WO1992020757A1 - A photo-luminescent calcium silicate material, concrete and gravel material containing it and a method of producing a photo-luminescent calcium silicate material - Google Patents
A photo-luminescent calcium silicate material, concrete and gravel material containing it and a method of producing a photo-luminescent calcium silicate material Download PDFInfo
- Publication number
- WO1992020757A1 WO1992020757A1 PCT/DK1991/000128 DK9100128W WO9220757A1 WO 1992020757 A1 WO1992020757 A1 WO 1992020757A1 DK 9100128 W DK9100128 W DK 9100128W WO 9220757 A1 WO9220757 A1 WO 9220757A1
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- WIPO (PCT)
- Prior art keywords
- photo
- luminescent
- calcium silicate
- mole
- activator
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 113
- 239000000378 calcium silicate Substances 0.000 title claims abstract description 37
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 37
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000004567 concrete Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 28
- 239000012190 activator Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000010456 wollastonite Substances 0.000 claims abstract description 28
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 238000001953 recrystallisation Methods 0.000 claims abstract description 8
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 7
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052745 lead Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 150000004679 hydroxides Chemical class 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000011372 high-strength concrete Substances 0.000 claims description 6
- 238000005424 photoluminescence Methods 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000004576 sand Substances 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001397173 Kali <angiosperm> Species 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000011455 calcium-silicate brick Substances 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- -1 chalk Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/666—Aluminates; Silicates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/043—Alkaline-earth metal silicates, e.g. wollastonite
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
- C09K11/592—Chalcogenides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
- C09K11/646—Silicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/676—Aluminates; Silicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/7442—Aluminates; Silicates
Definitions
- the present invention concerns a photo-luminescent calcium silicate material and a method of producing this material.
- the invention moreover concerns photo-luminescent con- crete, in particular high strength concrete, as well as a gravel material produced by crushing said concrete.
- US Patent No. 3 266 879 discloses a method of making a crystallizable glass material which in a subsequent devitrifying or recrystallization step may be devitrified or recrystallized to an end product consisting of syn ⁇ thetic fibro-crystalline wollastonite crystals disseminat ⁇ ed in a calcium silicate glass matrix, wherein a selected composition of raw materials suitable for forming a crystallizable glass material comprising calcareous and siliceous materials, such as chalk and sand, as well as preferably dolomite are partly introduced from the upper end of the rotary kiln, partly injected from the lower end of the rotary kiln in a manner such that part of the injected raw materials is distributed over the burning zone.
- the part of the raw materials injected in the lower end is preferably quartz sand.
- the raw material When introduced in the rotary kiln the raw material is gradually heated, calcined and melted.
- the resulting molten material flows out of the kiln and is solidified and granulated by cooling, preferably by quenching, in a water bath. Due to the quenching the resulting product is a glass containing fine crystalline material. Further crystallization may be obtained by re-heating this material. In this manner it is possible to produce a white or whitish, partially crystallized, granular material having a rough surface.
- the obtained product is extensive ⁇ ly used, i.a. in the manufacture of sand-lime bricks and as aggregate in white concrete or in bituminous road surfaces and can be produced from relatively readily accessible starting materials.
- US Patent No. 3 458 301 describes a development of the method disclosed in US Patent No. 3 266 879, which comprises mixing a thermally crystallizable vitreous material and quartz sand wherein the ratio of quartz to vitreous materials is no greater than 5:1 parts, heating the mixture of said vitreous material in a rotary kiln to form a kneadable mass in which the sand grains are embedded and subsequently thermally crystallizing the crystallizable vitreous material to produce a devitrified glass aggregate.
- US Patent No. 4 119 434 describes another development of the method disclosed in US Patent No. 3 266 879, which comprises injecting calcium sulfate, preferably in the form of powdered gypsum, optionally with simultaneous injection of sand into the lower end of the rotary kiln to produce a synthetic wollastonite having a particularly low content of cristobalite.
- the obtained materials are useful for numerous purposes, such as production of additives for ceramics, so-called low- emperature ceramics, as described in US Patent No. 4 157 907, and plate-shaped products, in particular corrugated plates, construction materials and road surfaces, as described in US Patent No. 4 202 851.
- photo-luminescent materials are defined as materials absorbing energy quanta from photons, and emitting at least part of the absorbed energy by emission of photons.
- the emitted photons will have a longer wavelength than the wavelength of the absorbed photons.
