CN1225079A - Ceramic compositions - Google Patents
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- CN1225079A CN1225079A CN 97196168 CN97196168A CN1225079A CN 1225079 A CN1225079 A CN 1225079A CN 97196168 CN97196168 CN 97196168 CN 97196168 A CN97196168 A CN 97196168A CN 1225079 A CN1225079 A CN 1225079A
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Abstract
Ceramic compositions which are of particular value in the handling or casting of steel, for example as lining materials or for producing nozzles or shrouds used in continuous casting, comprise a mixture of particles of boron nitride, zirconium diboride and at least one other refractory material, bonded together by carbon produced by the decomposition of an organic binder such as a resin or pitch. The other refractory material may be for example a refractory metal, an oxide, a carbide, a boride or a nitride. Zirconium oxide containing compositions comprising 5-70% by weight boron nitride, 5-60% by weight zirconium diboride and 5-80% by weight of zirconium oxide are particularly suitable for forming at least that part of a nozzle which in use is at the slag line in a molten steel vessel. Aluminum oxide containing compositions comprising 5-70% by weight boron nitride, 15-50% by weight zirconium diboride and 10-70% by weight aluminum oxide are particularly suitable for forming the inside of nozzles as they resist alumina build up and prevent clogging of the nozzles.
Description
The present invention relates to ceramic composition, said composition has special value for the processing and the casting of refractory metal such as iron and steel.
Utilizing carbon paste to close pottery (also claiming the black refractory materials), to make the goods be used to handle and cast as class molten metals such as steel are well-known technology.The example of this based article is container such as hot metal ladle, the sprue gate of tundish and encirclement flows into the metal logistics of another container from a container the guard shield that is used to contain molten metal.This class carbon paste close pottery by graphite, a kind of or several formed as aluminum oxide, magnesium oxide and zirconic oxide compound and as the mixture of class caking agents such as resol or pitch, wherein caking agent closes by decomposition generation carbon paste.
Above-mentioned carbon paste closes pottery and has a series of shortcomings.The ability of its heat shock resistance, and be easy to break, so that need and will make its thermal shocking that when being heated to comparatively high temps very soon, produces drop to minimum degree such as products similars such as sprue gate, guard shields with handling someway.This class material also because it contains higher carbon, mainly is graphite form, and makes its oxidation resistance low.This class material also the other shortcoming can occur in concrete the application.When for example molten metal was immersed at the sprue gate, its outside surface was subject to be present in the etch of the slag of molten metal surface, when the cast aluminum Fully Killed Steel, makes the sprue gate vestibule be easy to obstruction owing to generate aluminum oxide.
Have been found that at present, the carbon paste of being made up of the mixture of boron nitride, zirconium diboride and another kind of at least refractory materials closes the equivalent material that stupalith is a particularly suitable, and it can replace common graphitiferous carbon paste to close pottery to make the goods of handling and casting as steel one class molten metal.
First feature of the present invention provides a kind of ceramic composition, and it contains the mixture that granular boron nitride, zirconium diboride and another kind of at least refractory materials are formed, and said composition is decomposed the carbon fork-like farm tool used in ancient China gummed that produces by organic adhesive.
This another kind refractory materials can be for example a kind of refractory metal, a kind of oxide compound, a kind of carbide, a kind of boride or a kind of nitride.
This refractory metal can be a boron for example.
The example of suitable refractory oxide comprises aluminum oxide, zirconium white, magnesium oxide, ytterbium oxide, calcium oxide, chromic oxide and silicon oxide.Can adopt more than one oxide compound, and this oxide compound can be a kind of blended refractory oxide, for example mullite.
The example of suitable carbonization thing comprises silicon carbide, norbide, aluminium carbide and zirconium carbide.Can adopt more than one carbide.
The example of suitable boride comprises TiB2 and six calcium borides, and the example of suitable nitride comprises silicon nitride, aluminium nitride, titanium nitride, zirconium nitride and aluminium nitride-aluminium oxide-silicon oxide stupalith.Can adopt more than one boride and more than one nitride.
