CN103992095A - Self-propagating high-temperature synthesis and densification method of zirconolite-rich type man-made rock - Google Patents
Self-propagating high-temperature synthesis and densification method of zirconolite-rich type man-made rock Download PDFInfo
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- CN103992095A CN103992095A CN201410224871.1A CN201410224871A CN103992095A CN 103992095 A CN103992095 A CN 103992095A CN 201410224871 A CN201410224871 A CN 201410224871A CN 103992095 A CN103992095 A CN 103992095A
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Abstract
The invention discloses a self-propagating high-temperature synthesis and densification method of a zirconolite-rich type man-made rock. The method is characterized by comprising the steps of performing mixing, ball milling and screening on raw materials such as calcium nitrate tetrahydrate, calcium oxide, zirconium dioxide, titanium powder, titanium dioxide, barium oxide, aluminum oxide and the like to obtain a mixed material; putting the mixed material into a mold, and pressing to obtain a blank; preparing the blank into the densified zirconolite-rich type man-made rock by using a self-propagating pseudo isostatic pressing device. By adopting the self-propagating high-temperature synthesis and densification method, the prepared irconolite-rich type man-made rock has relatively large capacity on rare earth elements, actinide elements and the like, and is wide in element containment range. The self-propagating high-temperature synthesis and densification method disclosed by the invention adopts a high-temperature self-propagating synthetic method, is high in synthesis speed, short in production cycle and high in production efficiency, does not need a heat source provided externally, and is simple in process and strong in practicability; the prepared zirconolite-rich type man-made rock is suitable for solidification treatment of radioactive wastes.
Description
Technical field
The invention belongs to the preparation of artificial rock, the self propagating high temperature that relates to the artificial rock of zirconolite-rich type synthesizes and densifying method.The artificial rock of zirconolite-rich type that adopts the present invention to prepare is specially adapted to high-level atomic waste and processes; The artificial rock of zirconolite type is the main parasitic phase of actinide elements, for rare earth element, also has good pardon, has good development prospect processing high putting aspect waste material.
Background technology
It is an important material preparation technology that self propagating high temperature synthesizes (referred to as SHS) technology (that is: adopting the preparation method of self-spreading quasi isopressing device), it utilize chemical reaction self heat release maintain reaction continue carry out, thereby synthetic have a product of specifying composition and structure.Compare with traditional technology, SHS technology has the advantages such as speed of response is fast, energy consumption is little, equipment is simple, easy to operate, is subject to the great attention of each research institution both at home and abroad.From the former Russian scholar Merzhanov, in 1967, invent, over more than 40 year, SHS technology has obtained broad research, now developed into the new subject between combustion science and Materials science, adopt SHS technique can synthesize ceramic material, metal matrix and ceramic matric composite, intermetallic compound, gradient material, the contour technical pattern of high-temperature superconductor and functional materials, in industrial production, be used widely.
In prior art, the disposal that height is put waste material mainly contains temporary in underground storage tank, curing and stores for a long time.At present, the cured body material of application and research has glass, plastics, cement, pitch, artificial rock etc., and wherein glass and artificial rock are that many two kinds high of research are both at home and abroad put waste material curing substrate.Vitrification technology comparative maturity, but glass is subject to the impact of water or water vapour under the environment of High Temperature High Pressure, Industry organizations trucfure heating changes, finally cause the integral body of material to be destroyed, and artificial rock is because its high-compactness, strong, the anti-radiation property of chemical stability are strong and the strong advantage of anti leaching performance, cause the great attention of various countries and interest widely.
Artificial rock is divided into A, B, C, D, E, F system, and its main mine is zirconolite, hollandite, pyrrhite, uhligite, rutile, spinel, nepheline etc. mutually.A, B system are mainly solidified the high waste material of putting of typical case, and containing amount is 0～10wt.%; C system is solidified liking business power reactor aftertreatment high activity liquid waste, and containing amount is 5～22wt.%, and formula flexibly, and physicals is high, and chemical stability is good; D system is processed and is put waste material to liking military height, and containing amount is 60～70wt.%, and its containing amount is high; E system is solidified liking the high waste material of putting of power reactor, and containing amount is 0～10wt.%, and containing amount is less, little but heat is released rate, and chemical stability is high; F system is solidified liking " through type " spent fuel, and containing amount is 0～50wt.%, and the advantage of F system is to contain the waste liquid that uranium content is high.
