CN104529478A - Ceramic sintering additive and production method thereof - Google Patents
Ceramic sintering additive and production method thereof Download PDFInfo
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- CN104529478A CN104529478A CN201410804137.2A CN201410804137A CN104529478A CN 104529478 A CN104529478 A CN 104529478A CN 201410804137 A CN201410804137 A CN 201410804137A CN 104529478 A CN104529478 A CN 104529478A
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Abstract
The invention provides a ceramic sintering additive and a production method thereof. The ceramic sintering additive is composed of a multi-metal oxygen cluster and water soluble cationic polyelectrolyte, wherein the multi-metal oxygen cluster is composed of multiple metals, and multiple functional ingredients can be introduced by utilizing the multi-metal oxygen cluster as the sintering additive, and thus the multifunctionality and the excellent mechanical performance are given to a ceramic sintering body; the multi-metal oxygen cluster is an inorganic cathonic cluster of an uncertain structure in essence, and the cathonic polyelectrolyte is polyelectrolyte with positive charge on a polymer chain in essence, so that compounding of the cathonic polyelectrode and the multi-metal oxygen cluster is simple and feasible mixing of ions with opposite charges, universality is realized, stability of the multi-metal oxygen cluster is improved by virtue of the solubility property of the polyelectrode, and multiple functional factors supported by the multi-metal oxygen cluster can be dispersed in ceramic raw material powder relatively uniformly, so that functionality of a ceramic material is improved.
Description
Technical field
The present invention relates to sintering aid technical field, particularly relate to a kind of ceramic post sintering auxiliary agent and preparation method thereof.
Background technology
Stupalith is the class ceramic made through shaping and high temperature sintering with natural or synthetic compound.The mankind can trace back to the Neolithic Age before B.C. 8000 to the use of stupalith, have just occurred pottery the earliest at that time.Through very long historical development, stupalith from initial be the elementary composition conventional ceramic of silicon, oxygen, these three kinds, aluminium by natural matter as feldspar, clay and quartz etc. carry out sintering the large absolutely component obtained, develop structure and composition is more diversified and the advanced ceramics material of multifunction up till now gradually.
Along with the progress of science and technology, the development of stupalith is also always in rapid propelling.Along with the appearance of more demands, as structural ceramics and the insulating ceramic of anti-high atmospheric pressure required in motor car engine, anti-high-voltage, resistance to high temperature corrosion, or the piezoelectric ceramics required for performance such as other mechanics, light, sound, electricity, magnetic, heat, borrow some pottery, magnetic ceramics etc., research worker is devoted to research and develop always and preparation have different performance, the new ceramic material of performance excellence.
Research worker passes through to introduce functional factor in basic stupalith, as rare-earth elements of lanthanum, cerium, praseodymium, neodymium or transition metal chromium, manganese, molybdenum, tungsten etc., to give stupalith new function, and new life.In addition on the one hand, research worker is also constantly improving the processing technology of stupalith.By regulating in stupalith, there is the kind of crystalline phase, the space three-dimensional distribution of various crystalline phase, control etc. the means of porosity and glassy phase size between each crystalline phase, regulation and control and optimize the performance of stupalith.But at present, not yet there is a kind of comparatively pervasive method, can be obtained comparatively easily by simple adjustment feed composition uniform in material, the various and method of the stupalith of excellence of performance.
Multi-metal oxygen cluster is that the anion cluster that a class is formed by connecting by oxo bridge key by transition metal closes salt, its composition is various, common metal component has molybdenum, tungsten, vanadium, manganese etc., the multi-metal oxygen cluster also how be made up of as lanthanum, samarium, europium, cerium etc. report rare earth element in recent years.And as its say, two kinds, three kinds multiple even metallic element compositions may be included in a kind of multi-metal oxygen cluster, and its proportion of composing and geometry can be specified.Therefore, multi-metal oxygen cluster had obvious advantage as a kind of sintering aid of stupalith, namely just the several functions factor can disposablely be inserted as rare earth element in stupalith by adding a kind of sintering aid, and in this addition manner, the ratio between several functional factor can strictly be controlled.
Polyelectrolyte also claims polymer electrolyte, is the synthesis of a class line style or branching and water-soluble polymer, containing the group that can ionize on its structural unit, can be used as thickening material, dispersion agent, flocculation agent, emulsifying agent, suspension stabilizer, tackiness agent etc.The present inventor considers, multi-metal oxygen cluster and cationic polyelectrolyte is carried out compound and obtains ceramic post sintering auxiliary agent, have universality and pleiotropy.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of ceramic post sintering auxiliary agent and preparation method thereof, and the method step is simple, and this ceramic post sintering auxiliary agent has universality and pleiotropy.