- the material will be present in an excited state between the absorption of an incoming photon and the emission of an outgoing photon. The duration of this state determines whether fluorescence (brief duration, i.e. less than about 10 —8 s) or phosphorescence (longer duration, i.e. greater than about 10 —8 s) is involved.
- Photo-luminescent materials typically consist of a so-called base material which is not photo-luminescent per se, or only to a limited degree, but contains a relatively small amount of an activating material, typically an ele ⁇ ment, called an "activator" which gives rise to the photo- luminescent effect.
- M:A is used below for designating a photo- luminescent material with base material M and activator A.
- US Patent No. 2 297 108 describes a plurality of europium- activated silicates of alkaline earth metals, i.a.
- CaSiO tEu which fluoresces when irradiated with 365 nm photons.
- These materials are prepared by a sintering process comprising heating e.g. a mixture of calcium oxide and silica gel containing about 0.1% by weight Eu in air at 800 °C for 15 minutes; regrinding the product thus obtained; reheating the reground material at 800 °C in another 15 minutes in hydrogen; and cooling in a hydrogen atmosphere.
- photo-luminescent materials absorbing ultraviolet light, i.e. photons with a wave ⁇ length of typically 100-420 nm, and emitting visible light, i.e. photons with a wavelength of typically 420- 640 nm, for marking and illuminating roadways, illuminat- ing edges markings and the like is known.
- US Patent No. 4 208 300 concerns a type of paint comprising a synthetic binder, crystalline material, e.g. ground quartz, and one or more phosphorescent sulfides, which are applied to the objects to be marked.
- US Patent No. 3 253 146 concerns a similar material of the paint type, where, however, fluorescent organic pigments are used.
- GB Patent Application No. 2 043 673 describes a photo- luminescent composition which may be used for road markings.
- This composition comprises from 60 to 90% by weight of a hard porous or rough translucent support and from 40 to 10% by weight of a luminescent pigment retained in the pores or roughness of the support.
- the support is preferably particulate alumina, quartz or an alumino- silicate whose surface has been rendered porous or rough by etching and has a hardness not less than 7 on the Moh scale.
- the luminescent pigment may be Ce, Cs, Na or Pr uranates, or organic material.
- This composition is mixed with a styrene or di-isocyanate resin system which cures during moulding.
- GB Patent No. 1 034 037 describes small transparent glass spheres having diameters less than 50 mils, preferably between 0.5 and 10 mils, and containing 0.1-0.4% by weight of U0-., which flouresce in the presence of ultraviolet light. These materials may be used in e.g. painted highway markings and signs.
- JP Patent Application No. 60-176933 describes glass fibers and spherules containing a flourescent powder, e.g. ZnS.
- WO 90/02226 concerns a road surfacing material comprising a binder, e.g. tar, a crushed mineral material, e.g. quartzite, as well as 2-25, preferably 10-15% by weight of an UV excitable fluorescent material which has been produced by melting a mineral in a furnace of the kind used in the manufacture of mineral wool and doping said mineral with an activator by introducing said activator into the molten mineral-bath, granulating or casting the resulting melt, and crushing the solidified material to size corresponding to the size of the mineral material.
- a binder e.g. tar
- crushed mineral material e.g. quartzite
- an UV excitable fluorescent material which has been produced by melting a mineral in a furnace of the kind used in the manufacture of mineral wool and doping said mineral with an activator by introducing said activator into the molten mineral-bath, granulating or casting the resulting melt, and crushing the solidified material to size corresponding to the size of the mineral material.
- the object of the invention is to provide a photo-lumine cent material which is well suited for marking and illum nating roadways, which has improved weather and wear resistance compared with the known materials, and which can be produced in a simple way using environmentally acceptable, inexpensive and easy available raw materials.
- the invention is based on the finding that when incorpora ting one or more activators in a raw material mixture of the type described above in connection with production of materials consisting of synthetic wollastonite crystals disseminated in a calcium silicate glass matrix, it is possible to produce a partially crystallized material having photo-luminescent properties and excellent weather and wear resistance.
- the present invention relates to a photo- luminescent calcium silicate material, which is character ized by comprising photo-luminescent fibro-crystalline wollastonite crystals activated with an activator in a quantity effective for ensuring photo-luminescence, said activator comprising at least one element selected from the group consisting of Mn, Pb, Er, Tm, W, Nb, Ti, Cr, Sn, and Bi, and disseminated in a calcium silicate glass matrix having a low content of alkali metal oxides.
