CN106986377A - A kind of Gd2Ti2‑xZrxO7The self- propagating preparation method of pyrochlore - Google Patents
A kind of Gd2Ti2‑xZrxO7The self- propagating preparation method of pyrochlore Download PDFInfo
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Abstract
The invention discloses a kind of Gd2Ti2‑xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that：Ti, TiO are taken by a certain percentage2、ZrO2、Gd2O3, CuO powders be used as raw material；Through dry ball milling, mixing, drying, blank is pressed into；Blank is placed in self-spreading quasi isopressing device, reacted by the igniter blank that ignites, after-applied pressure is terminated in burning, that is, Gd is made2Ti2‑xZrxO7Pyrochlore.The present invention uses SHS process combination Rapid Densification Process of Preparing, it is only necessary to several minutes of times, that is, synthesizes the excellent pyrochlore-type prosthetic graft compact curing body of high thermal stability, high chemical stability, anti-radiation performance；Have the advantages that aggregate velocity is fast, production efficiency is high, reaction temperature is high, energy consumption is low, product purity is high, technique is simple, it is adaptable to the long-term safety curing process of actinium series nucleic and disposal in high-level waste.
Description
Technical field
The invention belongs to the preparation for the prosthetic graft for being used for radioactive waste curing process in field of Environment Protection, it is related to one kind
Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore.Pyrochlore-type prosthetic graft-Gd prepared by the present invention2Ti2-xZrxO7Burn
Green stone, is particularly suitable for use in long-term safety curing process and the disposal of actinium series nucleic in high-level waste.
Background technology
The processing of radwaste and the key link that disposal is nuclear industry development, the processing of current middle low-level waste and place
Put technology more ripe, high-level waste（Abbreviation HLW）Processing be still the weight of domestic and international radioactive-waste disposal
Point and difficult point.Prosthetic graft disposes HLW curing substrate as the second generation, is fixed radionuclide using isomorph principle
Among the lattice of ore deposit phase.Pyrochlore（Pyrochlore）As one of main mine phase in prosthetic graft, with high nucleic bag
Capacity, high thermal stability and chemical stability, and excellent anti-radiation performance, are preferable HLW curing mediums.At present, people
The preparation of lithogenesis stone is broadly divided into liquid phase method and solid phase method.Liquid phase method mainly includes hydroxide process and sol-gel process, liquid phase
Method prepares pyrochlore prosthetic graft firming body, and technique is more complicated, and cost of material is higher.Pyrochlore, work are prepared using solid phase method
Skill is simple, and raw material is easy to get and price is relatively low.Therefore, pyrochlore-type prosthetic graft is prepared with solid phase method and is more suitable for engineering application.
However, the problem of there is long preparation period in solid phase method, synthesis temperature is higher at present, it is desirable to obtain the high pyrochlore block of consistency
Body is, it is necessary to introduce the strong densification process such as HTHP, high temperature insostatic pressing (HIP), and equipment requirement is high, and technique is complex, and these factors are very
Pyrochlore-type prosthetic graft curing process HLW engineering application is hindered in big degree.
SHS process（Self-propagating High-temperature Synthesis, abbreviation SHS）It is
Proposed first by former Soviet Union scientist Merzhanov et al. in 1967.Compared with traditional handicraft, SHS technologies have synthesis
Speed is fast, low energy consumption, simple and easy to operate equipment the advantages of, receive the great attention of domestic and international each research institution.In view of
The plurality of advantages of SHS technologies, India scholar Muthuraman proposed this technology being applied to active nucleus waste matter in 1994
Curing process（M. Muthuraman etc., conbustion synthesis prepares oxide material solidification nuke rubbish, material science bulletin, and 1994,
17:977), Fe is used in Russia Borovinskaya in 1998 etc.2O3As oxidant, calcium titanium has been produced using SHS reactions
Ore deposit（CaTiO3）Solidify fission nuclide Sr（Borovinskaya etc., the SHS of class mineral material is prepared and its to radioactive waste
Curing process, international self- propagating magazine, 199,7：129）.
Pyrochlore（Chemical formula A2B2O7）As the derivative of fluorite structure, selectable A and B ion ranges are wide, so as to
Neutralized and ionic radius demand with the electricity price for meeting pyrochlore, allow a variety of radionuclides of solidification to be further possibly realized；A can
To be replaced by Na, Ca, Y and group of the lanthanides and actinides；And B can then be replaced by Ti, Zr, Nb, Hf, Ta, Sn and W；By
The brilliant position for entering pyrochlore in nucleic forms lattice solid solution, and its stability and long-term safety can be guaranteed；In addition, A and B
If position makes pyrochlore as the curing medium of actinium series nucleic occupied by Gd, Sm, Hf isotonic absorbent, can also be significantly
Degree improves the criticality safety of firming body.
In the prior art, pyrochlore synthetic method mainly includes：（1）Mechanical ball mill reaction method,（2）High temperature under normal pressure is consolidated
Phase reaction method,（3）High-temperature high-voltage reaction synthetic method.These synthesis techniques are relatively complicated, and synthesis cycle is long, are unfavorable for burning
The large-scale promotion of green stone curing process.
The content of the invention
The purpose of the present invention is intended to overcome that of the prior art not enough there is provided a kind of Gd2Ti2-xZrxO7Pyrochlore from climing
Prolong preparation method.The present invention uses SHS process（Abbreviation SHS）It is artificial that pyrochlore-type is prepared with reference to Quick-pressing technique
Rock, aggregate velocity is fast, low energy consumption, equipment operation are convenient, while can quickly apply pressure to sample after burning, can be when shorter
Between can obtain high densification sample, further increase Gd2Ti2-xZrxO7The nucleic curing performance of pyrochlore, is conducive to engineering
Using and promote.
