CN105503208B - A kind of method that metering nozzle is prepared using plural gel stabilizing zirconia as matrix - Google Patents
A kind of method that metering nozzle is prepared using plural gel stabilizing zirconia as matrix Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
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Abstract
The invention discloses a kind of method that metering nozzle is prepared using plural gel stabilizing zirconia as matrix, using magnesia partial stabilized zirconia as aggregate, necessarily required monoclinic zirconia micro mist and magnesium hydroxide, calcium hydroxide gel are equipped with through wet-milling, vacuum suction filter, fine powder dry, that mill forms altogether.The ratio of content of magnesia 2.5~3.0% in the common pulverized powder of control, silica and calcium oxide is 2:1, react altogether in pulverized powder in monoclinic zirconia sintering process, utilize the base strength difference of magnesia and calcium oxide, calcium oxide forms stable phase with oxidation pasc reaction first in sintering process, magnesia is no longer with aoxidizing pasc reaction, it is ensured that the accuracy of stabilized magnesium hydroxide agent addition and the ratio of part formation stabilizing zirconia quantity.Prevent the precipitation of stabilized magnesium hydroxide agent in particle.Show that stabilizer precipitation quantity is few in particle with rear residual sample microstructure analysis, zirconia particles rupture without phase-change substantially.
Description
Technical field
It is resistant to hard with control molten steel flow device the present invention relates to continuously casting tundish in related ferrous metallurgical industry
The preparation of fiery material, is specifically a kind of method that metering nozzle is prepared using plural gel stabilizing zirconia as matrix.
Background technology
Metering nozzle refers to the function element made installed in a kind of high-temperature structural ceramics of continuously casting tundish bottom.
Its main function is that Metal in Tundish static pressure remains unchanged substantially, and molten steel flows into crystallizer by metering nozzle, and crystallizer leads to
Big flow water cooling is crossed, liberated heat when taking away solidification of molten steel, makes molten steel solidification into base.The heat taken away due to crystallizer water cooling
It is limited, thus, the molten steel quantity that crystallizer is flowed into the unit interval must be within limits.It is cured in the aperture of metering nozzle
Greatly, the unit interval flows into crystallizer molten steel quantity the more, selects suitable aperture that tundish water nozzle is made, and is sizing water
Mouthful.The main reason for metering nozzle fails is due to be reacted with the stabilizer in zirconium oxide during MOLTEN STEEL FLOW, and stabilizer takes off
Molten, and then cause zirconium oxide unstability, particle is made an exception, and intensity is greatly lowered, and scour resistance, which declines, to be caused expanding, ties inflow
The molten steel solidification liberated heat of brilliant device is more than the heat that crystallizer cooling water can be taken away and exits use.
The content (wt%) of zirconium oxide is generally 95% or so in zirconium oxide metering nozzle, and actual life is small for 10
When or so.The main reason for service life is short is Zirconia-stabilized dose of precipitation, and stabilizer forms low with the other elements in steel, slag
Melting eutectic thing, eutectic are lost in, zirconium oxide unstability, breakage of particles, and intensity is greatly lowered, and scour resistance, which declines, to be caused to expand
Footpath, so as to cause zirconium oxide metering nozzle service life short.
The content of the invention
It is an object of the invention to provide a kind of method that metering nozzle is prepared using plural gel stabilizing zirconia as matrix,
The stabilizer that base portion adds in sintering process is prevented to be reacted with silicon oxide impurity by additive, it is ensured that it is solid-solution in list
Quantity in oblique zirconium oxide, forms the controllable stable phase content of ratio, improves the service life of zirconium oxide metering nozzle.
In order to realize above-mentioned task, the present invention takes following technical solution：
A kind of method that metering nozzle is prepared using plural gel stabilizing zirconia as matrix, including by aggregate, altogether pulverized powder
Through being kneaded, after ageing mixture shaping, firing obtains metering nozzle with bonding agent；
The aggregate is magnesia partial stabilized zirconia, and pulverized powder is by plural gel and monoclinic zirconia micro mist altogether
After mixing, the powder for grinding obtain altogether is dried, plural gel includes magnesium hydroxide gels and calcium hydroxide gel.