- This material has excellent strength properties because the fibro-crystalline wollastonite provides a strong fibro-crystalline reinforcement of the glass matrix. Due to the high surface/volume-ratio of the photo-luminescent component, i.e. the fibro-crystalline photo-luminescent wollastonite crystals typically having average particle sizes in the ⁇ m range, this material exhibits an intense photo-luminescence.
- the quantity of the added element/elements used as activa ⁇ tor necessary for ensuring a photo-luminescent end product is easily determined by laboratory tests comprising melt ⁇ ing mixtures prepared from a stock mixture of calcarious and siliceous materials having varying contents of activa ⁇ tors in a crucible, cooling the melted material, recrys- tallizing the cooled material, and subsequently subjecting the recrystallized material to a photo-luminescence test, e.g. as described below.
- said material contains 30-70% by weight photo- luminescent fibro-crystalline wollastonite crystals
- said material has the following analysis: a CaO content of about 20-30% by weight, a SiO-, content of about 65-80% by weight, an A1 2 0-. content less than about 5% by weight, an alkali metal oxide content less than about 5% by weight, and a mole ratio activator/CaO within the range 0.0005-0.35, preferably within the range 0.0010-0.25;
- said activator provides a photo-luminescent fibro- crystalline wollastonite which emits visible light when excitated by photons having a wavelength greater than 315 nm, in particular within the interval 315-400 nm;
- said photo-luminescent fibro-crystalline wollastonite crystals are activated with Mn as an activator in an amount of 0.044-0.20 mole Mn/mole CaO;
- said photo-luminescent fibro-crystalline wollastonite crystals are activated with Mn and Ti as activators, Mn in an amount of 0.044-0.20 mole Mn/mole CaO and Ti in an amount of 0.025-0.15 mole Ti/mole CaO;
- said photo-luminescent fibro-crystalline wollastonite crystals are activated with Nb as an activator in an amount of 0.005-0.20 mole Nb/mole CaO.
- the present invention relates to a method of producing said photo-luminescent calcium silicate material which is characterized by introducing a raw material comprising a mixture of calcareous and sili ⁇ ceous materials and activators in a quantity suitable for ensuring photo-luminescence, selected from the group con ⁇ sisting of oxides, hydroxides and salts of Mn, Pb, Er, Tm, W, Nb, Ti, Cr, Sn, and Bi, into a rotary kiln; melting said mixture at least partially; withdrawing the at least partially melted mixture from the rotary kiln; and cool ⁇ ing, preferably quenching the withdrawn material- to a par ⁇ tially crystallized product comprising photo-luminescent fibro-crystalline wollastonite crystals disseminated in a calcium silicate glass matrix.
- a raw material comprising a mixture of calcareous and sili ⁇ ceous materials and activators in a quantity suitable for ensuring photo-luminescence, selected from the group con ⁇ sisting
- the cooled, partially crystallized material withdrawn from the rotary kiln is subjected to recrystallization in a recrystallization and annealing step at a temperature within the range from about 900 °C to about 1100 °C for a period of time from about 0.5 to about 4 h.
- the raw material contains amorphous carbon in an amount corresponding to 2-3 times the stoichiometric amount needed for reducing an activator to a desired valency.
- the raw mixture has the following analysis: a CaO content of about 20-30% by weight, a SiO-, content of about 65-80% by weight, an Al ⁇ O-, content less than about 5% by weight, an alkali metal oxide content less than about 5% by weight, and a mole ratio activator/CaO within the range 0.0005-0.35, preferably within the range 0.0010-0.25.
- the activator is chosen to provide a photo-luminescent wollastonite which emits visible light when excitated by photons having a wavelength greater than 315 nm, in par ⁇ ticular within the interval 315-400 nm.
- the raw material contains Mn as an activator in an amount of 0.044-0.20 mole Mn/mole CaO.
- the raw material contains Mn and Ti as activators, Mn in an amount of 0.044-0.20 mole Mn/mole CaO and Ti in an amount of 0.025-0.15 mole Ti/mole CaO.
- the raw material contains Nb as an activator in an amount of 0.005-0.20 mole Nb/mole CaO.
- At least part of the raw material preferably of that injected from the lower end of the kiln, consists of filter dust collected in a filter arranged in connection with the rotary kiln.
- the method according to the invention can conveniently be performed in a rotary kiln of the type usually employed in the manufacture of materials comprising synthetic wollas ⁇ tonite disseminated in a calcium silicate glass matrix, e.g. as described in US Patent No. 3 266 879.
