CN103992095B - The SHS process of zirconolite-rich type prosthetic graft and densifying method - Google Patents
The SHS process of zirconolite-rich type prosthetic graft and densifying method Download PDFInfo
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- CN103992095B CN103992095B CN201410224871.1A CN201410224871A CN103992095B CN 103992095 B CN103992095 B CN 103992095B CN 201410224871 A CN201410224871 A CN 201410224871A CN 103992095 B CN103992095 B CN 103992095B
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Abstract
The invention discloses SHS process and the densifying method of zirconolite-rich type prosthetic graft, it is characterized in that: by raw material mixing, ball millings such as four water-calcium nitrate, calcium oxide, zirconium dioxide, titanium valve, titania, baryta, alundum (Al2O3)s, sieve, obtain compound; Compound is loaded mould, is pressed into blank; Adopt self-spreading quasi isopressing device, blank is made densification zirconolite-rich type prosthetic graft.Adopt the present invention, obtained zirconolite-rich type prosthetic graft is comparatively large for the containing such as rare earth element and actinide amount, and element range comprehension is wide; The present invention adopts self-propagating high-temperature synthetic method, and aggregate velocity is fast, with short production cycle, production efficiency is high, provide thermal source, technique simple, practical without the need to the external world; Zirconolite-rich type prosthetic graft prepared by the present invention is applicable to the solidification process of radioactive waste.
Description
Technical field
The invention belongs to the preparation of prosthetic graft, relate to SHS process and the densifying method of zirconolite-rich type prosthetic graft.The zirconolite-rich type prosthetic graft adopting the present invention to prepare is specially adapted to high-level radioactive waste process; Zirconolite type prosthetic graft is the main parasitic phase of actinide, also has good pardon for rare earth element, has good development prospect high the putting in waste material of process.
Background technology
SHS process (referred to as SHS) technology (that is: adopting the preparation method of self-spreading quasi isopressing device) is an important material preparation technology, what it utilized the maintenance of chemical reaction self-heat generation to react continues to carry out, thus synthesis has the product of specifying composition and structure.Compared with traditional handicraft, SHS technology has the advantages such as reaction velocity is fast, energy consumption is little, equipment is simple, easy to operate, is subject to the great attention of domestic and international each research institution.From the former Russian scholar Merzhanov invention in 1967, over more than 40 year, SHS technology obtains extensive research, now develop into the new disciplines between combustion science and material science, adopt SHS technique can synthesize ceramic material, Metal Substrate and ceramic matric composite, intermetallic compound, functionally gradient material (FGM), the contour technical pattern of high-temperature superconductor and functional material, be used widely in the industrial production.
In prior art, the disposal that height puts waste material mainly contains temporary in underground storage tank, solidification and long storage periods.At present, the firming body material of application and research has glass, plastics, cement, pitch, prosthetic graft etc., and wherein glass and prosthetic graft are that many two kinds high of research both at home and abroad put waste material curing substrate.Glass solidification Technical comparing is ripe, but glass is subject to the impact of water or water vapor under the environment of High Temperature High Pressure, Industry organizations trucfure heating change, the entirety of material is finally caused to be destroyed, and prosthetic graft is due to its high-compactness, chemical stability is strong, Flouride-resistani acid phesphatase strong and anti-leaching performance is strong advantage, cause great attention and the interest widely of various countries.
Prosthetic graft is divided into A, B, C, D, E, F system, and its main mine is zirconolite, hollandite, pyrochlore, perovskite, rutile, spinel, nepheline etc. mutually.The primary curing typical case of A, B system is high puts waste material, and containing amount is 0 ~ 10wt.%; The solidification of C system is to liking commercial drivers heap aftertreatment high activity liquid waste, and containing amount is 5 ~ 22wt.%, and formula flexibly, and physical property is high, and chemical stability is good; D system handling object is that military height puts waste material, and containing amount is 60 ~ 70wt.%, and its containing amount is high; The solidification of E system to as if power reactor is high puts waste material, containing amount is 0 ~ 10wt.%, and containing amount is less, but to release rate little for heat, and chemical stability is high; The solidification of F system is to liking " through type " spentnuclear fuel, and containing amount is that the advantage of 0 ~ 50wt.%, F system is to contain the high waste liquid of uranium content.