Specifically, monoclinic zirconia micro mist chemistry percentage by weight composition is：ZrO2+HfO2＞ 99%, SiO2＜
0.45%；The granularmetric composition of monoclinic zirconia micro mist is：d50=0.8~0.9 μm, d904.0 μm of ＜；In magnesium hydroxide gels
Magnesia solid concentration is 20~40g/L, and calcium oxide solid concentration is 28~56g/L in calcium hydroxide gel；
Monoclinic zirconia micro mist：Magnesia solid phase proportion is 97.0~97.5 in magnesium hydroxide gels：2.5~3.0；Hydrogen
Calcium oxide solid phase in calcium oxide gel：Siliconoxide mass ratio is 2 in monoclinic zirconia micro mist:1, by calcium hydroxide gel, hydrogen-oxygen
Change magnesium gel and monoclinic zirconia micro mist mix after, the dry obtained powder that grind altogether be common pulverized powder.
More specifically, the particle diameter of pulverized powder is d altogether904.0 μm of ＜.
Further, it is 45 according to the mass ratio of aggregate and monoclinic zirconia micro mist:55 by aggregate pulverized powder dispensing together,
By mass percentage, the addition of bonding agent for aggregate together pulverized powder total amount 8%.
More progressive one, the chemical composition of magnesia partial stabilized zirconia aggregate is (wt%)：ZrO2=95.12, HfO2
=2.14, MgO=2.69, CaO=0.02, Al2O3=0.03.
In addition, the firing temperature is 1700~1710 DEG C.
In addition, the preparation of the magnesium hydroxide gels includes：
By MgCl2·6H2O is configured to the mother liquor that concentration is 0.5~1.0mol/L, adds the scattered of mother liquor gross weight 1.2%
Agent, is adjusted to 7~10 by the pH value for the mother liquor for adding dispersant afterwards and obtains gel, then by after 8~16h of obtained gel ageing
By the Cl in gel-Removal obtains the magnesium hydroxide gels；
The preparation of the calcium hydroxide gel includes：
By CaCl2·6H2O is configured to the mother liquor that concentration is 0.5~1.0mol/L, adds the scattered of mother liquor gross weight 1.2%
Agent, is adjusted to 7~10 by the pH value for the mother liquor for adding dispersant afterwards and obtains gel, then by after 8~16h of obtained gel ageing
By the Cl in gel-Removal obtains the calcium hydroxide gel.
Advantages of the present invention is：
The present invention is equipped with monoclinic zirconia and magnesium hydroxide-magnesium hydroxide using magnesia partial stabilized zirconia as aggregate
Plural gel is the common pulverized powder of stabilizer composition, ensure that the uniformity and sub-micron of stabilizer calcium oxide and magnesium oxide dispersion
Level particle diameter, adds PVA bonding agents, through being kneaded, being aged aftershaping, metering nozzle is then burnt till in electrical kiln, the metering nozzle
Can exceed that all with the performance of the metering nozzle prepared by partially stabilized zirconia, service life up to 30 it is small when more than.With
Residual sample microstructure analysis shows that stabilizer precipitation quantity is few afterwards, and zirconia particles rupture without phase-change substantially.
Brief description of the drawings
Fig. 1 is the preparation technology flow chart of the zirconium oxide metering nozzle of the present invention.
Below in conjunction with drawings and examples, the present invention is described in further detail.
Embodiment
Applicant (Xi'an University of Architecture and Technology) assume responsibility for Jinan Quan Cheng scholar's construction project " ZrO2/ for 2010
The research of Al2O3 composite diphase materials and the application in continuous casting functional material ", application inventor obtain Jinan " spring city scholar " honor and claim
Number；2013, state natural sciences fund general project is assume responsibility on the basis of previous research work, and " zirconia metering nozzle was steady
Determine agent precipitation breakage of particles mechanism and the service life improve research " (project number 51372193).Aoxidized according to undertaken project research
Zirconia metering nozzle Wear mechanism and raising service life, achievement in research shows, since zirconia material is to use zircon sand
(ZrSiO4) desiliconization produces, preparation process, which determines, wherein necessarily contains a certain number of SiO2, with monoclinic zirconia and stabilizer
Altogether milling for matrix production zirconium oxide metering nozzle in, base portion in sintering process stabilizer MgO by diffusion with
ZrO2Solid solution stable phase is formed, and scanning electron microscope analysis is shown, MgO is uniform except solid solution stable phase is formed in diffusion process
Distribution is outer, and region present in MgO collection is also SiO2Rich region.EDS analysis results show, subregion MgO/SiO2Ratio
It is worth close to forsterite (2MgO.SiO2) composition.SiO in raw material2Presence, consume a certain number of stabilizers.SiO2Contain
The uncertainty of amount have impact on the unstable of stabilizer addition, so that stable phase content fluctuation.