- the method is extremely flexible since the kiln can be adjusted to provide differently photo-luminescent, materials by varying the amount and type of the raw materials, the points where they are introduced, the kiln temperature and the rotary speed of the kiln.
- the activators used in the method according to the present invention are introduced into the rotary kiln as a mixture with calcareous and siliceous materials.
- This raw mixture may be introduced into the rotary kiln as an aqueous suspension or as a dry powder.
- the raw material is completely melted in the rotary kiln.
- the process according to the invention may be performed using well-known technique from the state of the art, cf. the above-mentioned US patent specification, e.g. by pump ⁇ ing an aqueous suspension of the raw materials, such as sand, chalk, dolomite, and activators for calcium silicate in the rotary kiln, followed by continuous melting in the rotary kiln.
- the raw materials such as sand, chalk, dolomite, and activators for calcium silicate in the rotary kiln, followed by continuous melting in the rotary kiln.
- the molten mass may advantageously be crystallized during slow cooling, optionally followed by re-heating.
- the molten mass is transferred to a cold conveyor belt and allowed to stabilize in a layer having a suitable thickness of some centimeters by cooling of the surface with water and/or air to provide slow crystallization.
- Variation of the photo-luminescent properties of the end product may be obtained by varying the activator used.
- the activators are selected from the group consisting of oxides, hydroxides and salts of Mn, Pb, Er, Tm, W, Nb, Ti, Cr, Sn and Bi, which elements may be used alone or in a suitable combination.
- the selection will depend upon the desired excitation wavelength and the temperature at which the manufacturing process takes place. As mentioned, combination of various substances is possible and preferred in many cases.
- the activator may be mixed in a slurry of chalk, dolomite and sand.
- a suitable dosage shall at least amount to 0.2% of the total dry matter. However, in many cases 0.5% will be suitable, and a mixing percent of 5 will be acceptable as the upper limit. Melting, cooling and crystallization are performed according to the above-mentioned methods known per se in connection with the conventional production of partially crystallized glass material.
- the product produced by the above-mentioned embodiments of the method according to the invention can be obtained in alkali resistant form by suitable composition of the starting materials.
- This material is particularly suitable as aggregate in a photo-luminescent high strength concrete.
- a photo-luminescent concrete in particular high strength concrete
- This photo-luminescent concrete is characterized in that it contains the photo-luminescent calcium silicate material according to the present inven ⁇ tion as an aggregate, preferably together with an aggre ⁇ gate consisting of non photo-luminescent synthetic wollas- tonite disseminated in a glass matrix.
- the binder used in this concrete is preferentially Port ⁇ land cement and optionally a mixture of Portland cement and pozzolans in a ratio providing high strength and work ⁇ ability.
- the compressive strength shall preferably be at least 40 MPa. If desired, various additives may be used to improve the workability of the concrete and its strength, e.g. super plastifying agents.
- a photo-luminescent gravel material is provided.
- This gravel material is characterized in that it consists of the above-mentioned photo-luminescent concrete, preferentially of the above-mentioned photo-luminescent high strength concrete.
- This gravel material can be produced by crushing e.g. slabs of the above-mentioned photo-luminescent concrete.
- the gravel material is preferably crushed to fractions of e.g. 2-5 mm, in particular 5-8 mm, but also 8-12 mm and 12-16 mm.
- the gravel material can also be pro ⁇ quizd by breaking uncured photo-luminescent concrete into fragments of desired size and subsequently curing these fragments.
- This gravel material may also be produced by preparing single nodules or lumps of uncured photo- luminescent concrete of desired size, preferentially below 5 and 15 mm, and subsequently curing these nodules or lumps.
- For the preparation of the above-mentioned gravel material addition of a photo-luminescent calcium silicate material having a particle size within the interval from about 0 to about 5 mm is preferred.
- This gravel material is particularly useful as a wear and weather resistant photo-luminescent aggregate for road surfaces or the like based on as well bitumen as concrete.
- fig. 1-3 show flourescence spectra of selected materials according to the invention.
- a raw mixture was prepared as an aqueous well-mixed uni- form suspension of finely comminuted chalk and siliceous sand containing 2.80% by weight Mn0 2 equivalent to 0.126 mole Mn/mol CaO.
- Si0 2 71%; CaO: 25%; Al 2 0 3 : 2.4%; MgO: 1.7%; Na-,0: 0.6%; K 2 0: 0.8% and Fe 2 0-.: 0.4%, calculated without loss of ignition.
- This mixture was continuously introduced into a rotary kiln at the upper end of the kiln.