Zirconolite is widely studied due to its high pardon for actinide and rare earth element, 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 process, and liquid phase reactor legal system is for zirconolite type prosthetic graft firming body, and technique is more complicated, and the cost of raw material is higher.Solid phase method adopts solid reaction process, and technique is simple, and raw material is easy to get and price is lower.Therefore, prepare zirconolite-rich type prosthetic graft firming body with solid phase method and be more suitable for through engineering approaches application, but its synthesis cycle of existing solid phase method is long, and synthesis temperature is high, poor practicability, through engineering approaches application is still needed to improve its technique.
Summary of the invention
Object of the present invention is intended to overcome deficiency of the prior art, provides a kind of SHS process and densifying method of zirconolite-rich type prosthetic graft.Thus zirconolite-rich type prosthetic graft block and the synthetic method of a kind of effective raising containing amount and element range comprehension are provided.
Content of the present invention is: the SHS process of zirconolite-rich type prosthetic graft and densifying method, is characterized in that comprising the following steps:
A, batching: by 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%, titania (TiO
2) 5 ~ 35%, baryta (BaO) 1 ~ 5%, alundum (Al2O3) (Al
2o
3) 3 ~ 30% component and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 10 ~ 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10 ~ 100g compound and load in mould, adopt 5 ~ 100MPa pressure compound to be pressed into the cylinder blank (4) that diameter is 10 ~ 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel mold be made up of bottom (1), annular sidewall (2) and seaming chuck (3); See accompanying drawing 1, (1) bottom steel mold is paved with silica sand (7), blank (4) is placed in above silica sand, igniting tungsten filament (6) is placed in blank (4) side, and make both (fully) contacts, thermopair (5) is placed at blank (4) opposite side, and make both (fully) contacts, use silica sand (7) to fill up in steel mold again, close steel mold with seaming chuck (3); Subsequently to the logical direct current of igniting tungsten filament (6), power-on voltage is 5 ~ 30V, electric current is 30 ~ 100A, (can) be ignited when temperature reaches 2000 ~ 3000K blank (4), after self-propagating combustion terminates in 3 ~ 5 second time, 30 ~ 300MPa pressure is applied until blank (4) is cooled to normal temperature to seaming chuck (3); After cooling, blank (4) takes out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Obtained densification zirconolite-rich type prosthetic graft is prosthetic graft B system, this B system ore deposit is zirconolite, hollandite, perovskite mutually, and the mass percentage content scope of each ore deposit phase is: zirconolite 65 ~ 90%, hollandite 3 ~ 10%, perovskite 7 ~ 25%.
In content of the present invention: the (Ca (NO of four water-calcium nitrate described in step a
3)
2.4H
2o) di-iron trioxide (Fe can be replaced with
2o
3) or molybdenum trioxide (MoO
3), or replace with four water-calcium nitrate (Ca (NO
3)
2.4H
2o), di-iron trioxide (Fe
2o
3), molybdenum trioxide (MoO
3) in the potpourri of any two or three kinds of materials.
Another content of the present invention is: the SHS process of zirconolite-rich type prosthetic graft and densifying method, is characterized in that comprising the following steps:
A, batching: by 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%, titania (TiO
2) 15 ~ 40%, baryta (BaO) 1 ~ 5%, alundum (Al2O3) (Al
2o
3) 3 ~ 25% component and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 10 ~ 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10 ~ 100g compound and load in mould, adopt 5 ~ 100MPa pressure compound to be pressed into the cylinder blank (4) that diameter is 10 ~ 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel mold be made up of bottom (1), annular sidewall (2) and seaming chuck (3); See accompanying drawing 1, (1) bottom steel mold is paved with silica sand (7), blank (4) is placed in above silica sand, igniting tungsten filament (6) is placed in blank (4) side, and make both (fully) contacts, thermopair (5) is placed at blank (4) opposite side, and make both (fully) contacts, use silica sand (7) to fill up in steel mold again, close steel mold with seaming chuck (3); Subsequently to the logical direct current of igniting tungsten filament (6), power-on voltage is 5 ~ 30V, electric current is 30 ~ 100A, (can) be ignited when temperature reaches 2000 ~ 3000K blank (4), after self-propagating combustion terminates in 3 ~ 5 second time, 30 ~ 300MPa pressure is applied until blank (4) is cooled to normal temperature to seaming chuck (3); After cooling, blank (4) takes out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Obtained densification zirconolite-rich type prosthetic graft is prosthetic graft C system, this C system chats is zirconolite, hollandite, perovskite, rutile mutually, and the mass percentage content scope of each ore deposit phase is: zirconolite 60 ~ 85%, hollandite 3 ~ 5%, perovskite 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) di-iron trioxide (Fe can be replaced with
2o
3) or molybdenum trioxide (MoO
3), or replace with four water-calcium nitrate (Ca (NO
3)
2.4H
2o), di-iron trioxide (Fe
2o
3), molybdenum trioxide (MoO
3) in the potpourri of any two or three kinds of materials.