According to a preferred embodiment of the invention, this ceramic composition contains boron nitride, zirconium diboride and zirconic mixture, and this ceramic composition preferably contains 5-70% (weight), more preferred 1 5-50% (weight) boron nitride, 5-60% (weight), more preferred 15-50% (weight) zirconium diboride and 5-80% (weight), more preferred 10-60% (weight) zirconium white.
According to another preferred embodiment of the present invention, this ceramic composition contains the mixture of a kind of boron nitride, zirconium diboride and aluminum oxide, and this ceramic composition preferably contains 5-70% (weight), more preferred 15-50% (weight) boron nitride, 5-60% (weight), more preferred 15-50% (weight) zirconium diboride, 10-70% (weight), more preferred 15-60% (weight) aluminum oxide.
In the above-listed embodiment, the ratio of each component of ceramic composition is not all to consider the percentage ratio of the ceramic composition gross weight that carbon paste closes.
Decomposition with the organic adhesive that produces gummed can be, for example a class resol such as phenolic varnish or soluble phenolic resin, urea-formaldehyde resin, melamine-formaldehyde resin, Resins, epoxy, furane resin or pitch.
The preferred resol of organic adhesive, and preferably this resin uses with liquid state.Can adopt particulate state resol, but must be with this resin dissolves in The suitable solvent, for example furfural makes resin mix with other component and generates ceramic composition.The amount of used liquid phenolic resin is generally the 5-25% of other total component, and preferred 10-15% (weight) makes after the ceramic composition, and said composition generally contains the 2-12% (weight) that accounts for ceramic composition, preferred 5% carbon, and carbon decomposes generation by resin.
Make the present invention's ceramic composition, at first the particle of mixed nitride boron, zirconium diboride and another kind of refractory material adds liquid resin and stirring, then up to particle and resin uniform mixing.Mixture may need heating, to reduce the content liquid of resin, makes this mixture be suitable for moulding.Mixture forming is the shape of the phase of giving then, the preferred method that adopts mixture isobar pressurization in suitable mould.After the moulding, type spare heated 1 hour down at about 150-300 ℃, made resin solidification and crosslinked, again about 700-1200 ℃ of heating down, made the resin pyrolysis produce carbon paste and closed.
Though, ceramic composition of the present invention can be used for other field, for example be used for fusing and handle glass, or be used to melt, handle and cast the lower metal of fusing point such as aluminium and alloy thereof, but composition of the present invention is specially adapted to processing and casts refractory metal such as iron or steel.
When being used for processing and cast steel one metalloid, three components of ceramic composition of the present invention are all given the composition special nature.Boron nitride make composition have molten steel or molten slag in the presence of do not soaked into, therefore be used in the composition at sprue gate and can prevent that the aluminum oxide that the sprue gate is generated from stopping up.In addition, boron nitride makes composition have the ability of heat shock resistance, and helps to make the composition resistance to oxidation.Zirconium diboride give anti scuffing ability and with boron nitride mutually specific energy sludge proof ability (can reach about 1250 ℃) under the higher temperature is arranged, and improve the ability of composition refractory slag etch.In preferred embodiments, aluminum oxide and zirconium white both have the ability of improving the anti-molten steel etch of composition.
In order to improve composition in the higher temperature oxidation resistance under 1400 ℃ according to appointment, should in composition, add the silicon carbide that accounts for composition 5-20% (weight) and/or TiB2 at least as the part of the 3rd infusibility material.
The present invention's ceramic composition is at the processing of steel and lagging material and sprue gate and the guard shield that the Application in Casting example is as continuous casting is used.Above-mentionedly contain the position that zirconic composition is suitable for making the sprue gate especially, this position is used in the surface of molten steel and floats on the interface between the slag on molten steel top.Salic composition above-mentioned is suitable for making the inside at sprue gate especially because it easily and aluminum oxide-graphite material laminate, the latter forms the rest part at sprue gate, and it can prevent the generation of aluminum oxide and the obstruction at sprue gate.Although can make whole sprue gate with these compositions when needing, preferably make position, aforesaid sprue gate with it.The then available common carbon paste in all the other positions at sprue gate closes the stupalith manufacturing, for example the aluminum oxide that closes with carbon paste and the mixture of graphite.