Zirconolite is because its high pardon for actinide elements and rare earth element is widely studied, and in prior art, the preparation of zirconolite is mainly divided into liquid phase method and solid phase method.Liquid phase method mainly comprises hydroxide process, sol-gel method, and liquid phase reaction legal system is for the artificial rock cured body of zirconolite type, and technique is more complicated, and the cost of raw material is higher.Solid phase method adopts solid reaction process, and technique is simple, raw material be easy to get and price lower.Therefore, with solid phase method, prepare the artificial rock cured body of zirconolite-rich type and be more suitable in through engineering approaches application, but its synthesis cycle of existing solid phase method is long, and synthesis temperature is high, poor practicability, for through engineering approaches, application still needs to improve its technique.
Summary of the invention
Object of the present invention is intended to overcome deficiency of the prior art, provides the self propagating high temperature of the artificial rock of a kind of zirconolite-rich type to synthesize and densifying method.Thereby provide the artificial rock block of zirconolite-rich type and the synthetic method of a kind of effective raising containing amount and element range comprehension.
Content of the present invention is: the self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, it is characterized in that comprising the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15～35%, calcium oxide (CaO) 3～15%, zirconium dioxide (ZrO
2) 5～25%, titanium valve (Ti) 5～20%, titanium dioxide (TiO
2) 5～35%, barium oxide (BaO) 1～5%, aluminium sesquioxide (Al
2o
3) 3～30% component and mass percent get each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 10～30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10～100g compound and pack in mould, adopt 5～100MPa pressure that compound is pressed into the cylinder blank that diameter is 10～50mm (4);
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel die being formed by bottom (1), annular sidewall (2) and seaming chuck (3); Referring to accompanying drawing 1, with quartz sand (7), be paved with steel die bottom (1), blank (4) is placed in to quartz sand top, at blank (4), be sidelong and put igniting tungsten filament (6) and make both (fully) contacts, at blank (4) opposite side, place thermopair (5) and make both (fully) contacts, use again quartz sand (7) in steel die, to fill up, by seaming chuck (3) sealing steel die; Subsequently to the logical direct current of igniting tungsten filament (6), energising voltage is that 5～30V, electric current are 30～100A, blank (4) (can) ignite when temperature reaches 2000～3000K, after finishing, self-propagating combustion in 3～5 second time, mold (3) is applied to 30～300MPa pressure until blank (4) is cooled to normal temperature; Cooling rear blank (4) is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
The artificial rock behaviour of the densification zirconolite-rich type lithogenesis stone B system making, this B system ore deposit is zirconolite, hollandite, uhligite mutually, and the mass percentage content scope of each ore deposit phase is: zirconolite 65～90%, hollandite 3～10%, uhligite 7～25%.
In content of the present invention: the (Ca (NO of four water-calcium nitrate described in step a
3)
2.4H
2o) can replace with ferric oxide (Fe
2o
3) or molybdic oxide (MoO
3), or replace with four water-calcium nitrate (Ca (NO
3)
2.4H
2o), ferric oxide (Fe
2o
3), molybdic oxide (MoO
3) in the mixture of any two or three kinds of materials.
Another content of the present invention is: the self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, it is characterized in that comprising the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15～30%, calcium oxide (CaO) 3～10%, zirconium dioxide (ZrO
2) 5～20%, titanium valve (Ti) 10～20%, titanium dioxide (TiO
2) 15～40%, barium oxide (BaO) 1～5%, aluminium sesquioxide (Al
2o
3) 3～25% component and mass percent get each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 10～30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10～100g compound and pack in mould, adopt 5～100MPa pressure that compound is pressed into the cylinder blank that diameter is 10～50mm (4);
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel die being formed by bottom (1), annular sidewall (2) and seaming chuck (3); Referring to accompanying drawing 1, with quartz sand (7), be paved with steel die bottom (1), blank (4) is placed in to quartz sand top, at blank (4), be sidelong and put igniting tungsten filament (6) and make both (fully) contacts, at blank (4) opposite side, place thermopair (5) and make both (fully) contacts, use again quartz sand (7) in steel die, to fill up, by seaming chuck (3) sealing steel die; Subsequently to the logical direct current of igniting tungsten filament (6), energising voltage is that 5～30V, electric current are 30～100A, blank (4) (can) ignite when temperature reaches 2000～3000K, after finishing, self-propagating combustion in 3～5 second time, mold (3) is applied to 30～300MPa pressure until blank (4) is cooled to normal temperature; Cooling rear blank (4) is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
The artificial rock behaviour of the densification zirconolite-rich type lithogenesis stone C system making, this C system chats is zirconolite, hollandite, uhligite, rutile mutually, and the mass percentage content scope of each ore deposit phase is: zirconolite 60～85%, hollandite 3～5%, uhligite 7～20%, rutile 5～15%.