Content of the present invention can also be: the SHS process of zirconolite-rich type prosthetic graft and densifying method, is characterized in that comprising the following steps:
A, batching: by 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%, titania (TiO
2) 5 ~ 35%, baryta (BaO) 1 ~ 5%, alundum (Al2O3) (Al
2o
3) 3 ~ 30%, silicon dioxide (SiO
2) 1 ~ 10%, sodium oxide molybdena (Na
2o) 1 ~ 5%, the component of magnesium oxide (MgO) 1 ~ 15% and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 10 ~ 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10 ~ 100g compound and load in mould, adopt 5 ~ 100MPa pressure compound to be pressed into the cylinder blank (4) that diameter is 10 ~ 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel mold be made up of bottom (1), annular sidewall (2) and seaming chuck (3); See accompanying drawing 1, (1) bottom steel mold is paved with silica sand (7), blank (4) is placed in above silica sand, igniting tungsten filament (6) is placed in blank (4) side, and make both (fully) contacts, thermopair (5) is placed at blank (4) opposite side, and make both (fully) contacts, use silica sand (7) to fill up in steel mold again, close steel mold with seaming chuck (3); Subsequently to the logical direct current of igniting tungsten filament (6), power-on voltage is 5 ~ 30V, electric current is 30 ~ 100A, (can) be ignited when temperature reaches 2000 ~ 3000K blank (4), after self-propagating combustion terminates in 3 ~ 5 second time, 30 ~ 300MPa pressure is applied until blank (4) is cooled to normal temperature to seaming chuck (3); After cooling, blank (4) takes out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Obtained densification zirconolite-rich type prosthetic graft is prosthetic graft D system, this D system ore deposit is zirconolite, perovskite, nepheline, spinel mutually, and the mass percentage content scope of each ore deposit phase is: zirconolite 50 ~ 85%, perovskite 5 ~ 10%, nepheline 5 ~ 15%, spinel 5 ~ 25%.
(Ca (the NO of four water-calcium nitrate described in step a
3)
2.4H
2o) di-iron trioxide (Fe can be replaced with
2o
3) or molybdenum trioxide (MoO
3), or replace with four water-calcium nitrate (Ca (NO
3)
2.4H
2o), di-iron trioxide (Fe
2o
3), molybdenum trioxide (MoO
3) in the potpourri of any two or three kinds of materials.
In foregoing invention content: described in step a, component raw material is commercially available prod, can purchased from Aladdin Reagent Company;
Compared with prior art, the present invention has features and beneficial effect:
(1) due to zirconolite (CaZrTi
2o
7) stability be obviously better than perovskite, the fission nuclides such as Sr, Cs can not only be fixed in its crystalline network by it, and to long-life actinium series nucleic, also there is very good ability to cure, SHS process method is applied to the preparation of zirconolite base prosthetic graft curing substrate by the present invention, and the solidification process of zirconolite-rich type prosthetic graft to high-level waste of preparation must have better effect;
(2) adopt the present invention, the product obtained is zirconolite-rich type prosthetic graft block, large to the containing amount of nucleic, contains elemental range wide; Synthetic product main mine of the present invention is zirconolite mutually, prosthetic graft B, C, D system can be divided into again according to other ore deposit phase compositions, its element containing amount is between 0 ~ 70wt.%, element range comprehension is the metallic element such as Sr, Y, actinide, lanthanide series, Cs, Mg, Co, Ni, Mo, Ru, Sn, Mn, Cs, Pb, Na, K, Ba, Rb and Fe, Mn, Cr, and can adjust each ore deposit matched as the case may be; The present invention adopts 30 ~ 300MPa pressure in course of reaction, and product density is high, good stability; In the present invention, B system adds hollandite, and hollandite adopts the Ba type hollandite of principle mainly through prosthetic graft of the law of isomorphism, is that the mode that Cs is replaced by aliovalent or compensation is fixed in the tunnel structure of hollandite; Spinel and nepheline is added, spinel (AB in D system
2o
4) because isomorph replaces comparatively general, A position can be Mg, Fe, Zn, Mn, and B position can be Al, Cr, Fe, and the containing therefore for metallic element is better; Nepheline adopts the law of isomorphism principle K, Cs can be fixed on the Na position of nepheline;
