤p≤0.30 and 0.01≤z≤0.75 and x+y+z=1.
7. fluorescent screen that comprises one or more according to each described luminous metaborate material among the claim 1-6.
8. luminescent layer that comprises one or more according to each described luminous metaborate material among the claim 1-6.
Its diameter greater than the Radiant UV Power of 5mm, discharge greater than 200W/m 2Low-voltage mercury arc lamp, comprise be arranged in this lamp discharge vessel inboard one or more according to each described luminous metaborate material among the claim 1-6.
CN98115943A 1997-07-12 1998-07-10 Luminous silicate-borate substance Expired - Fee Related CN1105765C (en)

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DE19730005A DE19730005C2 (en) 1997-07-12 1997-07-12 Silicate borate phosphors
DE19730005.7 1997-07-12

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CN1105765C true CN1105765C (en) 2003-04-16

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DE19730005C2 (en) 1999-11-25
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JP3163284B2 (en) 2001-05-08
CN1206734A (en) 1999-02-03

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