In another content of the present invention: the (Ca (NO of four water-calcium nitrate described in step a
3)
2.4H
2o) can replace with ferric oxide (Fe
2o
3) or molybdic oxide (MoO
3), or replace with four water-calcium nitrate (Ca (NO
3)
2.4H
2o), ferric oxide (Fe
2o
3), molybdic oxide (MoO
3) in the mixture of any two or three kinds of materials.
Content of the present invention can also be: the self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, it is characterized in that comprising the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15～35%, calcium oxide (CaO) 3～15%, zirconium dioxide (ZrO
2) 5～25%, titanium valve (Ti) 5～20%, titanium dioxide (TiO
2) 5～35%, barium oxide (BaO) 1～5%, aluminium sesquioxide (Al
2o
3) 3～30%, silicon-dioxide (SiO
2) 1～10%, sodium oxide (Na
2o) 1～5%, component and the mass percent of magnesium oxide (MgO) 1～15% are got each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 10～30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10～100g compound and pack in mould, adopt 5～100MPa pressure that compound is pressed into the cylinder blank that diameter is 10～50mm (4);
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel die being formed by bottom (1), annular sidewall (2) and seaming chuck (3); Referring to accompanying drawing 1, with quartz sand (7), be paved with steel die bottom (1), blank (4) is placed in to quartz sand top, at blank (4), be sidelong and put igniting tungsten filament (6) and make both (fully) contacts, at blank (4) opposite side, place thermopair (5) and make both (fully) contacts, use again quartz sand (7) in steel die, to fill up, by seaming chuck (3) sealing steel die; Subsequently to the logical direct current of igniting tungsten filament (6), energising voltage is that 5～30V, electric current are 30～100A, blank (4) (can) ignite when temperature reaches 2000～3000K, after finishing, self-propagating combustion in 3～5 second time, mold (3) is applied to 30～300MPa pressure until blank (4) is cooled to normal temperature; Cooling rear blank (4) is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
The artificial rock behaviour of the densification zirconolite-rich type lithogenesis stone D system making, this D system ore deposit is zirconolite, uhligite, nepheline, spinel mutually, and the mass percentage content scope of each ore deposit phase is: zirconolite 50～85%, uhligite 5～10%, nepheline 5～15%, spinel 5～25%.
(Ca (the NO of four water-calcium nitrate described in step a
3)
2.4H
2o) can replace with ferric oxide (Fe
2o
3) or molybdic oxide (MoO
3), or replace with four water-calcium nitrate (Ca (NO
3)
2.4H
2o), ferric oxide (Fe
2o
3), molybdic oxide (MoO
3) in the mixture of any two or three kinds of materials.
In foregoing invention content: described in step a, component raw material is commercially available prod, can be purchased from Aladdin reagent company;
Compared with prior art, the present invention has following feature and beneficial effect:
(1) due to zirconolite (CaZrTi
2o
7) stability be obviously better than uhligite, it can not only be fixed on the fission nuclides such as Sr, Cs in its crystalline network, and long lifetime actinium series nucleic is also had to very good ability to cure, the present invention is applied to self propagating high temperature synthetic method the preparation of the artificial rock curing substrate of zirconolite base, and the artificial rock of zirconolite-rich type of preparation must have better effect to the solidification treatment of high-level waste;
(2) adopt the present invention, the product obtaining is the artificial rock block of zirconolite-rich type, large to the containing amount of nucleic, contains elemental range wide; Synthetic product main mine of the present invention is zirconolite mutually, according to other ore deposit phase composites, can be divided into again artificial rock B, C, D system, its element containing amount is between 0～70wt.%, element range comprehension is the metallic elements such as Sr, Y, actinide elements, lanthanon, Cs, Mg, Co, Ni, Mo, Ru, Sn, Mn, Cs, Pb, Na, K, Ba, Rb and Fe, Mn, Cr, and can adjust as the case may be each ore deposit matched; The present invention adopts 30～300MPa pressure in reaction process, and product density is high, good stability; In the present invention, B system has added hollandite, and hollandite adopts the principle of isomorphism mainly by the Ba type hollandite of artificial rock, is that the mode that Cs replaces by different valency or compensation is fixed in the tunnel structure of hollandite; Spinel and nepheline in D system, have been added, spinel (AB
2o
4) because isomorph replacement is more general, A position can be Mg, Fe, Zn, Mn, B position can be Al, Cr, Fe, therefore better for the containing of metallic element; Nepheline adopts isomorphism principle K, Cs can be fixed on the Na position of nepheline;