(3) the present invention is adopted, in the prosthetic graft B system of preparation, main mine is zirconolite mutually, perovskite, hollandite, wherein zirconolite and perovskite are for Sr, Y, actinide, lanthanide series has good solidification effect, good solidification effect is also showed to Cs simultaneously, in B system, hollandite adds, can to Mg, Co, Ni, Mo, Ru, Sn, Mn, Cs, the elements such as Pb solidify preferably, adding of hollandite not only increases solidification elemental range and dirigibility, also contribute to improving anti-leaching performance simultaneously, its element containing amount is 0 ~ 10 (wt.%), C system with the addition of Rutile Type on the basis of B system, and mainly improve its physical and chemical stability and ore deposit phase compatibility, element containing amount is increased to 5 ~ 22 (wt.%) on the basis of B system, in D system, main mine is zirconolite, perovskite, spinel, nepheline mutually, this system containing amount is large, usual element containing amount can reach 60 ~ 70 (wt.%), wherein be solidified with good result for metallic elements such as Fe, Mn, Cr adding of spinel, the solidification being added in Na, K, Ba, Rb of nepheline has remarkable effect, in the present invention, in each system, the proportion adjustment dirigibility of each ore deposit phase is comparatively large, can make suitable adjustment according to different situations,
(4) the present invention adopts self-propagating high-temperature synthetic method, and aggregate velocity is fast, with short production cycle, production efficiency is high, temperature of reaction is high, provide thermal source and energy without the need to the external world, and technique is simple, energy consumption is little, and equipment is simple, and product purity is high, easy to operate, practical.
Accompanying drawing explanation
Fig. 1 is the self-propagating isopressing device schematic diagram that the present invention adopts;
Fig. 2 is the XRD diffracting spectrum of the finished product that the embodiment of the present invention 2 obtains.
In Fig. 1: bottom 1-steel mold, 2-(steel mold) annular sidewalls, 3-(steel mold) seaming chucks, 4-blank, 5-thermopair, 6-igniting tungsten filament, 7-silica 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 SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise 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: the mass percent feeding of 1% also mixes;
(2) will the raw mill 20min that mix cross 100 mesh sieves, get the raw material that 30g fully grinds and load in punching block, cold briquetting under 50MPa pressure, the cylinder blank that acquisition diameter is 30mm, thickness is about 5mm;
(3) SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 20V, electric current is 50A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 100MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product); The relative density of synthetic sample is 97%, and product is the prosthetic graft B system block of zirconolite-rich type, wherein: zirconolite massfraction for about 80%, hollandite is about 6%, perovskite is about 14%.
Embodiment 2:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise 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: the mass percent feeding of 1.6% also mixes;
(2) will the raw mill 20min that mix cross 100 mesh sieves, get the raw material that 30g fully grinds and load in punching block, cold briquetting under 50MPa pressure, the cylinder blank that acquisition diameter is 30mm, thickness is about 4.8mm;
(3) SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 20V, electric current is 50A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 80MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product); The relative density of synthetic sample is 98%, and product is the prosthetic graft B system block of zirconolite-rich type, wherein: zirconolite massfraction is about 75%, hollandite is about 10%, perovskite is about 15%.
Embodiment 3:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise 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: the percent mass ratio feeding of 0.5% also mixes;
(2) will the raw mill 30min that mix cross 150 mesh sieves, get the raw material that 25g fully grinds and load in punching block, cold briquetting under 20MPa pressure, the cylinder blank that acquisition diameter is 30mm, thickness is about 4.6mm;
(3) SHS process prosthetic graft is adopted: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 50V, electric current is 40A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 50MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product); The relative density of synthetic sample is 96%, and product is zirconolite-rich type C system prosthetic graft block, wherein: zirconolite massfraction is about 80%, hollandite is about 5%, perovskite is about 10%, rutile is about 5%.