- the raw materials were thereby heated to the calcination temperature at which the C0 2 was expelled from the carbonate, and subsequently further heated to complete melting at a temperature about 1550 °C.
- the melt was withdrawn at the lower end of the rotary kiln and quenched in water providing an intermediate product, in the following referred to as the glass fritte.
- This glass fritte contains a limited number of a small wollas ⁇ tonite crystals disseminated in a calcium silicate glass matrix, the amount and size of crystalline material depending on the rate of cooling.
- the glass fritte is a brittle material exhibiting numerous cracks and therefore this intermediate product has only a low compressive strength and weak abrasion resistance.
- this glass fritte was reheated in a rotary kiln to a tempera- ture of 950 °C for 3 hours and to 1050 °C for 1 hour.
- This end product was consisting of photo-luminescent fibro-crystalline wollastonite crystals disseminated in a calcium silicate glass matrix having a low content of alkali metal oxides. It had a whitish colour and exhibited high compressive strength and good abrasion resistance.
- the product exhibited a distinct red fluorescence when excitated with white light, using a 415 nm primary filter.
- Example 2 Similar products were produced using the same composition as described in Example 1 the only difference being that Mn0 2 was added in an amount of 3.75 and 1.90% by weight in example 2 and 3, respectively, corresponding to Mn/CaO mole ratios of 0.169 and 0.085, respectively.
- the end products were also consisting of a photo-lumines ⁇ cent fibro-crystalline wollastonite crystals disseminated in a calcium silicate glass matrix having a low content of alkali metal oxides. They also had a whitish colour and exhibited high compressive strength and good abrasion resistance. Also these products exhibited a distinct red fluorescence when excitated with white light, using a 415 nm primary filter.
- the end products were also consisting of photo-luminescent fibro-crystalline wollastonite crystals disseminated in a calcium silicate glass matrix having a low content of al ⁇ kali metal oxides. They had a whitish colour and exhibited high compressive strength and good abrasion resistance.
- a similar product was produced using the same composition as described in Example 1 the only difference being that Nb was used as activator, added as Nb-,0-. in an amount of 1.65% by weight, corresponding to a Nb/CaO mole ratio of 0.082.
- the end product had the same texture as the products described in example 1-6. It had a whitish colour and exhibited high compressive strength and good abrasion resistance.
- a photo-luminescent high strength concrete having the following composition was produced:
- the material was mixed in a paddle mixer, with premixing of cement, microsilica and aggregate for two minutes. Then the water was added, with mixing for one minute. After addition of the super plastifying agent mixing was per ⁇ formed for another four minutes.
- the concrete mixture was cast as small slabs having the dimensions 200 x 200 x 150 mm, which was hardened at a relative air moisture of about 100% at about 20°C for 28 days.
- the slabs described above were crushed in a jaw crusher, followed by additional crushing in a cone crusher.
- the crushed material was then sorted according to size in an ordinary gravel sorting system in fractions of 2-5 mm, 5-8 mm, 8-12 mm and >12 mm.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Luminescent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP91911302A EP0584067A1 (en) | 1991-05-14 | 1991-05-14 | A photo-luminescent calcium silicate material, concrete and gravel material containing it and a method of producing a photo-luminescent calcium silicate material |
CA002102900A CA2102900A1 (en) | 1991-05-14 | 1991-05-14 | A photo-luminescent calcium silicate material, concrete and gravel material containing it and a method of producing a photo-luminescent calcium silicate material |
PCT/DK1991/000128 WO1992020757A1 (en) | 1991-05-14 | 1991-05-14 | A photo-luminescent calcium silicate material, concrete and gravel material containing it and a method of producing a photo-luminescent calcium silicate material |
NO1993934091A NO934091D0 (en) | 1991-05-14 | 1993-11-12 | PHOTOLUMINESCENT CALCIUM SILICATE MATERIAL, CONCRETE AND GROUND MATERIALS CONTAINING THIS AND A PROCEDURE FOR PREPARING A PHOTOLUMINESCING CALCIUM SILICATE MATERIAL |