With reference to Fig. 1, the preparation method of zirconium oxide metering nozzle of the invention, using magnesia partial stabilized zirconia as bone
Material, is equipped with the common pulverized powder of monoclinic zirconia and magnesium hydroxide-magnesium hydroxide plural gel for stabilizer composition, ensure that stabilization
The uniformity and submicron order particle diameter of agent calcium oxide and magnesium oxide dispersion, add PVA bonding agents, through being kneaded, being aged aftershaping, so
Burn till in electrical kiln, specifically carried out according to the following steps afterwards：
1) preparation of magnesium hydroxide gels and calcium hydroxide gel
Take MgCl respectively by weight percentage2·6H2O and CaCl2·6H20 prepares mother liquor, in mother liquor, MgCl2·6H2O and
CaCl2·6H20 concentration is 0.5~1.0mol/L, adds the dispersant PEG, NH of mother liquor gross weight 1.2%4(OH) positive titration,
Gel is made to pH=7~10 in stirring.Gel is aged 8h~16h, and deionized water washs to silver nitrate and can't detect Cl-Untill,
Respectively obtain magnesium hydroxide gels and calcium hydroxide gel.
2) preparation of pulverized powder altogether
Dispensing fine powder is made of monoclinic zirconia micro mist, magnesium hydroxide gels and calcium hydroxide gel.Wherein：
Chemical percentage by weight composition is in monoclinic zirconia micro mist：ZrO2+HfO2＞ 99%, SiO2＜ 0.45%, surplus
For impurity；The granularmetric composition of monoclinic zirconia is：d50=0.8~0.9 μm, d904.0 μm of ＜；
Magnesia solid concentration in magnesium hydroxide gels is 20~40g/L, the calcium oxide solid phase in calcium hydroxide gel
Content is 28~56g/L；
According to monoclinic zirconia micro mist：Magnesia solid phase proportion=(97.0~97.5) in magnesium hydroxide gels：(2.5
~3.0), calcium oxide solid phase in calcium hydroxide gel：Siliconoxide mass ratio=2 in monoclinic zirconia micro mist:1 determines magnesium hydroxide
The mixed amount of gel and calcium hydroxide gel and monoclinic zirconia micro mist.
Magnesium hydroxide gels and calcium hydroxide gel are added in monoclinic zirconia micro mist, more than wet-milling 4h, makes hydrogen-oxygen
Change magnesium-calcium hydroxide gel fully to mix with monoclinic zirconia fine powder.Slurry after mixing is made after drying and dehydrating through vacuum suction filter
Mixing fine powders are obtained, mixing fine powders are again dispensing fine powder through the levigate homogenizing of 4h.
The addition of magnesium hydroxide gels and calcium hydroxide gel ensures that institute's silicon oxide-containing is preferential in monoclinic zirconia micro mist
React with calcium oxide and generate saturation calcium silicates, magnesia no longer reacts with silica, it is ensured that stabilizer addition
Accuracy.
3) selection of magnesia partial stabilized zirconia aggregate
Available partially stabilized zirconia has the yttrium partially stabilized zirconium oxide of oxidation, magnesia partial stabilized currently on the market
Zirconium oxide, calcium oxide partially stabilized zirconia and magnesia calcium oxide composite portion stabilizing zirconia.In the present embodiment, aggregate is adopted
With magnesia partial stabilized zirconia, the chemical composition for the magnesia partial stabilized zirconia aggregate purchased is (wt%)：
ZrO2=95.12, HfO2=2.14, MgO=2.69, CaO=0.02, Al2O3=0.03.
4) aggregate is pressed：Monoclinic zirconia micro mist=45：55 dispensings, add the PVA bonding agents of dispensing total amount 8%, are kneaded 45
Minute, when the pug ageing mixture 24 being kneaded is small, then it is molded using 150t hydraulic presses；
It is qualified after dry when drying 24 is small in 105 ± 5 DEG C of baking oven after when base substrate natural drying 24 after shaping is small
Base substrate is in electrical kiln, and at a temperature of 1700 DEG C~1710 DEG C, 6 hours of insulation burn till obtained zirconium oxide metering nozzle.
It is the embodiment that inventor provides below.