(3) adopt the present invention, in the artificial rock B system of preparation, main mine is zirconolite mutually, uhligite, hollandite, wherein zirconolite and uhligite are for Sr, Y, actinide elements, lanthanon has good solidification effect, Cs is also showed to good solidification effect simultaneously, in B system, hollandite adds, can be to Mg, Co, Ni, Mo, Ru, Sn, Mn, Cs, the elements such as Pb solidify preferably, adding of hollandite not only improved curing elemental range and handiness, also contribute to improve anti leaching performance simultaneously, its element containing amount is 0～10 (wt.%), C system has been added Rutile Type on the basis of B system, is mainly to improve its physical and chemical stability and ore deposit phase consistency, and element containing amount is increased to 5～22 (wt.%) on the basis of B system, in D system, main mine is zirconolite, uhligite, spinel, nepheline mutually, this system containing amount is large, conventionally element containing amount can reach 60～70 (wt.%), adding for the metallic elements such as Fe, Mn, Cr are solidified with to good result of spinel wherein, being added on the solidifying of Na, K, Ba, Rb of nepheline has remarkable effect, in the present invention, in each system, the ratio flexible adjustment of each ore deposit phase is larger, can make suitable adjustment according to different situations,
(4) the present invention adopts self-propagating high-temperature synthesis method, and resultant velocity is fast, with short production cycle, production efficiency is high, temperature of reaction is high, without the external world, provide thermal source and energy, and technique is simple, and energy consumption is little, and equipment is simple, and product purity is high, easy to operate, practical.
Accompanying drawing explanation
Fig. 1 be the present invention adopt certainly spread isopressing device schematic diagram;
Fig. 2 is the XRD diffracting spectrum of the finished product that makes of the embodiment of the present invention 2.
In Fig. 1: 1-steel die bottom, 2-(steel die) annular sidewalls, 3-(steel die) seaming chucks, 4-blank, 5-thermopair, 6-igniting tungsten filament, 7-quartz sand.
Embodiment
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
(1) by raw material with Ca (NO
3)
2.4H
2o:41.3%, CaO:3%, ZrO
2: 24.5%, Ti:8.4%, TiO
2: 23.2%, BaO:1.5%, Al
2o
3: 1% mass percent feeding also mixes;
(2) by the former abrasive lapping 20min mixing and cross 100 mesh sieves, get the raw material that 30g fully grinds and pack in punching block, coldmoulding under 50MPa pressure, acquisition diameter is the cylinder blank that 30mm, thickness are about 5mm;
(3) self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 20V, electric current are 50A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 100MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product); The relative density of synthetic sample is 97%, and product is the artificial rock B system block of zirconolite-rich type, wherein: zirconolite massfraction is approximately 80%, hollandite is about 6%, uhligite is about 14%.
Embodiment 2:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
(1) by raw material with Ca (NO
3)
2.4H
2o:46.2%, CaO:4.7%, ZrO
2: 26.9%, Ti:7.6%, TiO
2: 26.9%, BaO:2.4%, Al
2o
3: 1.6% mass percent feeding also mixes;
(2) by the former abrasive lapping 20min mixing and cross 100 mesh sieves, get the raw material that 30g fully grinds and pack in punching block, coldmoulding under 50MPa pressure, acquisition diameter is the cylinder blank that 30mm, thickness are about 4.8mm;
(3) self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 20V, electric current are 50A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 80MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product); The relative density of synthetic sample is 98%, and product is the artificial rock B system block of zirconolite-rich type, wherein: zirconolite massfraction is about 75%, hollandite is about 10%, uhligite is about 15%.
Embodiment 3:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
(1) by feed proportioning:: by raw material with Ca (NO
3)
2.4H
2o:42.8%, CaO:1.5%, ZrO
2: 22.3%, Ti:8.7%, TiO
2: 22.6%, BaO:1.5%, Al
2o
3: 0.5% mass percent example feeding also mixes;
(2) by the former abrasive lapping 30min mixing and cross 150 mesh sieves, get the raw material that 25g fully grinds and pack in punching block, coldmoulding under 20MPa pressure, acquisition diameter is the cylinder blank that 30mm, thickness are about 4.6mm;
(3) adopt self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 50V, electric current are 40A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 50MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product); The relative density of synthetic sample is 96%, and product is the artificial rock block of zirconolite-rich type C system, wherein: zirconolite massfraction is about 80%, hollandite is about 5%, uhligite is about 10%, rutile is about 5%.