Following example is used to illustrate the present invention:
Example 1
Prepared a series of compositions are listed in table 1.The amount of each infusibility component represents that with the weight percentage of total amount liquid resinous amount is represented with the weight percentage of the total amount of infusibility component.
Table 1
The composition sequence number | BN | ?ZrB 2 | ?A1 2O 3 | ZrO 2 | ?SiC | Resin |
1 | ?20 | ?45 | ?35 | ?- | ?- | ?10 |
?2 | ?25 | ?40 | ?35 | ?- | ?- | ?13 |
?3 | ?30 | ?35 | ?35 | ?- | ?- | ?15 |
?4 | ?20 | ?35 | ?45 | ?- | ?- | ?10 |
?5 | ?30 | ?35 | ?30 | ?- | ?5 | ?15 |
?6 | ?15 | ?35 | ??- | ?50 | ?- | ?7 |
?7 | ?15 | ?25 | ??- | ?60 | ?- | ?7 |
?8 | ?50 | ?35 | ??- | ?15 | ?- | ?20 |
According to the present invention, if the preparation of ceramic composition is at first granular silicon nitride, particulate state zirconium diboride to be had also granular aluminum oxide, zirconium white and silicon carbide to be put into strong mixing tank and mix, add liquid phenolic resin then, remix is until particulate matter and resin uniform mixing.
Boron nitride is the infusibility level, and it contains 7% (weight) oxygen, and granularity is less than 10 microns, and the granularity of zirconium diboride is less than 45 microns.The particle of aluminum oxide and zirconium white be 50% (weight) less than 500 microns, 50% (weight) is less than 53 microns.The granularity of silicon carbide is less than 150 microns.
Resin is the liquefied phenol Novolac, and solids content is 60% (weight).
With particle and liquid resinous mixture heating up,, make mixture be suitable for moulding to reduce the content liquid of resin.Then mixture is placed mould to become sample with cold isobar pressurization.Take out from mould after the sample moulding, heating made resin solidification and crosslinked in 1 hour under 200 ℃.At last sample is heated down at 900 ℃, make the resin pyrolysis produce carbon paste and close.
Example 2
Composition in the example 11,2,3 and 4 is immersed in 1650 ℃ the molten steel, measures its erosion rate, estimating the ability of its anti-molten steel, and close aluminum oxide-graphite material with common carbon paste and compare.
Suppress diameter 50mm by example 1 described method equipressure, the rod of length 300mm is accurately measured its diameter.Rod use clamp clamps, immerses in the molten steel in the induction furnace 1 hour, measures excellent diameter during off-test again.
Gained the results are shown in table 2
Table 2
The composition sequence number | Erosion rate (during mm/) |
?1 | ?0.3 |
?2 | ?0.2 |
?3 | ?0.1 |
?4 | ?0.6 |
Aluminum oxide/graphite | ?2 |
Example 3
Composition 6,7 and 8 in the example 1 is immersed in 1580 ℃ the slag, measures its erosion rate, estimating the ability of its refractory slag, and closes zirconium white-graphite material with carbon paste and compares.
By the rod of the described method preparation of example 1, accurately measure its diameter with example 2 same sizes.Borosilicate glass are sprayed at molten steel surface in the induction furnace, and make it generate slag.With anchor clamps rod is clamped then, immersed in the molten steel 1 hour.Measure the diameter of the rod in the zone that contacts with slag during off-test again.