Embodiment 4:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise 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: the percent mass ratio feeding of 1.6% also mixes;
(2) will the raw mill 30min that mix cross 150 mesh sieves, get the raw material that 25g fully grinds and load in punching block, cold briquetting under 20MPa pressure, the cylinder blank that acquisition diameter is 30mm, thickness is about 4.5mm;
(3) SHS process prosthetic graft is adopted: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 20V, electric current is 40A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 80MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product); The relative density of synthetic sample is 96%, and product is zirconolite-rich type C system prosthetic graft block, wherein: zirconolite massfraction is about 80%, hollandite is about 10%, perovskite is about 5%, rutile is about 5%.
Embodiment 5:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise 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 percent mass ratio feeding of O:1.6%, MgO:1.1% also mixes;
(2) will the raw mill 35min that mix cross 100 mesh sieves, get the raw material that 35g fully grinds and load in punching block, cold briquetting under 100MPa pressure, the cylinder blank that acquisition diameter is 40mm, thickness is about 3.2mm;
(3) SHS process prosthetic graft is adopted: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 25V, electric current is 60A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 30MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product); Synthetic product is zirconolite-rich type D system prosthetic graft block, wherein: zirconolite massfraction is about 80%, perovskite is about 10%, nepheline is about 5%, magnesium aluminate spinel is about 5%.
Embodiment 6:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise 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 percent mass ratio feeding of O:1.7%, MgO:2.2% also mixes;
(2) will the raw mill 35min that mix cross 100 mesh sieves, get the raw material that 35g fully grinds and load in punching block, cold briquetting under 100MPa pressure, the cylinder blank that acquisition diameter is 40mm, thickness is about 3.4mm;
(3) SHS process prosthetic graft is adopted: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 25V, electric current is 60A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 30MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product); Synthetic product is zirconolite-rich type D system prosthetic graft block, wherein: zirconolite massfraction is about 70%, perovskite is about 10%, nepheline is about 10%, magnesium aluminate spinel is about 10%.
Embodiment 7:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 25%, calcium oxide (CaO) 9%, zirconium dioxide (ZrO
2) 15%, titanium valve (Ti) 12%, titania (TiO
2) 20%, baryta (BaO) 3%, alundum (Al2O3) (Al
2o
3) 16% component and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 20min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 55g compound and load in mould, adopt 60MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 30mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 18V, electric current is 65A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 160MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Embodiment 8:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15%, calcium oxide (CaO) 3%, zirconium dioxide (ZrO
2) 5%, titanium valve (Ti) 20%, titania (TiO
2) 35%, baryta (BaO) 5%, alundum (Al2O3) (Al
2o
3) 17% component and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 10min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10g compound and load in mould, adopt 5MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 10mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 30V, electric current is 30A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 30MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Embodiment 9:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 35%, calcium oxide (CaO) 15%, zirconium dioxide (ZrO
2) 25%, titanium valve (Ti) 5%, titania (TiO
2) 9%, baryta (BaO) 1%, alundum (Al2O3) (Al
2o
3) 10% component and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 100g compound and load in mould, adopt 100MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 30V, electric current is 100A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 300MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Embodiment 10 ~ 16:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by 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%, titania (TiO
2) 5 ~ 35%, baryta (BaO) 1 ~ 5%, alundum (Al2O3) (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: mixed by said components raw material and after dry ball milling 10 ~ 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10 ~ 100g compound and load in mould, adopt 5 ~ 100MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 10 ~ 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 5 ~ 30V, electric current is 30 ~ 100A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, 30 ~ 300MPa pressure is applied until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
The densification zirconolite-rich type prosthetic graft that above-mentioned enforcement 7 ~ 16 example obtains is prosthetic graft B system, this B system ore deposit is zirconolite, hollandite, perovskite mutually, and the content range of the mass percent of each ore deposit phase exists: in zirconolite 65 ~ 90%, hollandite 3 ~ 10%, perovskite 7 ~ 25%.