Embodiment 4:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
(1) by feed proportioning:: by raw material with Ca (NO
3)
2.4H
2o:37%, CaO:3.1%, ZrO
2: 19.3%, Ti:7.5%, TiO
2: 28.3%, BaO:3.1%, Al
2o
3: 1.6% mass percent example feeding also mixes;
(2) by the former abrasive lapping 30min mixing and cross 150 mesh sieves, get the raw material that 25g fully grinds and pack in punching block, coldmoulding under 20MPa pressure, acquisition diameter is the cylinder blank that 30mm, thickness are about 4.5mm;
(3) adopt self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 20V, electric current are 40A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 80MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product); The relative density of synthetic sample is 96%, and product is the artificial rock block of zirconolite-rich type C system, wherein: zirconolite massfraction is about 80%, hollandite is about 10%, uhligite is about 5%, rutile is about 5%.
Embodiment 5:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
(1) by feed proportioning:: by raw material with Ca (NO
3)
2.4H
2o:42.9%, CaO:1.6%, ZrO
2: 22.3%, Ti:8.7%, TiO
2: 16.8%, Al
2o
3: 4.1%, SiO
2: 1.6%, Na
2the mass percent example feeding of O:1.6%, MgO:1.1% also mixes;
(2) by the former abrasive lapping 35min mixing and cross 100 mesh sieves, get the raw material that 35g fully grinds and pack in punching block, coldmoulding under 100MPa pressure, acquisition diameter is the cylinder blank that 40mm, thickness are about 3.2mm;
(3) adopt self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 25V, electric current are 60A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 30MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product); Synthetic product is the artificial rock block of zirconolite-rich type D system, wherein: zirconolite massfraction is about 80%, uhligite is about 10%, nepheline is about 5%, magnesium-aluminium spinel is about 5%.
Embodiment 6:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
(1) by feed proportioning:: by raw material with Ca (NO
3)
2.4H
2o:37.4%, CaO:3.2%, ZrO
2: 19.5%, Ti:7.6%, TiO
2: 17.2%, Al
2o
3: 8.2%, SiO
2: 3.2%, Na
2the mass percent example feeding of O:1.7%, MgO:2.2% also mixes;
(2) by the former abrasive lapping 35min mixing and cross 100 mesh sieves, get the raw material that 35g fully grinds and pack in punching block, coldmoulding under 100MPa pressure, acquisition diameter is the cylinder blank that 40mm, thickness are about 3.4mm;
(3) adopt self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 25V, electric current are 60A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 30MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product); Synthetic product is the artificial rock block of zirconolite-rich type D system, wherein: zirconolite massfraction is about 70%, uhligite is about 10%, nepheline is about 10%, magnesium-aluminium spinel is about 10%.
Embodiment 7:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 25%, calcium oxide (CaO) 9%, zirconium dioxide (ZrO
2) 15%, titanium valve (Ti) 12%, titanium dioxide (TiO
2) 20%, barium oxide (BaO) 3%, aluminium sesquioxide (Al
2o
3) 16% component and mass percent get each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 20min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 55g compound and pack in mould, adopt 60MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 30mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 18V, electric current are 65A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 160MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
Embodiment 8:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15%, calcium oxide (CaO) 3%, zirconium dioxide (ZrO
2) 5%, titanium valve (Ti) 20%, titanium dioxide (TiO
2) 35%, barium oxide (BaO) 5%, aluminium sesquioxide (Al
2o
3) 17% component and mass percent get each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 10min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10g compound and pack in mould, adopt 5MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 10mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 30V, electric current are 30A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 30MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
Embodiment 9:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 35%, calcium oxide (CaO) 15%, zirconium dioxide (ZrO
2) 25%, titanium valve (Ti) 5%, titanium dioxide (TiO
2) 9%, barium oxide (BaO) 1%, aluminium sesquioxide (Al
2o
3) 10% component and mass percent get each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 100g compound and pack in mould, adopt 100MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 50mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 30V, electric current are 100A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 300MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
Embodiment 10～16:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15～35%, calcium oxide (CaO) 3～15%, zirconium dioxide (ZrO
2) 5～25%, titanium valve (Ti) 5～20%, titanium dioxide (TiO
2) 5～35%, barium oxide (BaO) 1～5%, aluminium sesquioxide (Al
2o
3) 3～30% component and mass percent get each component raw material; In each embodiment, the concrete mass percent consumption of each component raw material sees the following form:
B, abrasive material: said components raw material mixed and after dry ball milling 10～30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10～100g compound and pack in mould, adopt 5～100MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 10～50mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 5～30V, electric current are 30～100A, blank 4 (can) ignite when temperature reaches 2000～3000K, after finishing, self-propagating combustion in 3～5 second time, mold 3 is applied to 30～300MPa pressure until blank 4 is cooled to normal temperature; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
The artificial rock behaviour of the densification zirconolite-rich type lithogenesis stone B system that above-mentioned enforcement 7～16 examples make, this B system ore deposit is zirconolite, hollandite, uhligite mutually, and the content range of the mass percent of each ore deposit phase exists: in zirconolite 65～90%, hollandite 3～10%, uhligite 7～25%.