Gained the results are shown in table 3
Table 3
The composition sequence number | Erosion rate (during mm/) |
?6 | ?2 |
?7 | ?2.5 |
?8 | ?0.5 |
Zirconium white/graphite | 4 |
Example 4
All 8 compositions are in 1200 ℃ of following different times rate of oxidation at interval, to estimate its oxidation resistance in the measurement example 1.
The garden sheet sample for preparing diameter 30mm, height 10mm by example 1 described method.The weighing sample also puts it in the electric furnace, takes out, cools off weighing again through different time.
The result changes mg/cm with sample weight
2In/time, represented, is shown in table 4.
Table 4
The composition sequence number | 2 hours | 26 hours | 130 hours |
?1 | ????0.97 | -0.14 | ?0.0001 |
?2 | ????2.77 | -0.37 | -0.00005 |
?3 | ????1.74 | -0.60 | -0.00002 |
?4 | ????5.54 | ?2.97 | -0.0015 |
?5 | ????0.63 | ?0.20 | ?0.00001 |
?6 | ????15.10 | ?1.89 | ?0.00025 |
?7 | ????10.73 | ?1.69 | ?0.00008 |
?8 | ????0.54 | ?0.29 | ?0.00003 |
As shown in table 4, rate of oxidation sharply descends in time, in fact reaches zero after 130 hours.The lazy attitude oxidative phenomena of this available set compound intrinsic is explained.
Example 5
With composition 1 and 3 make pouring molten steels the sprue gate internal surface of process, estimate the ability that it suppresses the obstruction that caused by the aluminum oxide accumulation, and close aluminum oxide-graphite material with common carbon paste and compare.
The tubulose sprue gate for preparing external diameter 50mm, internal diameter 15mm, length 300mm by example 1 described method.It is in the steel with the full deoxidation of aluminium of 0.2% (weight) that aluminium content is immersed at this sprue gate.Immerse after the sprue gate, oxygen blast in steel is ceaselessly shaken the sprue gate oxygen distribution is opened.Finish test after 30 minutes, take out the sprue gate, again it is cut open, check the aluminum oxide accumulation.
Aluminum oxide-graphite material tamper is serious.Composition 3 is not seen tamper, and composition 1 has certain tamper, but significantly is better than aluminum oxide-graphite material.
Example 6
Prepare four kinds of compositions by example 1 described method, be listed in table 5.Used boron nitride, zirconium diboride, aluminum oxide and zirconium white are used identical with example 1.TiB2, boron and six calcium borides are granularity less than 50 microns powder.Magnesian granularity is the 53-500 micron.The method for expressing of each group component is with example 1.
Table 5
Component | Composition 9 | Composition 10 | Composition 11 | Composition 12 |
?BN | ?40 | ?20 | ?10 | ?40 |
?ZrB 2 | ?35 | ?30 | ?35 | ?30 |
?TiB 2 | ?15 | ?15 | ?10 | ?15 |
?B | ?10 | ?10 | ?- | ?- |
?Al 2O 3 | ??- | ?20 | ?10 | ?- |
?ZrO 2 | ??- | ?- | ?- | ?15 |
?CaB 6 | ??- | ?5 | ?- | ?- |
?MgO | ??- | ?- | ?35 | ?- |
Resin | ?18 | ?15 | ?15 | ?20 |
By the described method test of example 3 and estimated the ability of its refractory slag, by the described method test of example 4 and estimated its sludge proof ability.
Gained the results are shown in table 6.The result of resistance to oxidation test changes mg/cm with sample weight
2In/time, represented.
Table 6
The composition sequence number | Erosion rate (during mm/) | 2 hours | 26 hours | 130 hours |
??9 | ?0.4 | ?0.3 | ?0.2 | ?0 |
?10 | ?0.8 | ?0.4 | ?0.3 | ?0 |
?11 | ?0.7 | ?20 | ?4 | ?0.01 |
?12 | ?1 | ?0.4 | ?0.2 | ?0 |
Example 7
The mixture that has prepared following composition:
Boron nitride 20% (weight)
Zirconium diboride 20% (weight)
Zirconium dioxide 55% (weight)
Silicon carbide 5% (weight)
Four components are all as described in the example 1.