In view of this, the invention provides a kind of ceramic post sintering auxiliary agent, be made up of multi-metal oxygen cluster and water-soluble cationic polyelectrolyte.
Preferably, described multi-metal oxygen cluster comprises Keggin-type multi-metal oxygen cluster, Wells-Dawson type multi-metal oxygen cluster, Anderson type multi-metal oxygen cluster and Waugh type multi-metal oxygen cluster.
Preferably, the chemical formula of described multi-metal oxygen cluster is H
4[GeMo
12o
40] 8H
2o, H
6[W
9niO
30(OH)
2] 6H
2o or H
3[CrMo
6o
24h
6].
Preferably, described water-soluble cationic polyelectrolyte comprises quaternised polymine, quaternised polyvinylamine, quaternised polyvinyl pyridine and quaternised poly-aminopyridine.
Preferably, the molecular configuration of described water-soluble cationic polyelectrolyte is straight-chain polymer, branched chain polymer, hyperbranched polymer or branch-shape polymer.
Preferably, the molecule of described water-soluble cationic polyelectrolyte divides the mole number product of equal positive changes and water-soluble cationic polyelectrolyte to be greater than the negative charge number of multi-metal oxygen cluster center anion cluster and the mole number product of multi-metal oxygen cluster.
Preferably, the molecule of described water-soluble cationic polyelectrolyte divides the mole number product of equal positive changes and water-soluble cationic polyelectrolyte to be the negative charge number of multi-metal oxygen cluster center anion cluster and the mole number product of multi-metal oxygen cluster 1.2 times.
Accordingly, the present invention also provides a kind of preparation method of ceramic post sintering auxiliary agent, comprises the following steps:
By the water-soluble cationic polyelectrolyte aqueous solution and multi-metal oxygen cluster aqueous solution, adjust ph is 5 ~ 6, obtains ceramic post sintering auxiliary agent after stirring.
Preferably, described mixing step is specially:
The multi-metal oxygen cluster aqueous solution is obtained by soluble in water for multi-metal oxygen cluster;
The water-soluble cationic polyelectrolyte aqueous solution that concentration is 20% is added in the described multi-metal oxygen cluster aqueous solution.
Preferably, the time of described stirring is 0.5 ~ 2h.
The invention provides a kind of ceramic post sintering auxiliary agent and preparation method thereof, be made up of multi-metal oxygen cluster and water-soluble cationic polyelectrolyte.Compared with prior art, because multi-metal oxygen cluster is made up of various metals, utilize it by introducing various functional component, thus various functional and excellent mechanical property can be brought to ceramic sintered bodies as sintering aid, the essence of multi-metal oxygen cluster is that a class has the inorganic anion bunch determining structure simultaneously, cationic polyelectrolyte is then the polyelectrolyte with positive charge on a base polymer chain in itself, therefore cationic polyelectrolyte and multi-metal oxygen cluster carry out compound is a kind of simple Ar ion mixing with counter charges, there is universality, not only can improve the stability of multi-metal oxygen cluster in powder particles by the dissolving properties of polyelectrolyte, the several functions factor of multi-metal oxygen cluster load is more conducive to be evenly dispersed in ceramic raw material powder, thus make the overall homogeneity of the stupalith of the ceramic post sintering auxiliary agent that have employed cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound better, advantageously in improving the functional of prepared stupalith.
Accompanying drawing explanation
Fig. 1 is the EELS scanning result that the embodiment of the present invention 1 adopts the alumina sintered body of the ceramic post sintering auxiliary agent assisted sintering of cationic polyelectrolyte and multi-metal oxygen cluster compound, and X-coordinate is scanning yardstick, and ordinate zou is the relative abundance of Mo content;
Fig. 2 is the EELS scanning result that embodiment 2 adopts the alumina sintered body of the ceramic post sintering auxiliary agent assisted sintering of cationic polyelectrolyte and multi-metal oxygen cluster compound, and X-coordinate is scanning yardstick, and ordinate zou is the relative abundance of W content;
Fig. 3 is the EELS scanning result that embodiment 3 adopts the alumina sintered body of the ceramic post sintering auxiliary agent assisted sintering of cationic polyelectrolyte and multi-metal oxygen cluster compound, and X-coordinate is scanning yardstick, and ordinate zou is the relative abundance of Mo content.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of ceramic post sintering auxiliary agent, be made up of multi-metal oxygen cluster and water-soluble cationic polyelectrolyte.