The invention mainly includes：A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that：Adopt
With Ti powder as reducing agent, CuO powder uses SHS process as oxidant（Abbreviation SHS）With reference to quick pressure
Produce Gd2Ti2-xZrxO7Pyrochlore-type prosthetic graft block, its chemical equation（Ⅰ）For：
3Ti+(1-2x)TiO2+2xZrO2+2Gd2O3+6CuO = 2Gd2Ti2-xZrxO7+6Cu （Ⅰ）
Present disclosure is：A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, be in place of its feature include it is following
Step：
A, dispensing：By Ti：TiO2：ZrO2：Gd2O3：CuO = 3：(1-2x)：2x：2：6 mol ratio takes Ti, TiO2、ZrO2、
Gd2O3, CuO powders be used as raw material；
B, abrasive material：By said components raw material through dry ball milling 10~30 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound,
It is put into baking oven, is dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 10~50g to dry is fitted into Φ 20~50mm stainless steel moulds, using 10~
The compound of drying is pressed into 20~50mm's of diameter by 50MPa pressure（Cylinder）Blank（1）；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes：Connected or be connected as a single entity by bottom, lower end and bottom
The punching block that annular sidewall is constituted（4）, copper electrode（5）, with copper electrode（5）The tungsten filament of one end connection（3）, it is arranged at punching block（4）'s
The pressure head of upper end in annular sidewall（6）, and it is arranged at pressure head（6）The pressurization hydraulic press of top（7）；
Use quartz sand（2）It is paved with punching block（4）Inner bottom part, by blank（1）It is placed in quartz sand（2）On, blank（1）One side and company
It is connected on copper electrode（5）The tungsten filament of one end（3）Contact, then use quartz sand（2）By punching block（4）Inside fill up, use pressure head（6）Close punching block
（4）；
To tungsten filament（3）Logical direct current, power-on voltage is that 5~30V, electric current are 30~200A, when reaching 50~60A of setting electric current i.e.
Can be ignited tungsten filament（3）, pass through the tungsten filament of burning（3）Blank is lighted in heating（1）；
Within 5~30s times after burning terminates, using hydraulic press（7）To pressure head（6）Apply 50~200MPa pressure and keep
Press 20~100s, by blank after reaction（1）[i.e.：The blank lighted by tungsten filament (3) heating of burning（1）Terminate in burning
And the material obtained after being pressed] it is cooled to normal temperature；By blank after the reaction after cooling（1）Take out, be obtained（Height is caused
Density）Gd2Ti2-xZrxO7Pyrochlore（Block）.
In present disclosure：X values described in step a are between 0 to 0.5, as：0 ＜ x≤0.5.
In present disclosure：Quartz sand described in step d（2）Granularity preferably be not more than 70 mesh.
In present disclosure：The granularity of raw material is preferably less than 200 mesh described in step a.
In present disclosure：The purity of raw material described in step a is preferably higher than 99%.
The present invention it is another to the effect that：A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, its feature
It is：Using Ti powder as reducing agent, CuO powder uses SHS process as oxidant（Abbreviation SHS）With reference to Quick-pressing
Technology produces Gd2Ti2-xZrxO7Pyrochlore-type prosthetic graft block, its chemical equation（Ⅱ）For：
(2-x)Ti+xZrO2+Gd2O3+(4-2x)CuO = Gd2Ti2-xZrxO7+(4-2x)Cu （Ⅱ）
The present invention another content be：A kind of Gd2Ti2-xZrxO7It is to include in place of the self- propagating preparation method of pyrochlore, its feature
The following steps：
A, dispensing：By Ti：ZrO2：Gd2O3：CuO = (2-x)：x：1：The mol ratio of (4-2x) takes Ti, ZrO2、Gd2O3, CuO powder
Body is used as raw material；
B, abrasive material：By said components raw material through dry ball milling 10~30 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound,
It is put into baking oven, is dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 10~50g to dry is fitted into Φ 20~50mm stainless steel moulds, using 10~
The compound of drying is pressed into 20~50mm's of diameter by 50MPa pressure（Cylinder）Blank（1）；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes：Connected or be connected as a single entity by bottom, lower end and bottom
The punching block that annular sidewall is constituted（4）, copper electrode（5）, with copper electrode（5）The tungsten filament of one end connection（3）, it is arranged at punching block（4）'s
The pressure head of upper end in annular sidewall（6）, and it is arranged at pressure head（6）The pressurization hydraulic press of top（7）；
Use quartz sand（2）It is paved with punching block（4）Inner bottom part, by blank（1）It is placed in quartz sand（2）On, blank（1）One side and company
It is connected on copper electrode（5）The tungsten filament of one end（3）Contact, then use quartz sand（2）By punching block（4）Inside fill up, use pressure head（6）Close punching block
（4）；
Lead to direct current to tungsten filament (3), power-on voltage is that 5~30V, electric current are 30~200A, when reaching 50~60A of setting electric current i.e.
Can be ignited tungsten filament（3）, pass through the tungsten filament of burning（3）Blank is lighted in heating（1）；
Within 5~30s times after burning terminates, using hydraulic press（7）To pressure head（6）Apply 50~200MPa pressure and keep
Press 20~100s, by blank after reaction（1）[i.e.：The blank lighted by tungsten filament (3) heating of burning（1）Terminate in burning
And the material obtained after being pressed] it is cooled to normal temperature；By blank after the reaction after cooling（1）Take out, be obtained（Height is caused
Density）Gd2Ti2-xZrxO7Pyrochlore（Block）.
In another content of the present invention：X values are between 0.5 to 0.9 described in step a, i.e.,：0.5≤x≤0.9.
In another content of the present invention：Quartz sand described in step d（2）Granularity preferably be not more than 70 mesh.
In another content of the present invention：The granularity of raw material is preferably less than 200 mesh described in step a.
In another content of the present invention：The purity of raw material described in step a is preferably higher than 99%.