Embodiment 17:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 22%, calcium oxide (CaO) 6%, zirconium dioxide (ZrO
2) 12%, titanium valve (Ti) 15%, titanium dioxide (TiO
2) 27%, barium oxide (BaO) 3%, aluminium sesquioxide (Al
2o
3) 15% component and mass percent get each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 22min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 60g compound and pack in mould, adopt 52MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 30mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 17V, electric current are 60A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 160MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
Embodiment 18:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15%, calcium oxide (CaO) 3%, zirconium dioxide (ZrO
2) 5%, titanium valve (Ti) 10%, titanium dioxide (TiO
2) 37%, barium oxide (BaO) 5%, aluminium sesquioxide (Al
2o
3) 25% component and mass percent get each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 10min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10g compound and pack in mould, adopt 5MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 10mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 5V, electric current are 30A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 30MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
Embodiment 19:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 30%, calcium oxide (CaO) 10%, zirconium dioxide (ZrO
2) 20%, titanium valve (Ti) 10%, titanium dioxide (TiO
2) 15%, barium oxide (BaO) 1%, aluminium sesquioxide (Al
2o
3) 14% component and mass percent get each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 100g compound and pack in mould, adopt 100MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 50mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 30V, electric current are 100A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 300MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
Embodiment 20～26:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15～30%, calcium oxide (CaO) 3～10%, zirconium dioxide (ZrO
2) 5～20%, titanium valve (Ti) 10～20%, titanium dioxide (TiO
2) 15～40%, barium oxide (BaO) 1～5%, aluminium sesquioxide (Al
2o
3) 3～25% component and mass percent get each component raw material;
In each embodiment, the concrete mass percent consumption of each component raw material sees the following form:
B, abrasive material: said components raw material mixed and after dry ball milling 10～30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10～100g compound and pack in mould, adopt 5～100MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 10～50mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 5～30V, electric current are 30～100A, blank 4 (can) ignite when temperature reaches 2000～3000K, after finishing, self-propagating combustion in 3～5 second time, mold 3 is applied to 30～300MPa pressure until blank 4 is cooled to normal temperature; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
The artificial rock behaviour of the densification zirconolite-rich type lithogenesis stone C system that above-mentioned enforcement 17～26 examples make, this C system chats is zirconolite, hollandite, uhligite, rutile mutually, and the content range of the mass percent of each ore deposit phase exists: in zirconolite 60～85%, hollandite 3～5%, uhligite 7～20%, rutile 5～15%.
Embodiment 27:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 22%, calcium oxide (CaO) 8%, zirconium dioxide (ZrO
2) 13%, titanium valve (Ti) 11%, titanium dioxide (TiO
2) 16%, barium oxide (BaO) 2%, aluminium sesquioxide (Al
2o
3) 15%, silicon-dioxide (SiO
2) 5%, sodium oxide (Na
2o) 2%, component and the mass percent of magnesium oxide (MgO) 6% are got each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 21min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 60g compound and pack in mould, adopt 60MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 30mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 16V, electric current are 60A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 160MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
Embodiment 28:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15%, calcium oxide (CaO) 3%, zirconium dioxide (ZrO
2) 5%, titanium valve (Ti) 5%, titanium dioxide (TiO
2) 20%, barium oxide (BaO) 5%, aluminium sesquioxide (Al
2o
3) 17%, silicon-dioxide (SiO
2) 10%, sodium oxide (Na
2o) 5%, component and the mass percent of magnesium oxide (MgO) 15% are got each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 10min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10g compound and pack in mould, adopt 5MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 10mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 5V, electric current are 30A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 30MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
Embodiment 29:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 35%, calcium oxide (CaO) 15%, zirconium dioxide (ZrO
2) 25%, titanium valve (Ti) 8%, titanium dioxide (TiO
2) 10%, barium oxide (BaO) 1%, aluminium sesquioxide (Al
2o
3) 3%, silicon-dioxide (SiO
2) 1%, sodium oxide (Na