According to the present invention, described multi-metal oxygen cluster preferably includes Keggin-type multi-metal oxygen cluster, Wells-Dawson type multi-metal oxygen cluster, Anderson type multi-metal oxygen cluster and Waugh type multi-metal oxygen cluster, also preferably include the multi-metal oxygen cluster of other configurations, described multi-metal oxygen cluster includes but not limited to tungstate, vanadate and molybdate.Wherein, the negatively charged ion general formula of described Keggin-type multi-metal oxygen cluster is [XM
12o
40]
n-, X is P, Si, Ge or As, and M is Mo or W; The negatively charged ion general formula of described Wells-Dawson type multi-metal oxygen cluster is [X
2m
18o
62]
n-, X is preferably P, Si, Ge or As, and M is preferably Mo or W; The negatively charged ion general formula of described Anderson type multi-metal oxygen cluster is [XM
6o
24]
n-, X is preferably Mn, Al, I or Te, and M is preferably Mo or W.Preferred, the chemical formula of described multi-metal oxygen cluster is H
4[GeMo
12o
40] 8H
2o, H
6[W
9niO
30(OH)
2] 6H
2o or H
3[CrMo
6o
24h
6].Described anion cluster periphery be inorganic cation as counter ion, can be hydrogen ion, lithium ion, sodium ion, potassium ion etc.
Described water-soluble cationic polyelectrolyte is preferably polyquaternium, more preferably comprise quaternised polymine, quaternised polyvinylamine, quaternised polyvinyl pyridine and quaternised poly-amino and give a tongue-lashing pyridine, its molecular configuration is preferably straight-chain polymer, branched chain polymer, hyperbranched polymer or branch-shape polymer, also can be multipolymer.
In the stupalith sintering aid of above-mentioned cationic polyelectrolyte and multi-metal oxygen cluster compound, the compound condition of cationic polyelectrolyte and multi-metal oxygen cluster has, the molecule of water-soluble cationic polyelectrolyte divides the mole number product of equal positive changes and water-soluble cationic polyelectrolyte to be preferably greater than the negative charge number of multi-metal oxygen cluster center anion cluster and the mole number product of multi-metal oxygen cluster, preferred, the molecule of described water-soluble cationic polyelectrolyte divides the mole number product of equal positive changes and water-soluble cationic polyelectrolyte to be the negative charge number of multi-metal oxygen cluster center anion cluster and the mole number product of multi-metal oxygen cluster 1.2 times.With poly-4-vinyl N-methyl pyridinium chloride and H that the polymerization degree is 100
3[CrMo
6o
24h
6] be the H of example, 1mol
3[CrMo
6o
24h
6] needing more than 0.03mol 4-polyvinyl N-methyl pyridinium chloride, preferred 0.036mol gathers 4-vinyl N-methyl pyridinium chloride.
Accordingly, the present invention also provides a kind of preparation method of above-mentioned ceramic post sintering auxiliary agent, comprises the following steps:
By the water-soluble cationic polyelectrolyte aqueous solution and multi-metal oxygen cluster aqueous solution, adjust ph is 5 ~ 6, obtains ceramic post sintering auxiliary agent after stirring.
Wherein, described mixing step is specially:
The multi-metal oxygen cluster aqueous solution is obtained by soluble in water for multi-metal oxygen cluster;
In the described multi-metal oxygen cluster aqueous solution, add the water-soluble cationic polyelectrolyte aqueous solution that concentration is 20%, preferably constantly stir in the process adding the water-soluble cationic polyelectrolyte aqueous solution.
In the process preparing ceramic post sintering auxiliary agent, preferably stir 0.5 ~ 2h, be more preferably 1h, and the ph value continuing monitoring mixed solution is between 5 ~ 6.
The ceramic post sintering auxiliary agent now-making-now-using in the ordinary course of things of cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound, do not carry out standing storage, because standing storage likely can produce flocculation or precipitation, and be unfavorable for its mixing with ceramic material powder; Ceramic post sintering auxiliary agent desired raw material due to cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound obtains convenient, and therefore the impact that causes production process of now-making-now-using is extremely limited.