Embodiment 1：
Step 1, the preparation of dispensing fine powder (exemplified by preparing 550g)
Monoclinic zirconia micro mist chemical composition is (wt%)：ZrO2+HfO2=99.5, SiO2=0.25, Fe2O3=0.01,
Surplus is impurity；
The granularmetric composition of monoclinic zirconia is：d50=0.845 μm, d90=3.89 μm；
SiO in 550g monoclinic zirconia micro mists2Quality is 1.375g, according to monoclinic zirconia micro mist：Magnesium hydroxide gels
Middle magnesia solid phase proportion=97.0：3.0, calcium oxide solid phase in magnesium hydroxide gels：Silica in monoclinic zirconia micro mist
Mass ratio=2:1 determines the addition of magnesium hydroxide gels and calcium hydroxide gel.Calcium oxide in calcium hydroxide gel should be added
Solid phase is 2.75g, and magnesia solid phase is 17.0g in magnesium hydroxide gels.
Take MgCl respectively by weight percentage2·6H2O and CaCl2·6H20 mother liquor prepared, in mother liquor, MgCl2·6H2O
And CaCl2·6H20 concentration is 0.5Mol/L, i.e., magnesia, the solid concentration of calcium oxide are 20g/L and 28g/ respectively in mother liquor
L, takes MgCl respectively2·6H2O and CaCl2·6H20 mother liquor 850ml and 100ml, adds the dispersant of mother liquor gross weight 1.2%
PEG, NH4(OH) positive titration, is stirred to PH=7~10, and gel is made.Gel is aged 12h, and deionized water is washed to silver nitrate and examined
Cl is not detected-Untill, magnesium hydroxide gels and calcium hydroxide gel are made respectively.
Magnesium hydroxide gels and calcium hydroxide gel are added in monoclinic zirconia micro mist, more than wet-milling 4h, makes hydrogen-oxygen
Change magnesium-calcium hydroxide gel fully to mix with monoclinic zirconia micro mist.Slurry after mixing is made after drying and dehydrating through vacuum suction filter
Mixing fine powders are obtained, mixing fine powders are again dispensing fine powder through the levigate homogenizing of 4h, and the particle diameter of fine powder is d90=3.85 μm.
Step 2, the composition for choosing magnesia partial stabilized zirconia aggregate is (wt%)：ZrO2=95.12, HfO2=
2.14, MgO=2.69, CaO=0.02, Al2O3=0.03；Granularmetric composition is 0~0.5mm.
Step 3, compares aggregate according to quality：Monoclinic zirconia micro mist=45：55 by aggregate pulverized powder dispensing together, takes and matches somebody with somebody
Expect 1kg, additional PVA bonding agents 8%, i.e. 80g, is kneaded 45 minutes, is mixed to prepare blank.When the blank ageing 24 being kneaded is small.
Step 4, obtained blank load mould, are molded with 150t hydraulic presses in 150MPa, molding blank spontaneously dries 24
After hour, the re-dry 24h under the conditions of 105 ± 5 DEG C, then sinters at a temperature of 1710 DEG C, its use of obtained metering nozzle
Service life has reached 32h.Show that stabilizer precipitation quantity is few with rear residual sample microstructure analysis, zirconia particles are substantially without phase-change
Rupture.
Embodiment 2：
The present embodiment and embodiment 1 except that：Monoclinic zirconia micro mist chemistry somewhat lower purity in step 1, it is changed
It is (wt%) to learn composition：ZrO2+HfO2=99.2, SiO2=0.45, Fe2O3=0.03, surplus is impurity；
The granularmetric composition of monoclinic zirconia is：d50=0.813 μm, d90=3.79 μm；
According to monoclinic zirconia micro mist：Magnesia solid phase proportion=97.0 in magnesium hydroxide gels：3.0, magnesium hydroxide
Calcium oxide solid phase in gel：Siliconoxide mass ratio=2 in monoclinic zirconia micro mist:1 determines magnesium hydroxide gels and calcium hydroxide
The addition of gel.It is 4.95g that calcium oxide solid phase in calcium hydroxide gel, which should be added, and magnesia solid phase is in magnesium hydroxide gels
17.0g。
Take MgCl respectively by weight percentage2·6H2O and CaCl2·6H20 mother liquor prepared, in mother liquor, MgCl2·6H2O
And CaCl2·6H20 concentration is 0.5Mol/L, i.e., magnesia, the solid concentration of calcium oxide are 20g/L and 28g/ respectively in mother liquor
L, takes MgCl respectively2·6H2O and CaCl2·6H20 mother liquor 850ml and 177ml, remaining step are identical.Obtained metering nozzle gas
Porosity is less than 1 product of embodiment, its service life does not have difference with embodiment 1.Illustrate to use the monocline oxygen in the method fine powder
Changing zirconium purity can suitably reduce, and production cost can decline.