2o) 1%, component and the mass percent of magnesium oxide (MgO) 1% are got each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 100g compound and pack in mould, adopt 100MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 50mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 30V, electric current are 100A, the blank 4 that (can) ignite when temperature reaches 2000～3000K in 3～5 second time, applies 300MPa pressure until blank 4 is cooled to normal temperature to mold 3 after self-propagating combustion finishes; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
Embodiment 30～36:
The self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, comprises the following steps:
A, batching: press four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15～35%, calcium oxide (CaO) 3～15%, zirconium dioxide (ZrO
2) 5～25%, titanium valve (Ti) 5～20%, titanium dioxide (TiO
2) 5～35%, barium oxide (BaO) 1～5%, aluminium sesquioxide (Al
2o
3) 3～30%, silicon-dioxide (SiO
2) 1～10%, sodium oxide (Na
2o) 1～5%, component and the mass percent of magnesium oxide (MgO) 1～15% are got each component raw material;
In each embodiment, the concrete mass percent consumption of each component raw material sees the following form:
B, abrasive material: said components raw material mixed and after dry ball milling 10～30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10～100g compound and pack in mould, adopt 5～100MPa pressure that compound is pressed into the cylinder blank 4 that diameter is 10～50mm;
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel die being formed by bottom 1, annular sidewall 2 and seaming chuck 3; Referring to accompanying drawing 1, with quartz sand 7, be paved with steel die bottom 1, blank 4 is placed in to quartz sand top, at blank 4 one, be sidelong and put igniting tungsten filament 6 and make both (fully) contacts, at blank 4 opposite sides, place thermopair 5 and make both (fully) contacts, with quartz sand 7, will in steel die, fill up again, by seaming chuck 3 sealing steel die; Subsequently to the logical direct current of igniting tungsten filament 6, energising voltage is that 5～30V, electric current are 30～100A, blank 4 (can) ignite when temperature reaches 2000～3000K, after finishing, self-propagating combustion in 3～5 second time, mold 3 is applied to 30～300MPa pressure until blank 4 is cooled to normal temperature; Cooling rear blank 4 is taken out, make the artificial rock of densification zirconolite-rich type (block, i.e. finished product).
Above-described embodiment 27～36: the artificial rock behaviour of the densification zirconolite-rich type lithogenesis stone D system making, this D system ore deposit is zirconolite, uhligite, nepheline, spinel mutually, and the content range of the mass percent of each ore deposit phase exists: in zirconolite 50～85%, uhligite 5～10%, nepheline 5～15%, spinel 5～25%.
In above-described embodiment: the (Ca (NO of four water-calcium nitrate described in step a
3)
2.4H
2o) can replace with ferric oxide (Fe
2o
3) or molybdic oxide (MoO
3), or replace with four water-calcium nitrate (Ca (NO
3)
2.4H
2o), ferric oxide (Fe
2o
3), molybdic oxide (MoO
3) in the mixture of any two or three kinds of materials.
In above-described embodiment: each raw material adopting is commercially available prod, raw materials used in step a can be all purchased from Aladdin reagent company;
In above-described embodiment: in the percentage adopting, do not indicate especially, be quality (weight) percentage or well known to a person skilled in the art percentage; Described quality (weight) part can be all gram or kilogram; Described wt.% is mass percent.
In above-described embodiment: the processing parameter in each step (temperature, time, voltage, electric current, pressure etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of technology contents of narrating in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, all can implement and have described good result described in content of the present invention.
Claims (6)
1. the self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, it is characterized in that comprising the following steps:
A, batching: by the component of four water-calcium nitrate 15～35%, calcium oxide 3～15%, zirconium dioxide 5～25%, titanium valve 5～20%, titanium dioxide 5～35%, barium oxide 1～5%, aluminium sesquioxide 3～30% and mass percent, get each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 10～30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10～100g compound and pack in mould, adopt 5～100MPa pressure that compound is pressed into the cylinder blank that diameter is 10～50mm (4);
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel die being formed by bottom (1), annular sidewall (2) and seaming chuck (3); With quartz sand (7), be paved with steel die bottom (1), blank (4) is placed in to quartz sand top, at blank (4), be sidelong and put igniting tungsten filament (6) and both are contacted, at blank (4) opposite side, place thermopair (5) and both are contacted, use again quartz sand (7) in steel die, to fill up, by seaming chuck (3) sealing steel die; Subsequently to the logical direct current of igniting tungsten filament (6), energising voltage is that 5～30V, electric current are 30～100A, blank (4) ignites when temperature reaches 2000～3000K, after finishing, self-propagating combustion in 3～5 second time, mold (3) is applied to 30～300MPa pressure until blank (4) is cooled to normal temperature; Cooling rear blank (4) is taken out, make the artificial rock of densification zirconolite-rich type.