Compared with prior art, the present invention has following features and beneficial effect：
（1）The present invention uses SHS process（Abbreviation SHS）Self-spreading quasi isopressing device, i.e., using self- propagating combine
Quick-pressing preparation technology prepares Gd2Ti2-xZrxO7Pyrochlore block, aggregate velocity is fast, reaction temperature is high, product purity is high, production
Product consistency is high, energy consumption is low, technique is simple, while can quickly apply pressure to sample after burning, be able to can be obtained in the short period
High compaction sample；In addition, self-spreading quasi isopressing device only needs to simple repacking, it is possible to apply existing point
Fiery mode, such as laser ignition, radiant flux igniting, the thermal explosion of linear heat；By adjusting height of the sample in steel mold,
It can just realize that adjustment is ignited the position of sample, so as to constitute gradient sintering；
（2）Using the present invention, from nucleic range comprehension is wide, nucleic inclusion quantity is big, anti-radiation performance is good, hot and chemical stability
High pyrochlore as the main mine of prosthetic graft there is provided a kind of Ti powder as reducing agent, CuO is as oxidant, from climing
Prolong high―temperature nuclei（Abbreviation SHS）The side of the pyrochlore-type prosthetic graft firming body of high-compactness is prepared with reference to Quick-pressing technique
Method, for disposing high-level waste, can fundamentally ensure the stability and long-term safety of actinium series nucleic firming body；According to
The characteristics of SHS chemically reacts, because reaction is an exothermic reaction, so, reaction is once avoiding the need for external heat source
Maintain；The present invention uses Ti powder for reducing agent, and CuO powder is oxidant, and fixed Ti is 1 with CuO mol ratios：In the case of 2, design
Ti and TiO in reaction equation2The difference of ratio, so that SHS reaction temperature is adjusted, so as to the high-level waste for heterogeneity,
Different proportionings is chosen flexibly to carry out curing process；
（3）Pyrochlore-type prosthetic graft prepared by the present invention（That is Gd2Ti2-xZrxO7Pyrochlore）, its main mine is mutually Gd2Ti2- xZrxO7With Ni metal phase；Gd2Ti2O7Gd positions can be replaced by Na, Ca, Y and group of the lanthanides and actinides；And Ti then may be used
To be replaced by Zr, Nb, Hf, Ta, Sn and W, there is Ni metal phase in product in addition, can be synthesized with the metallic element formation in HLW
Phase, so as to further improve the inclusion quantity of firming body；
（4）The present invention uses SHS process combination Rapid Densification Process of Preparing, it is only necessary to several minutes of times, you can synthesis hyperpyrexia
The excellent pyrochlore-type prosthetic graft compact curing body of stability, high chemical stability, anti-radiation performance；With aggregate velocity
It hurry up, the advantages of production efficiency is high, reaction temperature high, energy consumption is low, product purity is high, technique is simple, obtained high-compactness
Gd2Ti2-xZrxO7Pyrochlore the long-term safety curing process of actinium series nucleic and disposal suitable for high-level waste, for pyrochlore
The engineering application of curing process and disposal HLW has larger impetus, practical.
Brief description of the drawings
Fig. 1 is that self- propagating combination Quick-pressing of the present invention prepares Gd2Ti2-xZrxO7In the schematic diagram of pyrochlore, figure：1-base
Material, 2-quartz sand, 3-tungsten filament, 4-punching block, 5-copper electrode, 6-pressure head, 7-hydraulic press.
Fig. 2 be the gained sample of embodiment 1 [i.e.：It is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore（Block）] X penetrate
Ray diffraction diagram is composed, visible in figure：Using reaction equation（Ⅰ）Obtained sample only includes Gd2Ti1.7Zr0.3O7Two kinds of things of pyrochlore and Cu
Phase；
Fig. 3 be the gained sample of embodiment 2 [i.e.：It is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore（Block）] X-ray spread out
Penetrate visible in collection of illustrative plates, figure：Using reaction equation（Ⅱ）Obtained sample only includes Gd2Ti1.5Zr0.5O7Two kinds of thing phases of pyrochlore and Cu；
Fig. 4 be the gained sample of embodiment 3 [i.e.：It is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore（Block）] X-ray spread out
Penetrate visible in collection of illustrative plates, figure：Using reaction equation（Ⅱ）Obtained sample only includes Gd2Ti1.3Zr0.7O7Two kinds of thing phases of pyrochlore and Cu；
Fig. 5 be the gained sample of embodiment 4 [i.e.：It is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore（Block）] X-ray spread out
Penetrate visible in collection of illustrative plates, figure：Using reaction equation（Ⅱ）Obtained sample only includes Gd2Ti1.1Zr0.9O7Two kinds of thing phases of pyrochlore and Cu.
Embodiment
The invention will be further described for example given below plan, but is not to be construed as to the scope of the present invention
Limitation, some nonessential improvement and tune that person skilled in art makes according to the content of the invention described above to the present invention
It is whole, still fall within protection scope of the present invention.
Embodiment 1：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, is comprised the following steps that：
（1）Using Ti as reducing agent, CuO is oxidant, by following reaction equation（Ⅰ）Carry out dispensing：
3Ti+0.4TiO2+0.6ZrO2+2Gd2O3+6CuO=2Gd2Ti1.7Zr0.3O7+6Cu （Ⅰ）
The mol ratio of each reactant raw material is Ti：TiO2：ZrO2：Gd2O3：CuO =15：2：3：10：30, according to respective molecule
Measure and content, corresponding mass percentage content is：Ti：10.1%, TiO2：2.25%, ZrO2：5.2%, Gd2O3：50.99%,
CuO：31.46%；
（2）By said components raw material through dry ball milling 30 minutes, it is well mixed, through 100 mesh sieves, obtains compound, be placed on baking oven
In, dried 30 minutes under the conditions of 80 DEG C.Take 20g compounds to be fitted into Φ 25mm stainless steel moulds, will be mixed using 20MPa pressure
Material is pressed into the cylinder blank 1 that diameter 25mm, thickness are about 20mm；
（3）SHS is molded crude green body（It is i.e. described：Cylinder blank 1）Be put into self-spreading quasi isopressing device, using tungsten filament as
SHS seed materials, it is ensured that tungsten filament connection is intact and is completely attached to reaction blank, is then used as biography using 70~100 mesh quartz sands
Pressure medium embeds crude green body completely.Tungsten filament is ignited in the case where voltage is the direct current electro ultrafiltration that 20V, electric current are 50A first, passes through tungsten
The high temperature that silk burning is produced lights reaction mass, the 25s after combustion reaction terminates, to sample（I.e.：The cylinder blank 1 fires
Burn the material obtained after reaction terminates）Apply 50MPa pressure and pressurize 60s, after after sample completely cooling, take out by quartz sand bag
The sample wrapped up in, that is, obtain the pyrochlore-type prosthetic graft bulk of densification.