Embodiment 3：
The present embodiment and embodiment 2 except that：Since product gas porosity is less than 1 product of embodiment in embodiment 2, step
Firing temperature is adjusted to 1700 DEG C in rapid 3, its service life of obtained zirconium oxide metering nozzle is also up to 32h.Firing temperature
Being adjusted to 1700 DEG C of power consumptions by 1710 DEG C reduces, and heater service life can increase substantially, and production cost declines.
Comparative example 1：
The present embodiment is as different from Example 1：Plural gel is directly mixed to the preparation for carrying out metering nozzle with aggregate,
It is added without monoclinic zirconia micro mist；
Since without stabilizer solid solution reaction, sintering process high yield rate is but former in embodiment 1 about 0.5% in sintering process
Expect poor activity, under the premise of the same porosity is reached, firing temperature is higher than about 20 DEG C of embodiment 1, product thermal shock resistance index
Not as good as the 20% of embodiment 1, open during pouring to occur opening pouring and burst phenomenon and account for 5%.When average life is 16 small or so.
Comparative example 2：
The present embodiment is as different from Example 1：It is used for stabilized monoclinic zirconia micro mist only with magnesium hydroxide gels, its
Firing temperature is 1720 DEG C；
The porosity of obtained metering nozzle is slightly below embodiment 1, and product thermal shock resistance index is 4 times of comparative example 1,
Open to occur without to open to pour substantially during pouring and burst phenomenon, service life up to 30 it is small when.But microstructure analysis is shown, part oxygen
Change magnesium and generate the forsterite (2MgO.SiO for being difficult to sinter with impurity in monoclinic zirconia2), consume the oxidation in gel
Magnesium, reduces the effect of magnesium hydroxide gels.
Comparative example 3：
The present embodiment is as different from Example 1：Plural gel is not used, is used to stablize only with calcium hydroxide gel single
Oblique zirconium oxide, the calcium oxide in calcium hydroxide gel, which can also be solid-solution in monoclinic zirconia, forms stable phase.
But since oxidation calc-alkaline is better than magnesia, it is easy to react with acidic oxide, the oxidation of stable calcium oxide
Zirconium corrosion resistance is poor, product service life only have 24 it is small when or so.The introducing of calcium oxide can make firing temperature reduce by 10 DEG C of left sides
It is right.
The result of summary embodiment is understood：Only use plural gel, that is, magnesium hydroxide gels and calcium hydroxide gel
At the same time in use, the magnesia in magnesium hydroxide gels forms the Zirconia-stabilized phase of stabilized magnesium hydroxide, hydrogen with monoclinic zirconia
The silicon oxide impurity in calcium oxide and monoclinic zirconia in calcium oxide gel preferentially generates dicalcium silicate, prevents magnesia and oxygen
SiClx is reacted, and prepared metering nozzle service life and comprehensive performance are best.
Claims (6)
- A kind of 1. method that metering nozzle is prepared using plural gel stabilizing zirconia as matrix, it is characterised in that including by aggregate, Through being kneaded, after ageing mixture shaping, firing obtains metering nozzle to pulverized powder with bonding agent altogether；The aggregate is magnesia partial stabilized zirconia, and pulverized powder is to mix plural gel and monoclinic zirconia micro mist altogether Afterwards, dry to grind obtained powder altogether, plural gel includes magnesium hydroxide gels and calcium hydroxide gel；Monoclinic zirconia micro mist chemistry percentage by weight forms：ZrO2+HfO2＞ 99%, SiO2＜ 0.45%；Monoclinic zirconia The granularmetric composition of micro mist is：d50=0.8~0.9 μm, d904.0 μm of ＜；Magnesia solid concentration in magnesium hydroxide gels is 20 ~40g/L, calcium oxide solid concentration is 28~56g/L in calcium hydroxide gel；Monoclinic zirconia micro mist：Magnesia solid phase proportion is 97.0~97.5 in magnesium hydroxide gels：2.5~3.0；Hydroxide Calcium oxide solid phase in calcium gel：Siliconoxide mass ratio is 2 in monoclinic zirconia micro mist:1, by calcium hydroxide gel, magnesium hydroxide Gel and monoclinic zirconia micro mist mix after, the dry obtained powder that grind altogether be common pulverized powder.