The mixture of this ceramic composition and the liquefied phenol Novolac mixed with resin that accounts for 6.5% (weight) of 4 ceramic composition gross weights, the solids content of this varnish is 60% as described in example 1.
Prepare the ceramic coupon of diameter 4cm, length 30cm by example 1 described method, accurately measure the diameter of rod.
The slag that will contain 7% (weight) fluorochemical be fused to remain on 1650 ℃, capacity be 250kg high-frequency induction furnace molten steel above.
Then with the rod clamp clamps, immersed in the molten steel 2 hours, estimate its heat shock resistance ability, molten steel and slag penetration level and in the rate of oxidation of slag/metal interface.Prepare the rod that similar carbon paste closes zirconium white-graphite material, and similarly test.Two types rod has enough good heat-resistant impact ability and the anti-ability that penetrates.But, aspect the erosion rate of rod on slag/metal interface of composition manufacturing of the present invention, be superior.Carbon paste closes zirconium white-graphite rod when the erosion rate of slag circle is 3.05mm/, and the erosion rate of the rod that composition of the present invention is made is only when the 0.95mm/.
Example 8
The mixture that has prepared following composition:
Boron nitride 25% (weight)
Zirconium diboride 20% (weight)
Aluminum oxide 55% (weight)
Three components are all as described in the example 1.
This ceramic composition mixture and the liquefied phenol Novolac mixed with resin that accounts for 7.5% (weight) of three ceramic composition gross weights, it is 60% as described in example 1 that the latter's solid contains heavy.
The ceramic coupon for preparing diameter 4cm, length 30cm by example 1 described method.
With anchor clamps rod is clamped then, the immersion capacity is containing in 0.05-0.1% (weight) the aluminium Fully Killed Steel in the high-frequency induction furnace of 250kg.Surperficial topped one deck rice husk (ricehusks) of molten steel, and for preventing the over oxidation of steel in the process of the test, the surface of adopting the argon shield steel.The temperature of molten steel is 1570-1580 ℃, and the immersion time is 2 hours.The similar coupon that closes aluminum oxide-graphite material preparation with carbon paste has carried out similar test.
During off-test, the aluminum oxide of going up accumulation by the prepared rod surface of composition of the present invention is starkly lower than with carbon paste and closes the prepared excellent lip-deep accumulation of aluminum oxide-graphite material.
Claims (15)
1. a ceramic composition is characterized in that, the granular mixture of said composition nitrogen boron, zirconium diboride and at least a other infusibility material, and the carbon paste that is produced by the organic adhesive decomposition lumps together.
2. the ceramic composition of claim 1 is characterized in that, the awkward molten metal of at least a infusibility material, oxide compound, carbide, boride or nitride.
3. the ceramic composition of claim 2 is characterized in that, this refractory metal is a boron.
4. the ceramic composition of claim 2 is characterized in that, this oxide compound is one or more of aluminum oxide, zirconium white, magnesium oxide, ytterbium oxide, calcium oxide, chromic oxide and silicon oxide.
5. the ceramic composition of claim 2 is characterized in that, this carbide is one or more of silicon carbide, norbide, aluminium carbide and zirconium carbide.
6. the ceramic composition of claim 2 is characterized in that, this boride is TiB2 and/or six calcium borides.
7. the ceramic composition of claim 2 is characterized in that, this nitride is one or more of silicon nitride, aluminium nitride, titanium nitride, zirconium nitride and aluminium nitride-aluminium oxide-silicon oxide stupalith.
8. the ceramic composition of claim 4 is characterized in that, not consider the gross weight of the ceramic composition that carbon paste closes, said composition contains 5-70% (weight) boron nitride, 5-60% (weight) zirconium diboride and 5-80% (weight) zirconium white.
9. the ceramic composition of claim 8 is characterized in that, said composition contains 1 5-50% (weight) boron nitride, 1 5-50% (weight) zirconium diboride and 10-60% (weight) zirconium white.