FI935009A FI935009L (en) | 1991-05-14 | 1993-11-12 | FOTOLUMINERANDE CALCIUMSILICATMATERIAL, BETONG OCH GRUSMATERIAL INNEHAOLLANDE DET OCH ETT FOERFARANDE FOER FRAMSTAELLNING AV FOTOLUMINERANDE CALCIUMSILICATMATERIAL |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002102900A CA2102900A1 (en) | 1991-05-14 | 1991-05-14 | A photo-luminescent calcium silicate material, concrete and gravel material containing it and a method of producing a photo-luminescent calcium silicate material |
PCT/DK1991/000128 WO1992020757A1 (en) | 1991-05-14 | 1991-05-14 | A photo-luminescent calcium silicate material, concrete and gravel material containing it and a method of producing a photo-luminescent calcium silicate material |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992020757A1 true WO1992020757A1 (en) | 1992-11-26 |
Family
ID=88405069
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DK1991/000128 WO1992020757A1 (en) | 1991-05-14 | 1991-05-14 | A photo-luminescent calcium silicate material, concrete and gravel material containing it and a method of producing a photo-luminescent calcium silicate material |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0584067A1 (en) |
CA (1) | CA2102900A1 (en) |
FI (1) | FI935009L (en) |
NO (1) | NO934091D0 (en) |
WO (1) | WO1992020757A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL1036967C2 (en) * | 2009-05-18 | 2010-11-22 | Next Generation B V | LUMINOUS CONCRETE USING PHOTO-LIGHTING PIGMENTS PROCESSED IN GLASS AND PLASTIC. |
RU2498967C1 (en) * | 2012-05-30 | 2013-11-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Национальный исследовательский Томский политехнический университет" | Method of producing wollastonite ceramic pigments based on dicalcium silicates |
US8846784B2 (en) | 2005-08-10 | 2014-09-30 | Construction Research & Technology Gmbh | Additive with applications in construction chemistry |
EP3865762A1 (en) | 2020-02-17 | 2021-08-18 | Lhotellier SA | System and method for ambient lighting, and related computer program |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5948157A (en) * | 1996-12-10 | 1999-09-07 | Fording Coal Limited | Surface treated additive for portland cement concrete |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3266879A (en) * | 1962-10-23 | 1966-08-16 | Krphiyer Karl Kristian Kobs | Process of making a crystallizable glass material |
FR1600137A (en) * | 1968-05-06 | 1970-07-20 | ||
FR2168685A5 (en) * | 1972-01-20 | 1973-08-31 | Gravisse Philippe | Photoluminescent concrete - or mortar, contg zinc sulphide |
-
1991
- 1991-05-14 WO PCT/DK1991/000128 patent/WO1992020757A1/en not_active Application Discontinuation
- 1991-05-14 CA CA002102900A patent/CA2102900A1/en not_active Abandoned
- 1991-05-14 EP EP91911302A patent/EP0584067A1/en not_active Withdrawn
-
1993
- 1993-11-12 NO NO1993934091A patent/NO934091D0/en unknown
- 1993-11-12 FI FI935009A patent/FI935009L/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3266879A (en) * | 1962-10-23 | 1966-08-16 | Krphiyer Karl Kristian Kobs | Process of making a crystallizable glass material |
FR1600137A (en) * | 1968-05-06 | 1970-07-20 | ||
FR2168685A5 (en) * | 1972-01-20 | 1973-08-31 | Gravisse Philippe | Photoluminescent concrete - or mortar, contg zinc sulphide |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8846784B2 (en) | 2005-08-10 | 2014-09-30 | Construction Research & Technology Gmbh | Additive with applications in construction chemistry |
NL1036967C2 (en) * | 2009-05-18 | 2010-11-22 | Next Generation B V | LUMINOUS CONCRETE USING PHOTO-LIGHTING PIGMENTS PROCESSED IN GLASS AND PLASTIC. |
WO2010134805A1 (en) * | 2009-05-18 | 2010-11-25 | Next Generation B.V. | Light emitting concrete comprising photoluminescent pigment containing glass particles |
RU2498967C1 (en) * | 2012-05-30 | 2013-11-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Национальный исследовательский Томский политехнический университет" | Method of producing wollastonite ceramic pigments based on dicalcium silicates |
EP3865762A1 (en) | 2020-02-17 | 2021-08-18 | Lhotellier SA | System and method for ambient lighting, and related computer program |
FR3107335A1 (en) | 2020-02-17 | 2021-08-20 | Lhotellier Sa | Ambient space lighting system and method, and associated computer program |
Also Published As
Publication number | Publication date |
---|---|
NO934091L (en) | 1993-11-12 |
FI935009A0 (en) | 1993-11-12 |
CA2102900A1 (en) | 1992-11-15 |
NO934091D0 (en) | 1993-11-12 |
FI935009L (en) | 1993-11-12 |
EP0584067A1 (en) | 1994-03-02 |
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