Preparation method's step of ceramic post sintering auxiliary agent provided by the invention is simple, and feasibility is high.Multi-metal oxygen cluster is various as a class composition, the construction unit that structure-rich is colorful, not only synthesis technique is simple, serialization scale operation can be carried out, and it can be made up of various metals, especially can by rare earth element as lanthanum, cerium, europium etc. be formed, the elemental range that heteroatoms contained by it can adopt is more extensive, utilizes it can bring various functional and excellent mechanical property by introducing various functional component such as rare earth element etc. to ceramic sintered bodies as sintering aid, essence due to multi-metal oxygen cluster is that a class has the inorganic anion bunch determining structure, cationic polyelectrolyte is then the polyelectrolyte with positive charge on a base polymer chain in itself, therefore cationic polyelectrolyte and multi-metal oxygen cluster carry out compound is a kind of simple Ar ion mixing with counter charges, not only can improve the stability of multi-metal oxygen cluster in powder particles by the dissolving properties of polyelectrolyte, the several functions factor of multi-metal oxygen cluster load is more conducive to be evenly dispersed in ceramic raw material powder, thus make the overall homogeneity of the stupalith of the ceramic post sintering auxiliary agent that have employed cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound better, advantageously functional in what improve that prepared stupalith expects.
The method of the alumina sintered body of the polyoxometallate sintering aid employing multielement of the present invention composition being carried out to EELS test is:
Transmission electron microscope (Tecnai G2F20) alumina sintered body to the ceramic post sintering auxiliary agent employing cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound that use is equipped with electronic energy loss spectrometer (EELS) annex carries out EELS sweep test under acceleration voltage is 200kV condition, and draws to respective element.
After preparing ceramic post sintering auxiliary agent, preferably ceramic post sintering auxiliary agent is added in ceramic raw material powder together with other binding agent, dispersion agent, softening agent, defrother etc. and form slurry, drying is carried out by spraying dry, then obtain by laser granulation the material grain that particle diameter is about 100 ~ 200 μm, now cationic polyelectrolyte of the present invention mixes with ceramic raw material powder with the stupalith sintering aid of multi-metal oxygen cluster compound, only need forming process, after sintering processing, just can obtain the various stupalith of performance.The present invention is for binding agent, dispersion agent, softening agent, defrother and ceramic raw material powder etc. and have no special requirements, and preferably adopts binding agent well known to those skilled in the art, dispersion agent, softening agent, defrother and ceramic raw material powder.
Embodiment of the present invention is just in order to set forth the universality of the ceramic post sintering auxiliary agent of cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound and pleiotropy simply; The ceramic post sintering auxiliary agent of cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound is not limited in the combination of several multi-metal oxygen cluster and the cationic polyelectrolyte used in embodiment, but widely, the combination of water miscible multi-metal oxygen cluster and cationic polyelectrolyte all belongs to the ceramic post sintering auxiliary agent of cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound.
In the following example, if no special instructions, all formula per-cent all by weight.
Embodiment 1
Select Keggin-type molybdenum germanium heteropolyacid, molecular formula is H
4[GeMo
12o
40] 8H
2o, concentration be 20% the poly-4-vinyl N-methyl pyridinium chloride aqueous solution carry out the preparation of the ceramic post sintering auxiliary agent of cationic polyelectrolyte and multi-metal oxygen cluster compound.
Take 20g Keggin-type molybdenum germanium heteropolyacid (H
4[GeMo
12o
40] 8H
2o), be dissolved in 1L pure water, completely after dissolving, in solution, add the poly-4-vinyl N-methyl pyridinium chloride aqueous solution that 2L mass concentration is 20% lentamente, constantly stir in adition process and be between 5 ~ 6 with the pH value of hydrochloric acid control mixed solution simultaneously; Add complete after, continue stir 1h, and continue monitoring mixed solution ph value be between 5 ~ 6; So just obtain poly-4-vinyl N-methyl pyridinium chloride and the Keggin-type molybdenum germanium heteropolyacid (H of fresh preparation
4[GeMo
12o
40] 8H
2o) the ceramic post sintering auxiliary agent of compound is for subsequent use.