Embodiment 17:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 22%, calcium oxide (CaO) 6%, zirconium dioxide (ZrO
2) 12%, titanium valve (Ti) 15%, titania (TiO
2) 27%, baryta (BaO) 3%, alundum (Al2O3) (Al
2o
3) 15% component and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 22min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 60g compound and load in mould, adopt 52MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 30mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 17V, electric current is 60A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 160MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Embodiment 18:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15%, calcium oxide (CaO) 3%, zirconium dioxide (ZrO
2) 5%, titanium valve (Ti) 10%, titania (TiO
2) 37%, baryta (BaO) 5%, alundum (Al2O3) (Al
2o
3) 25% component and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 10min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10g compound and load in mould, adopt 5MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 10mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 5V, electric current is 30A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 30MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Embodiment 19:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 30%, calcium oxide (CaO) 10%, zirconium dioxide (ZrO
2) 20%, titanium valve (Ti) 10%, titania (TiO
2) 15%, baryta (BaO) 1%, alundum (Al2O3) (Al
2o
3) 14% component and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 100g compound and load in mould, adopt 100MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 30V, electric current is 100A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 300MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Embodiment 20 ~ 26:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by 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%, titania (TiO
2) 15 ~ 40%, baryta (BaO) 1 ~ 5%, alundum (Al2O3) (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: mixed by said components raw material and after dry ball milling 10 ~ 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10 ~ 100g compound and load in mould, adopt 5 ~ 100MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 10 ~ 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 5 ~ 30V, electric current is 30 ~ 100A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, 30 ~ 300MPa pressure is applied until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
The densification zirconolite-rich type prosthetic graft that above-mentioned enforcement 17 ~ 26 example obtains is prosthetic graft C system, this C system chats is zirconolite, hollandite, perovskite, rutile mutually, and the content range of the mass percent of each ore deposit phase exists: in zirconolite 60 ~ 85%, hollandite 3 ~ 5%, perovskite 7 ~ 20%, rutile 5 ~ 15%.
Embodiment 27:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 22%, calcium oxide (CaO) 8%, zirconium dioxide (ZrO
2) 13%, titanium valve (Ti) 11%, titania (TiO
2) 16%, baryta (BaO) 2%, alundum (Al2O3) (Al
2o
3) 15%, silicon dioxide (SiO
2) 5%, sodium oxide molybdena (Na
2o) 2%, the component of magnesium oxide (MgO) 6% and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 21min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 60g compound and load in mould, adopt 60MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 30mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 16V, electric current is 60A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 160MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Embodiment 28:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 15%, calcium oxide (CaO) 3%, zirconium dioxide (ZrO
2) 5%, titanium valve (Ti) 5%, titania (TiO
2) 20%, baryta (BaO) 5%, alundum (Al2O3) (Al
2o
3) 17%, silicon dioxide (SiO
2) 10%, sodium oxide molybdena (Na
2o) 5%, the component of magnesium oxide (MgO) 15% and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 10min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10g compound and load in mould, adopt 5MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 10mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 5V, electric current is 30A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 30MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Embodiment 29:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by four water-calcium nitrate (Ca (NO
3)
2.4H
2o) 35%, calcium oxide (CaO) 15%, zirconium dioxide (ZrO
2) 25%, titanium valve (Ti) 8%, titania (TiO
2) 10%, baryta (BaO) 1%, alundum (Al2O3) (Al
2o
3) 3%, silicon dioxide (SiO
2) 1%, sodium oxide molybdena (Na
2o) 1%, the component of magnesium oxide (MgO) 1% and mass percent get each component raw material;
B, abrasive material: mixed by said components raw material and after dry ball milling 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 100g compound and load in mould, adopt 100MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 30V, electric current is 100A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, applies 300MPa pressure until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Embodiment 30 ~ 36:
The SHS process of zirconolite-rich type prosthetic graft and densifying method, comprise the following steps:
A, batching: by 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%, titania (TiO
2) 5 ~ 35%, baryta (BaO) 1 ~ 5%, alundum (Al2O3) (Al
2o
3) 3 ~ 30%, silicon dioxide (SiO
2) 1 ~ 10%, sodium oxide molybdena (Na
2o) 1 ~ 5%, the component of magnesium oxide (MgO) 1 ~ 15% 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: mixed by said components raw material and after dry ball milling 10 ~ 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10 ~ 100g compound and load in mould, adopt 5 ~ 100MPa pressure compound to be pressed into the cylinder blank 4 that diameter is 10 ~ 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair 5, igniting tungsten filament 6, and the steel mold be made up of bottom 1, annular sidewall 2 and seaming chuck 3; See accompanying drawing 1,1 is paved with bottom steel mold with silica sand 7, blank 4 is placed in above silica sand, igniting tungsten filament 6 is placed in blank 4 side, and make both (fully) contacts, place thermopair 5 at blank 4 opposite side, and make both (fully) contacts, fill up in steel mold with silica sand 7 again, close steel mold with seaming chuck 3; Subsequently direct current is led to igniting tungsten filament 6, power-on voltage is 5 ~ 30V, electric current is 30 ~ 100A, (can) be ignited when temperature reaches 2000 ~ 3000K blank 4, after self-propagating combustion terminates in 3 ~ 5 second time, 30 ~ 300MPa pressure is applied until blank 4 is cooled to normal temperature to seaming chuck 3; Blank 4 after cooling is taken out, i.e. obtained densification zirconolite-rich type prosthetic graft (block, i.e. finished product).