Sample thing mutually only includes Gd2Ti1.7Zr0.3O7Pyrochlore and Ni metal two-phase, its thing is determined using X-ray diffractometer
Phase composition result is as shown in Figure 2.
Embodiment 2：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, is comprised the following steps that：
（1）Using Ti as reducing agent, CuO is oxidant, by following reaction equation（Ⅱ）Carry out dispensing：
3Ti+ZrO2+2Gd2O3+6CuO=2Gd2Ti1.5Zr0.5O7+6Cu （Ⅱ）
The mol ratio of each reactant raw material is Ti：ZrO2：Gd2O3：CuO=3：1：2：6, it is right according to respective molecular weight and content
The mass percentage content answered is：Ti：9.77%, ZrO2：8.39%, Gd2O3：49.35%, CuO：30.45%；
（2）By said components raw material through dry ball milling 30 minutes, it is well mixed, through 100 mesh sieves, obtains compound, be placed on baking oven
In, dried 30 minutes under the conditions of 80 DEG C.Take 20g compounds to be fitted into Φ 25mm stainless steel moulds, will be mixed using 20MPa pressure
Material is pressed into diameter 25mm, the cylinder blank 1 that thickness is about 20mm；
（3）SHS is molded crude green body（It is i.e. described：Cylinder blank 1）Be put into self-spreading quasi isopressing device, using tungsten filament as
SHS seed materials, it is ensured that tungsten filament connection is intact and is completely attached to reaction blank, is then used as biography using 70~100 mesh quartz sands
Pressure medium embeds crude green body completely.Tungsten filament is ignited in the case where voltage is the direct current electro ultrafiltration that 20V, electric current are 50A first, passes through tungsten
The high temperature that silk burning is produced lights reaction mass, the 25s after combustion reaction terminates, to sample（I.e.：The cylinder blank 1 fires
Burn the material obtained after reaction terminates）Apply 50MPa pressure and pressurize 60s, after after sample completely cooling, take out by quartz sand bag
The sample wrapped up in, that is, obtain the pyrochlore-type prosthetic graft bulk of densification.
Sample thing mutually only includes Gd2Ti1.5Zr0.5O7Pyrochlore and Ni metal two-phase, its thing is determined using X-ray diffractometer
Phase composition result is as shown in Figure 3.
Embodiment 3：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, is comprised the following steps that：
（1）Using Ti as reducing agent, CuO is oxidant, by reaction equation（Ⅱ）Carry out dispensing：
13Ti+7ZrO2+10Gd2O3+26CuO=10Gd2Ti1.3Zr0.7O7+26Cu （Ⅱ）
The mol ratio of each reactant feed is Ti：ZrO2：Gd2O3：CuO=13：7：10：26, according to respective molecular weight and content,
Corresponding weight/mass percentage composition is：Ti：8.67%, ZrO2：12.02%, Gd2O3：50.50%, CuO：28.81%；
（2）By said components raw material through dry ball milling 30 minutes, it is well mixed, through 100 mesh sieves, obtains compound, be placed on baking oven
In, dried 30 minutes under the conditions of 80 DEG C.Take 20g compounds to be fitted into Φ 25mm stainless steel moulds, will be mixed using 20MPa pressure
Material is pressed into diameter 25mm, the cylinder blank 1 that thickness is about 20mm；
（3）SHS is molded crude green body（It is i.e. described：Cylinder blank 1）Be put into self-spreading quasi isopressing device, using tungsten filament as
SHS seed materials, it is ensured that tungsten filament connection is intact and is completely attached to reaction blank, is then used as biography using 70~100 mesh quartz sands
Pressure medium embeds crude green body completely.Tungsten filament is ignited in the case where voltage is the direct current electro ultrafiltration that 20V, electric current are 50A first, passes through tungsten
The high temperature that silk burning is produced lights reaction mass, the 25s after combustion reaction terminates, to sample（I.e.：The cylinder blank 1 fires
Burn the material obtained after reaction terminates）Apply 50MPa pressure and pressurize 60s, after after sample completely cooling, take out by quartz sand bag
The sample wrapped up in, that is, obtain the pyrochlore-type prosthetic graft bulk of densification.
Sample thing mutually only includes Gd2Ti1.3Zr0.7O7Pyrochlore and Ni metal two-phase, its thing is determined using X-ray diffractometer
Phase composition result is as shown in Figure 4.
Embodiment 4：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, is comprised the following steps that：
（1）Using Ti as reducing agent, CuO is oxidant, by reaction equation（Ⅱ）Carry out dispensing：
11Ti+9ZrO2+10Gd2O3+22CuO=10Gd2Ti1.1Zr0.9O7+22Cu （Ⅱ）
The mol ratio of each reactant raw material is Ti：TiO2：ZrO2：Gd2O3：CuO=11：9：10：22, according to respective molecular weight and
Content, corresponding mass percentage content is：Ti：7.51%, ZrO2：15.82%, Gd2O3：51.71%, CuO：24.96%；
（2）By said components raw material through dry ball milling 30 minutes, it is well mixed, through 100 mesh sieves, obtains compound, be placed on baking oven
In, dried 30 minutes under the conditions of 80 DEG C.Take 20g compounds to be fitted into Φ 25mm stainless steel moulds, will be mixed using 20MPa pressure
Material is pressed into diameter 25mm, the cylinder blank 1 that thickness is about 20mm；
（3）SHS is molded crude green body（It is i.e. described：Cylinder blank 1）Be put into self-spreading quasi isopressing device, using tungsten filament as
SHS seed materials, it is ensured that tungsten filament connection is intact and is completely attached to reaction blank, is then used as biography using 70~100 mesh quartz sands
Pressure medium embeds crude green body completely.Tungsten filament is ignited in the case where voltage is the direct current electro ultrafiltration that 20V, electric current are 50A first, passes through tungsten
The high temperature that silk burning is produced lights reaction mass, the 25s after combustion reaction terminates, to sample（I.e.：The cylinder blank 1 fires
Burn the material obtained after reaction terminates）Apply 50MPa pressure and pressurize 60s, after after sample completely cooling, take out by quartz sand bag
The sample wrapped up in, that is, obtain the pyrochlore-type prosthetic graft bulk of densification.