Following formula is adopted to carry out mixing to prepare slurry:
(1) aluminum oxide (purity 99.99%) 87%
(2) the poly-4-vinyl N-methyl pyridinium chloride of fresh preparation and Keggin-type molybdenum germanium heteropolyacid (H
4[GeMo
12o
40] 8H
2o) the ceramic post sintering auxiliary agent 12% of compound
(3) ammonium citrate 0.6%
(4) ammonium persulphate 0.1%
(5) polyoxyethylene glycol 0.3%
The slurry that mixes is used spray-drying process spraying dry, and is a granulated into by laser diffractometry and there is median size at the powder of 100 ~ 200 μm.
The powder of granulation is used the products formed that 100MPa isostatic pressing is 10mm × 10mm × 3mm, sinters by the sintering procedure set below:
DEG C about 30 DEG C/hours, room temperature ~ 200
200 DEG C ~ 300 DEG C about 50 DEG C/hours
300 DEG C ~ 700 DEG C about 60 DEG C/hours
700 DEG C ~ 800 DEG C about 50 DEG C/hours
800 DEG C ~ 1500 DEG C about 100 DEG C/hours are incubated 1.5 hours
Sinter and completely just obtain poly-4-vinyl N-methyl pyridinium chloride and Keggin-type molybdenum germanium heteropolyacid (H
4[GeMo
12o
40] 8H
2o) the alumina insulation pottery of the ceramic post sintering auxiliary agent assisted sintering of compound.
The alumina sintered body that obtains is pulverized, gets broken end carry out transmissioning electric mirror test so that copper mesh is sticky.
Use is equipped with the transmission electron microscope (Tecnai G2F20) of electronic energy loss spectrometer (EELS) annex, the fragment of random choose five pieces of sizes about 200 μm in the copper mesh visual field, on every block fragment, random selecting line is swept direction and is detected, sweep length is 200 μm, gathers the signal of molybdenum and draws.
Fig. 1 is the EELS scanning result that embodiment 1 adopts the alumina sintered body of the ceramic post sintering auxiliary agent assisted sintering of cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound, can see that Mo fignal center spacing is even significantly, general at about 20 ~ 30 μm, the overall good uniformity of the alumina sintered body of the ceramic post sintering auxiliary agent assisted sintering adopting cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound can be described, have the primary condition possessing excellent properties.
Embodiment 2
Select Waugh type tungsten nickel heteropolyacid, molecular formula is H
6[W
9niO
30(OH)
2] 6H
2o, concentration be 20% the poly-4-vinyl N-methyl pyridinium chloride aqueous solution carry out the preparation of the ceramic post sintering auxiliary agent of cationic polyelectrolyte and multi-metal oxygen cluster compound.
Take 25g Waugh type tungsten nickel heteropolyacid (H
6[W
9niO
30(OH)
2] 6H
2o), be dissolved in 1L pure water, completely after dissolving, in solution, add the poly-4-vinyl N-methyl pyridinium chloride aqueous solution that 2L concentration is 20% lentamente, constantly stir in adition process and be between 5 ~ 6 with the pH value of hydrochloric acid control mixed solution simultaneously; Add complete after, continue stir 1h, and continue monitoring mixed solution ph value be between 5 ~ 6; So just obtain poly-4-vinyl N-methyl pyridinium chloride and the Waugh type tungsten nickel heteropolyacid (H of fresh preparation
6[W
9niO
30(OH)
2] 6H
2o) the ceramic post sintering auxiliary agent of compound is for subsequent use.
Following formula is adopted to carry out mixing to prepare slurry:
(1) aluminum oxide (purity 99.99%) 87%
(2) the poly-4-vinyl N-methyl pyridinium chloride of fresh preparation and Waugh type tungsten nickel heteropolyacid (Na
6[W
9niO
30(OH)
2] 6H
2o) the ceramic post sintering auxiliary agent 12% of compound
(3) ammonium citrate 0.6%
(4) ammonium persulphate 0.1%
(5) polyoxyethylene glycol 0.3%
The slurry that mixes is used spray-drying process spraying dry, and is a granulated into by laser diffractometry and there is median size at the powder of 100 ~ 200 μm.
The powder of granulation is used the products formed that 100MPa isostatic pressing is 10mm × 10mm × 3mm, sinters by the sintering procedure set below:
DEG C about 30 DEG C/hours, room temperature ~ 200
200 DEG C ~ 300 DEG C about 50 DEG C/hours
300 DEG C ~ 700 DEG C about 60 DEG C/hours
700 DEG C ~ 800 DEG C about 50 DEG C/hours
800 DEG C ~ 1500 DEG C about 100 DEG C/hours are incubated 1.5 hours
Sinter and completely just obtain poly-4-vinyl N-methyl pyridinium chloride and Waugh type tungsten nickel heteropolyacid (H
6[W
9niO
30(OH)
2] 6H
2o) the alumina insulation pottery of the ceramic post sintering auxiliary agent assisted sintering of compound.