- 2. preparing the method for metering nozzle using plural gel stabilizing zirconia as matrix as claimed in claim 1, its feature exists In the particle diameter of pulverized powder is d altogether904.0 μm of ＜.
- 3. the method for metering nozzle is prepared using plural gel stabilizing zirconia as matrix as claimed in claim 1 or 2, its feature It is, is 45 according to the mass ratio of aggregate and monoclinic zirconia micro mist:55 by aggregate pulverized powder dispensing together, by mass percentage Meter, the addition of bonding agent for aggregate together pulverized powder total amount 8%.
- 4. preparing the method for metering nozzle using plural gel stabilizing zirconia as matrix as claimed in claim 3, its feature exists In the chemical composition of magnesia partial stabilized zirconia aggregate is (wt%)：ZrO2=95.12, HfO2=2.14, MgO= 2.69, CaO=0.02, Al2O3=0.03.
- 5. the method for metering nozzle is prepared using plural gel stabilizing zirconia as matrix as claimed in claim 1 or 2, its feature It is, the firing temperature is 1700~1710 DEG C.
- 6. the method for metering nozzle is prepared using plural gel stabilizing zirconia as matrix as claimed in claim 1 or 2, its feature It is,The preparation of the magnesium hydroxide gels includes：By MgCl2·6H2O is configured to the mother liquor that concentration is 0.5~1.0mol/L, adds the dispersant of mother liquor gross weight 1.2%, The pH value for the mother liquor for adding dispersant is adjusted to 7~10 afterwards and obtains gel, then is incited somebody to action after obtained gel is aged 8~16h Cl in gel-Removal obtains the magnesium hydroxide gels；The preparation of the calcium hydroxide gel includes：By CaCl2·6H2O is configured to the mother liquor that concentration is 0.5~1.0mol/L, adds the dispersant of mother liquor gross weight 1.2%, The pH value for the mother liquor for adding dispersant is adjusted to 7~10 afterwards and obtains gel, then is incited somebody to action after obtained gel is aged 8~16h Cl in gel-Removal obtains the calcium hydroxide gel.
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| CN201510941285.3A Expired - Fee Related CN105503208B (en) | 2015-12-15 | 2015-12-15 | A kind of method that metering nozzle is prepared using plural gel stabilizing zirconia as matrix |
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| CN114956799A (en) * | 2022-08-02 | 2022-08-30 | 佛山市道易生科技有限公司 | Dry-method powder-making ceramic tile/board and preparation method thereof |
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| CN102241522A (en) * | 2010-05-13 | 2011-11-16 | 郑州振中电熔锆业有限公司 | Electrofusion manufacture method of magnesium stabilized zirconia |
| CN103979980A (en) * | 2014-05-07 | 2014-08-13 | 西安建筑科技大学 | Preparation method of zirconia metering nozzle |
| CN104876596A (en) * | 2015-04-21 | 2015-09-02 | 西安建筑科技大学 | Preparation method and equipment of zirconia metering nozzle |
| CN104876595A (en) * | 2015-04-21 | 2015-09-02 | 西安建筑科技大学 | Method and equipment for preparing zirconia metering nozzle employing magnesium oxide nano powder |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102241522A (en) * | 2010-05-13 | 2011-11-16 | 郑州振中电熔锆业有限公司 | Electrofusion manufacture method of magnesium stabilized zirconia |
| CN103979980A (en) * | 2014-05-07 | 2014-08-13 | 西安建筑科技大学 | Preparation method of zirconia metering nozzle |
| CN104876596A (en) * | 2015-04-21 | 2015-09-02 | 西安建筑科技大学 | Preparation method and equipment of zirconia metering nozzle |
| CN104876595A (en) * | 2015-04-21 | 2015-09-02 | 西安建筑科技大学 | Method and equipment for preparing zirconia metering nozzle employing magnesium oxide nano powder |
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| Study on Wearing Mechanism of Zirconia Non-swirl Nozzle;LI Xiang.etal.;《硅酸盐通报》;20121231;第31卷(第6期);1523-1528 * |
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