2. by the self propagating high temperature of the artificial rock of zirconolite-rich type described in claim 1, synthesize and densifying method, it is characterized in that: four water-calcium nitrate described in step a replaces with ferric oxide or molybdic oxide, or replace with in four water-calcium nitrate, ferric oxide, molybdic oxide the mixture of any two or three kinds of materials.
3. the self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, it is characterized in that comprising the following steps:
A, batching: by the component of four water-calcium nitrate 15～30%, calcium oxide 3～10%, zirconium dioxide 5～20%, titanium valve 10～20%, titanium dioxide 15～40%, barium oxide 1～5%, aluminium sesquioxide 3～25% and mass percent, get each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 10～30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10～100g compound and pack in mould, adopt 5～100MPa pressure that compound is pressed into the cylinder blank that diameter is 10～50mm (4);
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel die being formed by bottom (1), annular sidewall (2) and seaming chuck (3); With quartz sand (7), be paved with steel die bottom (1), blank (4) is placed in to quartz sand top, at blank (4), be sidelong and put igniting tungsten filament (6) and both are contacted, at blank (4) opposite side, place thermopair (5) and both are contacted, use again quartz sand (7) in steel die, to fill up, by seaming chuck (3) sealing steel die; Subsequently to the logical direct current of igniting tungsten filament (6), energising voltage is that 5～30V, electric current are 30～100A, blank (4) ignites when temperature reaches 2000～3000K, after finishing, self-propagating combustion in 3～5 second time, mold (3) is applied to 30～300MPa pressure until blank (4) is cooled to normal temperature; Cooling rear blank (4) is taken out, make the artificial rock of densification zirconolite-rich type.
4. by the self propagating high temperature of the artificial rock of zirconolite-rich type described in claim 3, synthesize and densifying method, it is characterized in that: four water-calcium nitrate described in step a replaces with ferric oxide or molybdic oxide, or replace with in four water-calcium nitrate, ferric oxide, molybdic oxide the mixture of any two or three kinds of materials.
5. the self propagating high temperature of the artificial rock of zirconolite-rich type synthesizes and densifying method, it is characterized in that comprising the following steps:
A, batching: by the component of four water-calcium nitrate 15～35%, calcium oxide 3～15%, zirconium dioxide 5～25%, titanium valve 5～20%, titanium dioxide 5～35%, barium oxide 1～5%, aluminium sesquioxide 3～30%, silica 1～10%, sodium oxide 1～5%, magnesium oxide 1～15% and mass percent, get each component raw material;
B, abrasive material: said components raw material mixed and after dry ball milling 10～30min, sieve, obtaining compound and make the particle diameter of compound be less than 20 orders;
C, compression moulding: get 10～100g compound and pack in mould, adopt 5～100MPa pressure that compound is pressed into the cylinder blank that diameter is 10～50mm (4);
D, self propagating high temperature synthesis of artificial rock: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel die being formed by bottom (1), annular sidewall (2) and seaming chuck (3); With quartz sand (7), be paved with steel die bottom (1), blank (4) is placed in to quartz sand top, at blank (4), be sidelong and put igniting tungsten filament (6) and both are contacted, at blank (4) opposite side, place thermopair (5) and both are contacted, use again quartz sand (7) in steel die, to fill up, by seaming chuck (3) sealing steel die; Subsequently to the logical direct current of igniting tungsten filament (6), energising voltage is that 5～30V, electric current are 30～100A, blank (4) ignites when temperature reaches 2000～3000K, after finishing, self-propagating combustion in 3～5 second time, mold (3) is applied to 30～300MPa pressure until blank (4) is cooled to normal temperature; Cooling rear blank (4) is taken out, make the artificial rock of densification zirconolite-rich type.
6. by the self propagating high temperature of the artificial rock of zirconolite-rich type described in claim 5, synthesize and densifying method, it is characterized in that: four water-calcium nitrate described in step a replaces with ferric oxide or molybdic oxide, or replace with in four water-calcium nitrate, ferric oxide, molybdic oxide the mixture of any two or three kinds of materials.
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| CN104496398A (en) * | 2014-12-04 | 2015-04-08 | 西南科技大学 | Preparation method for zirconolite type manmade rock |
| CN104773758A (en) * | 2015-04-10 | 2015-07-15 | 西南科技大学 | Preparation method for high-purity zirconolite powder |
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| CN104773758A (en) * | 2015-04-10 | 2015-07-15 | 西南科技大学 | Preparation method for high-purity zirconolite powder |
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