10. the ceramic composition of claim 4 is characterized in that, in the ceramic composition gross weight of not considering that carbon paste closes, said composition contains 5-70% (weight) boron nitride, 5-60% (weight) zirconium diboride and 10-70% (weight) aluminum oxide.
11. the ceramic composition of claim 10 is characterized in that, said composition contains 15-50% (weight) boron nitride, 15-50% (weight) zirconium diboride and 15-60% (weight) aluminum oxide.
12. the ceramic composition one of among the claim 1-11 is characterized in that this organic adhesive is novolac resin, soluble phenolic resin, urea-formaldehyde resin, melamine-formaldehyde resin, Resins, epoxy or pitch.
13. the ceramic composition one of among the claim 1-12 is characterized in that said composition contains 2-12% (weight) carbon, this carbon is decomposed by organic adhesive and produces.
14. the ceramic composition one of among the claim 1-13 is characterized in that, to other infusibility material of small part be silicon carbide and/or TiB2.
15. the ceramic composition of claim 14 is characterized in that, said composition contains 5-20% (weight) norbide and/or TiB2.
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CN 97196168 CN1225079A (en) | 1996-07-05 | 1997-06-24 | Ceramic compositions |
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GB9614188.2 | 1996-07-05 | ||
CN 97196168 CN1225079A (en) | 1996-07-05 | 1997-06-24 | Ceramic compositions |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101081735B (en) * | 2005-10-07 | 2013-03-13 | 苏舍美特科(美国)公司 | Optimized high temperature thermal heat barrier |
CN1922119B (en) * | 2004-02-20 | 2013-11-13 | 戴蒙得创新股份有限公司 | Sintered compact |
CN104058753A (en) * | 2013-03-21 | 2014-09-24 | 宝山钢铁股份有限公司 | Preparation method of zirconia zirconium diboride carbonaceous melt delivery tube |
CN102026937B (en) * | 2008-01-31 | 2015-02-25 | 德斯特奇公司 | Molding composition and method using same to form displacements for use in a metal casting process |
CN112341993A (en) * | 2020-11-23 | 2021-02-09 | 新乡市炬能耐材有限公司 | Production process of composite non-oxide grinding material with cross crystal structure |
CN113526960A (en) * | 2021-07-20 | 2021-10-22 | 宁波东联密封件有限公司 | Silicon carbide ceramic and hot isostatic pressing sintering process thereof |
-
1997
- 1997-06-24 CN CN 97196168 patent/CN1225079A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1922119B (en) * | 2004-02-20 | 2013-11-13 | 戴蒙得创新股份有限公司 | Sintered compact |
CN101081735B (en) * | 2005-10-07 | 2013-03-13 | 苏舍美特科(美国)公司 | Optimized high temperature thermal heat barrier |
CN102026937B (en) * | 2008-01-31 | 2015-02-25 | 德斯特奇公司 | Molding composition and method using same to form displacements for use in a metal casting process |
CN104058753A (en) * | 2013-03-21 | 2014-09-24 | 宝山钢铁股份有限公司 | Preparation method of zirconia zirconium diboride carbonaceous melt delivery tube |
CN104058753B (en) * | 2013-03-21 | 2016-03-02 | 宝山钢铁股份有限公司 | A kind of preparation method of zirconium white zirconium diboride carbonaceous catheter |
CN112341993A (en) * | 2020-11-23 | 2021-02-09 | 新乡市炬能耐材有限公司 | Production process of composite non-oxide grinding material with cross crystal structure |
CN112341993B (en) * | 2020-11-23 | 2021-10-29 | 新乡市炬能耐材有限公司 | Production process of composite non-oxide grinding material with cross crystal structure |
CN113526960A (en) * | 2021-07-20 | 2021-10-22 | 宁波东联密封件有限公司 | Silicon carbide ceramic and hot isostatic pressing sintering process thereof |
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