Sample thing mutually only includes Gd2Ti1.1Zr0.9O7Pyrochlore and Ni metal two-phase, its thing is determined using X-ray diffractometer
Phase composition result is as shown in Figure 5.
Embodiment 5：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅰ）For：
3Ti+(1-2x)TiO2+2xZrO2+2Gd2O3+6CuO = 2Gd2Ti2-xZrxO7+6Cu （Ⅰ）
Formula（Ⅰ）In： x = 0.1；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：TiO2：ZrO2：Gd2O3：CuO = 3：(1-2x)：2x：2：6 mol ratio takes Ti, TiO2、ZrO2、
Gd2O3, CuO powders be used as raw material；
B, abrasive material：By said components raw material through dry ball milling 10 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 10g to dry is fitted into Φ 20mm stainless steel moulds, will be dried using 10MPa pressure
Dry compound is pressed into diameter 20mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
The inner bottom part of punching block 4 is paved with quartz sand 2, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electrode
The tungsten filament 3 of 5 one end（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 30V, electric current are 200A, when reaching that 50~60A of setting electric current can ignite tungsten
Silk 3, blank 1 is lighted by the heating of tungsten filament 3 of burning；
Within the 5s times after burning terminates, 50MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 20s that presses is kept, will be anti-
Answer rear blank 1 [i.e.：The material that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning]
It is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore（Block
Body）.
Embodiment 6：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅰ）For：
3Ti+(1-2x)TiO2+2xZrO2+2Gd2O3+6CuO = 2Gd2Ti2-xZrxO7+6Cu （Ⅰ）
Formula（Ⅰ）In： x = 0.2；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：TiO2：ZrO2：Gd2O3：CuO = 3：(1-2x)：2x：2：6 mol ratio takes Ti, TiO2、ZrO2、
Gd2O3, CuO powders be used as raw material；
B, abrasive material：By said components raw material through dry ball milling 20 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 30g to dry is fitted into Φ 35mm stainless steel moulds, will be dried using 30MPa pressure
Dry compound is pressed into diameter 35mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
The inner bottom part of punching block 4 is paved with quartz sand 2, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electrode
The tungsten filament 3 of 5 one end（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 18V, electric current are 115A, when reaching that 50~60A of setting electric current can ignite tungsten
Silk 3, blank 1 is lighted by the heating of tungsten filament 3 of burning；
Within the 18s times after burning terminates, 125MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 60s that presses is kept, will
Blank 1 is [i.e. after reaction：The thing that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning
Material] it is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore
（Block）.
Embodiment 7：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅰ）For：
3Ti+(1-2x)TiO2+2xZrO2+2Gd2O3+6CuO = 2Gd2Ti2-xZrxO7+6Cu （Ⅰ）
Formula（Ⅰ）In： x = 0.4；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：TiO2：ZrO2：Gd2O3：CuO = 3：(1-2x)：2x：2：6 mol ratio takes Ti, TiO2、ZrO2、
Gd2O3, CuO powders be used as raw material；
B, abrasive material：By said components raw material through dry ball milling 30 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 50g to dry is fitted into Φ 50mm stainless steel moulds, will be dried using 50MPa pressure
Dry compound is pressed into diameter 50mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
The inner bottom part of punching block 4 is paved with quartz sand 2, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electrode
The tungsten filament 3 of 5 one end（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 5V, electric current are 30A, when reaching that setting electric current can ignite tungsten filament 3, pass through combustion
Blank 1 is lighted in the heating of tungsten filament 3 of burning；
Within the 30s times after burning terminates, 200MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 100s that presses is kept, will
Blank 1 is [i.e. after reaction：The thing that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning
Material] it is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore
（Block）.
Embodiment 8：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅰ）For：
3Ti+(1-2x)TiO2+2xZrO2+2Gd2O3+6CuO = 2Gd2Ti2-xZrxO7+6Cu （Ⅰ）
Formula（Ⅰ）In： x = 0.4；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：TiO2：ZrO2：Gd2O3：CuO = 3：(1-2x)：2x：2：6 mol ratio takes Ti, TiO2、ZrO2、
Gd2O3, CuO powders be used as raw material；
B, abrasive material：By said components raw material through dry ball milling 30 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 50g to dry is fitted into Φ 50mm stainless steel moulds, will be dried using 50MPa pressure
Dry compound is pressed into diameter 50mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
The inner bottom part of punching block 4 is paved with quartz sand 2, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electrode
The tungsten filament 3 of 5 one end（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 30V, electric current are 200A, when reaching that 50~60A of setting electric current can ignite tungsten
Silk 3, blank 1 is lighted by the heating of tungsten filament 3 of burning；
Within the 30s times after burning terminates, 200MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 100s that presses is kept, will
Blank 1 is [i.e. after reaction：The thing that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning
Material] it is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore
（Block）.