Above-described embodiment 27 ~ 36: obtained densification zirconolite-rich type prosthetic graft is prosthetic graft D system, this D system ore deposit is zirconolite, perovskite, nepheline, spinel mutually, and the content range of the mass percent of each ore deposit phase exists: in zirconolite 50 ~ 85%, perovskite 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) di-iron trioxide (Fe can be replaced with
2o
3) or molybdenum trioxide (MoO
3), or replace with four water-calcium nitrate (Ca (NO
3)
2.4H
2o), di-iron trioxide (Fe
2o
3), molybdenum trioxide (MoO
3) in the potpourri of any two or three kinds of materials.
In above-described embodiment: each raw material adopted is commercially available prod, raw materials used in step a can all purchased from Aladdin Reagent Company;
In above-described embodiment: in the percentage adopted, 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.% and mass percent.
In above-described embodiment: the technological parameter (temperature, time, voltage, electric current, pressure etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The concrete same prior art of technology contents described in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (6)
1. the SHS process of zirconolite-rich type prosthetic graft and densifying method, is characterized in that comprising the following steps:
A, batching: get each component raw material by the component of four water-calcium nitrate 15 ~ 35%, calcium oxide 3 ~ 15%, zirconium dioxide 5 ~ 25%, titanium valve 5 ~ 20%, titania 5 ~ 35%, baryta 1 ~ 5%, alundum (Al2O3) 3 ~ 30% and mass percent;
B, abrasive material: mixed by said components raw material and after dry ball milling 10 ~ 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10 ~ 100g compound and load in mould, adopt 5 ~ 100MPa pressure compound to be pressed into the cylinder blank (4) that diameter is 10 ~ 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel mold be made up of bottom (1), annular sidewall (2) and seaming chuck (3); (1) bottom steel mold is paved with silica sand (7), blank (4) is placed in above silica sand, igniting tungsten filament (6) is placed in blank (4) side, and make both contacts, thermopair (5) is placed at blank (4) opposite side, and make both contacts, then use silica sand (7) to fill up in steel mold, close steel mold with seaming chuck (3); Subsequently to the logical direct current of igniting tungsten filament (6), power-on voltage is 5 ~ 30V, electric current is 30 ~ 100A, ignite when temperature reaches 2000 ~ 3000K blank (4), after self-propagating combustion terminates in 3 ~ 5 second time, 30 ~ 300MPa pressure is applied until blank (4) is cooled to normal temperature to seaming chuck (3); After cooling, blank (4) takes out, i.e. obtained densification zirconolite-rich type prosthetic graft.
2. by SHS process and the densifying method of zirconolite-rich type prosthetic graft described in claim 1, it is characterized in that: four water-calcium nitrate described in step a replaces with di-iron trioxide or molybdenum trioxide, or to replace with in four water-calcium nitrate, di-iron trioxide, molybdenum trioxide the potpourri of any two or three kinds of materials.