The alumina sintered body that obtains is pulverized, gets broken end carry out transmissioning electric mirror test so that copper mesh is sticky.
Use is equipped with the transmission electron microscope (Tecnai G2F20) of electronic energy loss spectrometer (EELS) annex, the fragment of random choose five pieces of sizes about 200 μm in the copper mesh visual field, on every block fragment, random selecting line is swept direction and is detected, sweep length is 200 μm, gathers the signal of molybdenum and draws.
Fig. 2 is the EELS scanning result that embodiment 2 adopts the alumina sintered body of the ceramic post sintering auxiliary agent assisted sintering of cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound, can see that W fignal center spacing is even significantly, general at about 70 μm, the overall good uniformity of the alumina sintered body of the ceramic post sintering auxiliary agent assisted sintering adopting cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound can be described, have the primary condition possessing excellent properties.
Embodiment 3
Select Anderson type molybdenum germanium heteropolyacid, molecular formula is H
3[CrMo
6o
24h
6], concentration be 20% the poly-4-vinyl N-methyl pyridinium chloride aqueous solution carry out the preparation of the ceramic post sintering auxiliary agent of cationic polyelectrolyte and multi-metal oxygen cluster compound.
Take 11g Anderson type molybdenum chromium heteropolyacid (H
3[CrMo
6o
24h
6]), be dissolved in 1L pure water, completely after dissolving, in solution, add the poly-4-vinyl N-methyl pyridinium chloride aqueous solution that 2L concentration is 20% lentamente, constantly stir in adition process and be between 5 ~ 6 with the pH value of hydrochloric acid control mixed solution simultaneously; Add complete after, continue stir 1h, and continue monitoring mixed solution ph value be between 5 ~ 6; So just obtain poly-4-vinyl N-methyl pyridinium chloride and the Anderson type molybdenum chromium heteropolyacid (H of fresh preparation
3[CrMo
6o
24h
6]) the ceramic post sintering auxiliary agent of compound is for subsequent use.
Following formula is adopted to carry out mixing to prepare slurry:
(1) aluminum oxide (purity 99.99%) 93%
(2) the poly-4-vinyl N-methyl pyridinium chloride of fresh preparation and Anderson type molybdenum chromium heteropolyacid (H
3[CrMo
6o
24h
6]) the ceramic post sintering auxiliary agent 6% of compound
(3) ammonium citrate 0.6%
(4) ammonium persulphate 0.1%
(5) polyoxyethylene glycol 0.3%
The slurry that mixes is used spray-drying process spraying dry, and is a granulated into by laser diffractometry and there is median size at the powder of 100 ~ 200 μm.
The powder of granulation is used the products formed that 100MPa isostatic pressing is 10mm × 10mm × 3mm, sinters by the sintering procedure set below:
DEG C about 30 DEG C/hours, room temperature ~ 200
200 DEG C ~ 300 DEG C about 50 DEG C/hours
300 DEG C ~ 700 DEG C about 60 DEG C/hours
700 DEG C ~ 800 DEG C about 50 DEG C/hours
800 DEG C ~ 1500 DEG C about 100 DEG C/hours are incubated 1.5 hours
Sinter and completely just obtain poly-4-vinyl N-methyl pyridinium chloride and Anderson type molybdenum chromium heteropolyacid (H
3[CrMo
6o
24h
6]) the alumina insulation pottery of the ceramic post sintering auxiliary agent assisted sintering of compound.
The alumina sintered body that obtains is pulverized, gets broken end carry out transmissioning electric mirror test so that copper mesh is sticky.
Use is equipped with the transmission electron microscope (Tecnai G2F20) of electronic energy loss spectrometer (EELS) annex, the fragment of random choose five pieces of sizes about 200 μm in the copper mesh visual field, on every block fragment, random selecting line is swept direction and is detected, sweep length is 200 μm, gathers the signal of molybdenum and draws.