Embodiment 9：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅰ）For：
3Ti+(1-2x)TiO2+2xZrO2+2Gd2O3+6CuO = 2Gd2Ti2-xZrxO7+6Cu （Ⅰ）
Formula（Ⅰ）In： x = 0.3；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：TiO2：ZrO2：Gd2O3：CuO = 3：(1-2x)：2x：2：6 mol ratio takes Ti, TiO2、ZrO2、
Gd2O3, CuO powders be used as raw material；
B, abrasive material：By said components raw material through dry ball milling 15 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 25g to dry is fitted into Φ 30mm stainless steel moulds, will be dried using 25MPa pressure
Dry compound is pressed into diameter 30mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
The inner bottom part of punching block 4 is paved with quartz sand 2, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electrode
The tungsten filament 3 of 5 one end（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 10V, electric current are 80A, when reaching that 50~60A of setting electric current can ignite tungsten filament
3, blank 1 is lighted by the heating of tungsten filament 3 of burning；
Within 5~30s time after burning terminates, 90MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 40s that presses is kept,
By blank 1 after reaction [i.e.：The thing that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning
Material] it is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore
（Block）.
Embodiment 10：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅱ）For：
(2-x)Ti+xZrO2+Gd2O3+(4-2x)CuO = Gd2Ti2-xZrxO7+(4-2x)Cu （Ⅱ）
Formula（Ⅱ）In： x = 0.9；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：ZrO2：Gd2O3：CuO = (2-x)：x：1：The mol ratio of (4-2x) takes Ti, ZrO2、Gd2O3, CuO powder
Body is used as raw material；
B, abrasive material：By said components raw material through dry ball milling 30 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 50g to dry is fitted into Φ 50mm stainless steel moulds, will be dried using 50MPa pressure
Dry compound is pressed into diameter 50mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
The inner bottom part of punching block 4 is paved with quartz sand 2, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electrode
The tungsten filament 3 of 5 one end（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 30V, electric current are 200A, when reaching that 50~60A of setting electric current can ignite tungsten
Silk 3, blank 1 is lighted by the heating of tungsten filament 3 of burning；
Within the 30s times after burning terminates, 200MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 100s that presses is kept, will
Blank 1 is [i.e. after reaction：The thing that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning
Material] it is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore
（Block）.
Embodiment 11：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅱ）For：
(2-x)Ti+xZrO2+Gd2O3+(4-2x)CuO = Gd2Ti2-xZrxO7+(4-2x)Cu （Ⅱ）
Formula（Ⅱ）In： x = 0.7；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：ZrO2：Gd2O3：CuO = (2-x)：x：1：The mol ratio of (4-2x) takes Ti, ZrO2、Gd2O3, CuO powder
Body is used as raw material；
B, abrasive material：By said components raw material through dry ball milling 10 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 10g to dry is fitted into Φ 20mm stainless steel moulds, will be dried using 10MPa pressure
Dry compound is pressed into diameter 20mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
The inner bottom part of punching block 4 is paved with quartz sand 2, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electrode
The tungsten filament 3 of 5 one end（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 5V, electric current are 30A, when reaching that setting electric current can ignite tungsten filament 3, pass through combustion
Blank 1 is lighted in the heating of tungsten filament 3 of burning；
Within the 5s times after burning terminates, 50MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 20s that presses is kept, will be anti-
Answer rear blank 1 [i.e.：The material that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning]
It is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore（Block
Body）.
Embodiment 12：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅱ）For：
(2-x)Ti+xZrO2+Gd2O3+(4-2x)CuO = Gd2Ti2-xZrxO7+(4-2x)Cu （Ⅱ）
Formula（Ⅱ）In： x = 0.6；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：ZrO2：Gd2O3：CuO = (2-x)：x：1：The mol ratio of (4-2x) takes Ti, ZrO2、Gd2O3, CuO powder
Body is used as raw material；
B, abrasive material：By said components raw material through dry ball milling 10 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 10g to dry is fitted into Φ 20mm stainless steel moulds, will be dried using 10MPa pressure
Dry compound is pressed into diameter 20mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
The inner bottom part of punching block 4 is paved with quartz sand 2, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electrode
The tungsten filament 3 of 5 one end（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 10V, electric current are 70A, when reaching that 50~60A of setting electric current can ignite tungsten filament
3, blank 1 is lighted by the heating of tungsten filament 3 of burning；
Within the 5s times after burning terminates, 50MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 20s that presses is kept, will be anti-
Answer rear blank 1 [i.e.：The material that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning]
It is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore（Block
Body）.
Embodiment 13：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅱ）For：
(2-x)Ti+xZrO2+Gd2O3+(4-2x)CuO = Gd2Ti2-xZrxO7+(4-2x)Cu （Ⅱ）
Formula（Ⅱ）In： x = 0.5；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：ZrO2：Gd2O3：CuO = (2-x)：x：1：The mol ratio of (4-2x) takes Ti, ZrO2、Gd2O3, CuO powder
Body is used as raw material；
B, abrasive material：By said components raw material through dry ball milling 20 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 30g to dry is fitted into Φ 35mm stainless steel moulds, will be dried using 30MPa pressure
Dry compound is pressed into diameter 35mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
The inner bottom part of punching block 4 is paved with quartz sand 2, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electrode
The tungsten filament 3 of 5 one end（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 17V, electric current are 115A, when reaching that 50~60A of setting electric current can ignite tungsten
Silk 3, blank 1 is lighted by the heating of tungsten filament 3 of burning；
Within the 17s times after burning terminates, 125MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 60s that presses is kept, will
Blank 1 is [i.e. after reaction：The thing that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning
Material] it is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore
（Block）.
Embodiment 14：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅱ）For：
(2-x)Ti+xZrO2+Gd2O3+(4-2x)CuO = Gd2Ti2-xZrxO7+(4-2x)Cu （Ⅱ）
Formula（Ⅱ）In： x = 0.7；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：ZrO2：Gd2O3：CuO = (2-x)：x：1：The mol ratio of (4-2x) takes Ti, ZrO2、Gd2O3, CuO powder
Body is used as raw material；
B, abrasive material：By said components raw material through dry ball milling 15 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 20g to dry is fitted into Φ 30mm stainless steel moulds, will be dried using 20MPa pressure
Dry compound is pressed into diameter 30mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
Use quartz sand（2）The inner bottom part of punching block 4 is paved with, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electricity
The tungsten filament 3 of the one end of pole 5（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 13V, electric current are 100A, when reaching that 50~60A of setting electric current can ignite tungsten
Silk 3, blank 1 is lighted by the heating of tungsten filament 3 of burning；
Within the 10s times after burning terminates, 100MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 40s that presses is kept, will
Blank 1 is [i.e. after reaction：The thing that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning
Material] it is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore
（Block）.