3. the SHS process of zirconolite-rich type prosthetic graft and densifying method, is characterized in that comprising the following steps:
A, batching: get each component raw material by the component of four water-calcium nitrate 15 ~ 30%, calcium oxide 3 ~ 10%, zirconium dioxide 5 ~ 20%, titanium valve 10 ~ 20%, titania 15 ~ 40%, baryta 1 ~ 5%, alundum (Al2O3) 3 ~ 25% and mass percent;
B, abrasive material: mixed by said components raw material and after dry ball milling 10 ~ 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10 ~ 100g compound and load in mould, adopt 5 ~ 100MPa pressure compound to be pressed into the cylinder blank (4) that diameter is 10 ~ 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel mold be made up of bottom (1), annular sidewall (2) and seaming chuck (3); (1) bottom steel mold is paved with silica sand (7), blank (4) is placed in above silica sand, igniting tungsten filament (6) is placed in blank (4) side, and make both contacts, thermopair (5) is placed at blank (4) opposite side, and make both contacts, then use silica sand (7) to fill up in steel mold, close steel mold with seaming chuck (3); Subsequently to the logical direct current of igniting tungsten filament (6), power-on voltage is 5 ~ 30V, electric current is 30 ~ 100A, ignite when temperature reaches 2000 ~ 3000K blank (4), after self-propagating combustion terminates in 3 ~ 5 second time, 30 ~ 300MPa pressure is applied until blank (4) is cooled to normal temperature to seaming chuck (3); After cooling, blank (4) takes out, i.e. obtained densification zirconolite-rich type prosthetic graft.
4. by SHS process and the densifying method of zirconolite-rich type prosthetic graft described in claim 3, it is characterized in that: four water-calcium nitrate described in step a replaces with di-iron trioxide or molybdenum trioxide, or to replace with in four water-calcium nitrate, di-iron trioxide, molybdenum trioxide the potpourri of any two or three kinds of materials.
5. the SHS process of zirconolite-rich type prosthetic graft and densifying method, is characterized in that comprising the following steps:
A, batching: get each component raw material by the component of four water-calcium nitrate 15 ~ 35%, calcium oxide 3 ~ 15%, zirconium dioxide 5 ~ 25%, titanium valve 5 ~ 20%, titania 5 ~ 35%, baryta 1 ~ 5%, alundum (Al2O3) 3 ~ 30%, silica 1 ~ 10%, sodium oxide molybdena 1 ~ 5%, magnesium oxide 1 ~ 15% and mass percent;
B, abrasive material: mixed by said components raw material and after dry ball milling 10 ~ 30min, sieve, obtain compound and make the particle diameter of compound be less than 20 orders;
C, compressing: to get 10 ~ 100g compound and load in mould, adopt 5 ~ 100MPa pressure compound to be pressed into the cylinder blank (4) that diameter is 10 ~ 50mm;
D, SHS process prosthetic graft: adopt self-spreading quasi isopressing device, the composition of this device comprises thermopair (5), igniting tungsten filament (6), and the steel mold be made up of bottom (1), annular sidewall (2) and seaming chuck (3); (1) bottom steel mold is paved with silica sand (7), blank (4) is placed in above silica sand, igniting tungsten filament (6) is placed in blank (4) side, and make both contacts, thermopair (5) is placed at blank (4) opposite side, and make both contacts, then use silica sand (7) to fill up in steel mold, close steel mold with seaming chuck (3); Subsequently to the logical direct current of igniting tungsten filament (6), power-on voltage is 5 ~ 30V, electric current is 30 ~ 100A, ignite when temperature reaches 2000 ~ 3000K blank (4), after self-propagating combustion terminates in 3 ~ 5 second time, 30 ~ 300MPa pressure is applied until blank (4) is cooled to normal temperature to seaming chuck (3); After cooling, blank (4) takes out, i.e. obtained densification zirconolite-rich type prosthetic graft.
6. by SHS process and the densifying method of zirconolite-rich type prosthetic graft described in claim 5, it is characterized in that: four water-calcium nitrate described in step a replaces with di-iron trioxide or molybdenum trioxide, or to replace with in four water-calcium nitrate, di-iron trioxide, molybdenum trioxide the potpourri of any two or three kinds of materials.
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| CN2695150Y (en) * | 2004-03-18 | 2005-04-27 | 北京科技大学 | Self-straggle high temperature synthesis quasi-isostatic pressure device |
| CN102568636A (en) * | 2012-02-21 | 2012-07-11 | 浙江大学 | CaTiZr (calcium, titanium and zirconium)-phase glass ceramic waste forms and preparation method thereof |
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| CN2695150Y (en) * | 2004-03-18 | 2005-04-27 | 北京科技大学 | Self-straggle high temperature synthesis quasi-isostatic pressure device |
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