Fig. 3 is the EELS scanning result that embodiment 3 adopts the alumina sintered body of the ceramic post sintering auxiliary agent assisted sintering of cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound, can see that Mo fignal center spacing is even significantly, general at about 50 ~ 60 μm, the overall good uniformity of the alumina sintered body of the ceramic post sintering auxiliary agent assisted sintering adopting cationic polyelectrolyte of the present invention and multi-metal oxygen cluster compound can be described, have the primary condition possessing excellent properties.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a ceramic post sintering auxiliary agent, is characterized in that, is made up of multi-metal oxygen cluster and water-soluble cationic polyelectrolyte.
2. ceramic post sintering auxiliary agent according to claim 1, is characterized in that, described multi-metal oxygen cluster comprises Keggin-type multi-metal oxygen cluster, Wells-Dawson type multi-metal oxygen cluster, Anderson type multi-metal oxygen cluster and Waugh type multi-metal oxygen cluster.
3. ceramic post sintering auxiliary agent according to claim 1, is characterized in that, the chemical formula of described multi-metal oxygen cluster is H
4[GeMo
12o
40] 8H
2o, H
6[W
9niO
30(OH)
2] 6H
2o or H
3[CrMo
6o
24h
6].
4. ceramic post sintering auxiliary agent according to claim 1, is characterized in that, described water-soluble cationic polyelectrolyte comprises quaternised polymine, quaternised polyvinylamine, quaternised polyvinyl pyridine and quaternised poly-aminopyridine.
5. ceramic post sintering auxiliary agent according to claim 1, is characterized in that, the molecular configuration of described water-soluble cationic polyelectrolyte is straight-chain polymer, branched chain polymer, hyperbranched polymer or branch-shape polymer.
6. ceramic post sintering auxiliary agent according to claim 1, it is characterized in that, the molecule of described water-soluble cationic polyelectrolyte divides the mole number product of equal positive changes and water-soluble cationic polyelectrolyte to be greater than the negative charge number of multi-metal oxygen cluster center anion cluster and the mole number product of multi-metal oxygen cluster.
7. ceramic post sintering auxiliary agent according to claim 6, it is characterized in that, the molecule of described water-soluble cationic polyelectrolyte divides the mole number product of equal positive changes and water-soluble cationic polyelectrolyte to be the negative charge number of multi-metal oxygen cluster center anion cluster and the mole number product of multi-metal oxygen cluster 1.2 times.
8. a preparation method for the ceramic post sintering auxiliary agent described in claim 1 ~ 7 any one, is characterized in that, comprise the following steps:
By the water-soluble cationic polyelectrolyte aqueous solution and multi-metal oxygen cluster aqueous solution, adjust ph is 5 ~ 6, obtains ceramic post sintering auxiliary agent after stirring.
9. preparation method according to claim 8, is characterized in that, described mixing step is specially:
The multi-metal oxygen cluster aqueous solution is obtained by soluble in water for multi-metal oxygen cluster;
The water-soluble cationic polyelectrolyte aqueous solution that concentration is 20% is added in the described multi-metal oxygen cluster aqueous solution.
10. preparation method according to claim 8, is characterized in that, the time of described stirring is 0.5 ~ 2h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108367492A (en) * | 2016-02-25 | 2018-08-03 | 惠普发展公司，有限责任合伙企业 | It is printed using sintering aid/fixer fluid and the three-dimensional (3D) of liquid functional material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102225899A (en) * | 2011-04-14 | 2011-10-26 | 东北师范大学 | Ionic liquid based on Dawson-type polyoxometalate and synthesis method thereof |
| CN104119232A (en) * | 2014-07-29 | 2014-10-29 | 北京理工大学 | Polyoxometalate cluster organic amine salt and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225899A (en) * | 2011-04-14 | 2011-10-26 | 东北师范大学 | Ionic liquid based on Dawson-type polyoxometalate and synthesis method thereof |
| CN104119232A (en) * | 2014-07-29 | 2014-10-29 | 北京理工大学 | Polyoxometalate cluster organic amine salt and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108367492A (en) * | 2016-02-25 | 2018-08-03 | 惠普发展公司，有限责任合伙企业 | It is printed using sintering aid/fixer fluid and the three-dimensional (3D) of liquid functional material |
| CN108367492B (en) * | 2016-02-25 | 2020-03-06 | 惠普发展公司，有限责任合伙企业 | Three-dimensional (3D) printing using sintering aid/fixer fluids and liquid functional materials |
| US11020874B2 (en) | 2016-02-25 | 2021-06-01 | Hewlett-Packard Development Company, L.P. | Three-dimensional (3D) printing with a sintering aid/fixer fluid and a liquid functional material |
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