Embodiment 15：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅱ）For：
(2-x)Ti+xZrO2+Gd2O3+(4-2x)CuO = Gd2Ti2-xZrxO7+(4-2x)Cu （Ⅱ）
Formula（Ⅱ）In： x = 0.6；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：ZrO2：Gd2O3：CuO = (2-x)：x：1：The mol ratio of (4-2x) takes Ti, ZrO2、Gd2O3, CuO powder
Body is used as raw material；
B, abrasive material：By said components raw material through dry ball milling 22 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 25g to dry is fitted into Φ 30mm stainless steel moulds, will be dried using 350MPa pressure
Dry compound is pressed into diameter 30mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
The inner bottom part of punching block 4 is paved with quartz sand 2, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electrode
The tungsten filament 3 of 5 one end（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 15V, electric current are 150A, when reaching that 50~60A of setting electric current can ignite tungsten
Silk 3, blank 1 is lighted by the heating of tungsten filament 3 of burning；
Within the 20s times after burning terminates, 150MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 70s that presses is kept, will
Blank 1 is [i.e. after reaction：The thing that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning
Material] it is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore
（Block）.
Embodiment 16：
A kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, using Ti powder as reducing agent, CuO powder is used as oxidation
Agent, chemical equation（Ⅱ）For：
(2-x)Ti+xZrO2+Gd2O3+(4-2x)CuO = Gd2Ti2-xZrxO7+(4-2x)Cu （Ⅱ）
Formula（Ⅱ）In： x = 0.8；
The Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore comprises the following steps：
A, dispensing：By Ti：ZrO2：Gd2O3：CuO = (2-x)：x：1：The mol ratio of (4-2x) takes Ti, ZrO2、Gd2O3, CuO powder
Body is used as raw material；
B, abrasive material：By said components raw material through dry ball milling 26 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound, be put into
In baking oven, dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 40g to dry is fitted into Φ 40mm stainless steel moulds, will be dried using 40MPa pressure
Dry compound is pressed into diameter 40mm's（Cylinder）Blank 1；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes:Connected or be connected as a single entity by bottom, lower end and bottom
In the punching block 4 that annular sidewall is constituted, copper electrode 5, the tungsten filament 3 being connected with the one end of copper electrode 5, the annular sidewall for being arranged at punching block 4
The pressure head 6 of upper end, and it is arranged at the pressurization hydraulic press 7 of the top of pressure head 6；
The inner bottom part of punching block 4 is paved with quartz sand 2, blank 1 is placed on quartz sand 2, the one side of blank 1 is with being connected to copper electrode
The tungsten filament 3 of 5 one end（Closely）Contact, then will be filled up with quartz sand 2 in punching block 4, close punching block 4 with pressure head 6；
Lead to direct current to tungsten filament 3, power-on voltage is that 25V, electric current are 180A, when reaching that 50~60A of setting electric current can ignite tungsten
Silk 3, blank 1 is lighted by the heating of tungsten filament 3 of burning；
Within the 25s times after burning terminates, 180MPa pressure is applied to pressure head 6 using hydraulic press 7 and the 80s that presses is kept, will
Blank 1 is [i.e. after reaction：The thing that the blank 1 lighted terminates and obtained after being pressed in burning is heated by the tungsten filament 3 of burning
Material] it is cooled to normal temperature；Blank 1 after reaction after cooling is taken out, is obtained（High-compactness）Gd2Ti2-xZrxO7Pyrochlore
（Block）.
In above-described embodiment 5~16：The granularity of quartz sand 2 is not more than 70 mesh described in step d.
In above-described embodiment 5~16：The granularity of raw material described in step a is less than 200 mesh.
In above-described embodiment 5~16：The purity of raw material described in step a is higher than 99%.
In above-described embodiment：Each raw material used is commercially available prod.
In above-described embodiment：In the percentage used, do not indicate especially, be quality（Weight）Percentage or
Well known to a person skilled in the art percentage；The quality（Weight）Part can be gram or kilogram.
In above-described embodiment：Technological parameter (temperature, time, pressure etc.) and each component numerical quantity in each step etc. are
Scope, any point is applicable.
The technology contents being not specifically delineated in present invention and above-described embodiment are compared with technology.
It can implement the invention is not restricted to above-described embodiment, described in present invention and with the good result.
Claims (10)
1. a kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that comprising the following steps：
A, dispensing：By Ti：TiO2：ZrO2：Gd2O3：CuO = 3：(1-2x)：2x：2：6 mol ratio takes Ti, TiO2、ZrO2、
Gd2O3, CuO powders be used as raw material；
B, abrasive material：By said components raw material through dry ball milling 10~30 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound,
It is put into baking oven, is dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 10~50g to dry is fitted into Φ 20~50mm stainless steel moulds, using 10~
The compound of drying is pressed into 20~50mm of diameter blank by 50MPa pressure（1）；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes：Connected or be connected as a single entity by bottom, lower end and bottom
The punching block that annular sidewall is constituted（4）, copper electrode（5）, with copper electrode（5）The tungsten filament of one end connection（3）, it is arranged at punching block（4）'s
The pressure head of upper end in annular sidewall（6）, and it is arranged at pressure head（6）The pressurization hydraulic press of top（7）；
Use quartz sand（2）It is paved with punching block（4）Inner bottom part, by blank（1）It is placed in quartz sand（2）On, blank（1）One side and company
It is connected on copper electrode（5）The tungsten filament of one end（3）Contact, then use quartz sand（2）By punching block（4）Inside fill up, use pressure head（6）Close punching block
（4）；
To tungsten filament（3）Logical direct current, power-on voltage is that 5~30V, electric current are 30~200A, when reaching 50~60A of setting electric current i.e.
Can be ignited tungsten filament（3）, pass through the tungsten filament of burning（3）Blank is lighted in heating（1）；
Within 5~30s times after burning terminates, using hydraulic press（7）To pressure head（6）Apply 50~200MPa pressure and keep
Press 20~100s, by blank after reaction（1）It is cooled to normal temperature；By blank after the reaction after cooling（1）Take out, be obtained
Gd2Ti2-xZrxO7Pyrochlore.
2. the Gd as described in claim 12Ti2-xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that：X described in step a
It is worth and is：0 ＜ x≤0.5.
3. the Gd as described in claim 1 or 22Ti2-xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that：Institute in step d
State quartz sand（2）Granularity be not more than 70 mesh.
4. the Gd as described in claim 1 or 22Ti2-xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that：Institute in step a
The granularity for stating raw material is less than 200 mesh.
5. the Gd as described in claim 1 or 22Ti2-xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that：Institute in step a
The purity for stating raw material is higher than 99%.
6. a kind of Gd2Ti2-xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that comprising the following steps：
A, dispensing：By Ti：ZrO2：Gd2O3：CuO = (2-x)：x：1：The mol ratio of (4-2x) takes Ti, ZrO2 、Gd2O3、CuO
Powder is used as raw material；
B, abrasive material：By said components raw material through dry ball milling 10~30 minutes, it is well mixed, crosses 100 mesh sieves, obtain compound,
It is put into baking oven, is dried 30 minutes at a temperature of 80 DEG C, obtain the compound of drying；
C, crude green body are compressing：The compound for taking 10~50g to dry is fitted into Φ 20~50mm stainless steel moulds, using 10~
The compound of drying is pressed into 20~50mm of diameter blank by 50MPa pressure（1）；
d、Gd2Ti2-xZrxO7The SHS process of pyrochlore-type prosthetic graft and densification：
Using self-spreading quasi isopressing device, the composition of the device includes：Connected or be connected as a single entity by bottom, lower end and bottom
The punching block that annular sidewall is constituted（4）, copper electrode（5）, with copper electrode（5）The tungsten filament of one end connection（3）, it is arranged at punching block（4）'s
The pressure head of upper end in annular sidewall（6）, and it is arranged at pressure head（6）The pressurization hydraulic press of top（7）；
Use quartz sand（2）It is paved with punching block（4）Inner bottom part, by blank（1）It is placed in quartz sand（2）On, blank（1）One side and company
It is connected on copper electrode（5）The tungsten filament of one end（3）Contact, then use quartz sand（2）By punching block（4）Inside fill up, use pressure head（6）Close punching block
（4）；
Lead to direct current to tungsten filament (3), power-on voltage is that 5~30V, electric current are 30~200A, when reaching 50~60A of setting electric current i.e.
Can be ignited tungsten filament（3）, pass through the tungsten filament of burning（3）Blank is lighted in heating（1）；
Within 5~30s times after burning terminates, using hydraulic press（7）To pressure head（6）Apply 50~200MPa pressure and keep
Press 20~100s, by blank after reaction（1）It is cooled to normal temperature；By blank after the reaction after cooling（1）Take out, be obtained
Gd2Ti2-xZrxO7Pyrochlore.
7. the Gd as described in claim 62Ti2-xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that：X described in step a
It is worth and is：0.5≤x≤0.9.
8. the Gd as described in claim 6 or 72Ti2-xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that：Institute in step d
State quartz sand（2）Granularity be not more than 70 mesh.
9. the Gd as described in claim 6 or 72Ti2-xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that：Institute in step a
The granularity for stating raw material is less than 200 mesh.
10. the Gd as described in claim 6 or 72Ti2-xZrxO7The self- propagating preparation method of pyrochlore, it is characterized in that：Institute in step a
The purity for stating raw material is higher than 99%.
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| CN108022665A (en) * | 2017-08-04 | 2018-05-11 | 西南科技大学 | A kind of self- propagating curing of radioactive pollution sand |
| CN111533557A (en) * | 2020-03-27 | 2020-08-14 | 东华大学 | Pyrochlore type high-entropy oxide solidified body and preparation method thereof |
| CN114105672A (en) * | 2020-08-31 | 2022-03-01 | 厦门稀土材料研究所 | Zirconium-tantalum composite rare earth-based porous high-entropy ceramic and preparation method thereof |
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| CN102643089A (en) * | 2012-03-31 | 2012-08-22 | 西南科技大学 | High-temperature and high-pressure rapid synthesis method of Gd2Zr2O7 pyrochlore ceramic |
| CN104528813A (en) * | 2014-12-04 | 2015-04-22 | 西南科技大学 | Y2Ti2O7 pyrochlore self-propagating high-temperature synthesis and densification method |
| CN104773754A (en) * | 2015-04-10 | 2015-07-15 | 西南科技大学 | Preparation method of rare-earth titanate pyrochlore powder |
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| CN102643089A (en) * | 2012-03-31 | 2012-08-22 | 西南科技大学 | High-temperature and high-pressure rapid synthesis method of Gd2Zr2O7 pyrochlore ceramic |
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| CN108022665A (en) * | 2017-08-04 | 2018-05-11 | 西南科技大学 | A kind of self- propagating curing of radioactive pollution sand |
| CN111533557A (en) * | 2020-03-27 | 2020-08-14 | 东华大学 | Pyrochlore type high-entropy oxide solidified body and preparation method thereof |
| CN111533557B (en) * | 2020-03-27 | 2021-11-09 | 东华大学 | Pyrochlore type high-entropy oxide solidified body and preparation method thereof |
| CN114105672A (en) * | 2020-08-31 | 2022-03-01 | 厦门稀土材料研究所 | Zirconium-tantalum composite rare earth-based porous high-entropy ceramic and preparation method thereof |
| CN114105672B (en) * | 2020-08-31 | 2023-04-18 | 厦门稀土材料研究所 | Zirconium-tantalum composite rare earth-based porous high-entropy ceramic and preparation method thereof |
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