CN103936285B - A kind of production method of high-strength wearable complex phase polycrystalline project plate - Google Patents
A kind of production method of high-strength wearable complex phase polycrystalline project plate Download PDFInfo
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Abstract
The production method of a kind of high-strength wearable complex phase polycrystalline project plate, relates to artificial stone or the production technical field of part engineering material.By hot melt after calcium base waste material, auxiliary material, fining agent of fluxing mixing, homogenized, clarification after formed high-temperature fusant, high-temperature fusant is passed through calendering or cast or basis amorphous plate or pellet are made in shrend, then through Crystallizing treatment, form high-strength wearable complex phase polycrystalline project plate.The invention comprehensively utilizes solid waste, physical and mechanical property is good, processing characteristics is excellent to provide one, can substitute for lithotome or part engineering, and physical and mechanical property and chemical stability are better than the high-strength wearable complex phase polycrystalline project plate of lithotome or part engineering material, can be widely applied to the fields such as chemical industry, metallurgy, building decoration, oil.
Description
Technical field
The present invention relates to a kind of artificial stone or the production technical field of part engineering material, be directed to chemical industry, metallurgy, build
Build the technical fields such as decoration, oil.
Background technology
At building field, lithotome, as a kind of non-renewable resources, more needs special concern.China's nonmetallic minerals money
Source reserves are placed in the middle in world rankings, that is be not very non-lipid.It is very long that lithotome generates the age, belongs to non-renewable money
Source.But being as nation-building and each side demand increases, the use of lithotome is the most universal.Especially at building decoration
Aspect, thus efficiently, reasonably comprehensively utilize, can be that country saves more valuable natural resources and is beneficial to improve ecological ring
Border.At present, domestic stone mining and processing enterprise, often it is merely observed that into waste rate, volume recovery and processing technology etc., and seldom close
The comprehensive utilization of note lithotome.Some is engaged in material mine exploitation, the personnel producing, processing, construct, and even includes building industry
Interior design engineer, the utilization to lithotome leftover bits and pieces is paid little attention at all, is typically only considered as waste.Lithotome
Having about 50% to become non-specification rubble and rubble in recovery process, calculate with regard to national existing rough stone block yield, this is
One considerable numeral, if can make full use of, existing economic interests, can economize on resources again.Mistake at processing lithotome
Cheng Zhong, it will produce and be about famine material 5%, the tailing of hair plates total amount about 1/3.If abandoned as waste material, Hai get Fu
Go out economic cost to transport, stack and improper also hinder environmental protection.Each procedure of processing of stone factory (saw, grind, cut), all produces
Barren rock is starched, if carelessly discharging, quite pollutes environment.
Therefore, reduce lithotome loss in exploitation and process, except active adoption new technology, new technology, new
Equipment improves outside technical merit and the quality of operator, the most important comprehensive utilization being exactly to develop further lithotome,
Turn waste into wealth, turn bane into boon.On the other hand, some important equipments and critical component in chemical industry, oil, electric power, metallurgy industry
Often being faced with high temperature, rapidly difference variation, high corrosion, high abrasion, medium meets water, and to burst thump etc. a series of the harshest
Working environment.And the products such as the marble applied in the market, cast stone, cast iron, manganese steel are due to the various elder generations of self material
Nature defect so that it is be the most all difficult in adapt to above-mentioned working environment.
Summary of the invention
Present invention aim at comprehensively utilize solid waste provide intensity high, wear-resistant, anticorrosive, to human body without radiation
Property harm the production method of complex phase polycrystalline engineering material.
Technical solution of the present invention has two kinds:
The first is: by calcium base waste material, auxiliary material, flux fining agent and water mix after put into melting furnaces, homogenized,
Form high-temperature fusant after clarification, then high-temperature fusant is made basis amorphous plate through calendering or cast, basis amorphous plate is passed through
Crystallizing treatment forms complex phase polycrystalline project plate blank flat；Described calcium base waste material is lime stone waste material or marble wastes or calcite
Waste material；Described auxiliary material is quartz sand or silica or soda ash or aluminum oxide or zinc oxide or brium carbonate or potassium carbonate or magnesia
Or at least four material in fluorite or sodium nitrate；Described fining agent of fluxing is CeO2、Na2O、Al2O3、SiO2、CaO、Li2O、
NH4NO3、NaNO3Or Na2SO4In at least any one.
The second is: by calcium base waste material, auxiliary material, flux fining agent and water mix after put into melting furnaces, homogenized,
Form high-temperature fusant after clarification, then high-temperature fusant is made amorphous state pellet through shrend, by amorphous state pellet through sinter
Chemical conversion complex phase polycrystalline project plate blank flat；Described calcium base waste material is lime stone waste material or marble wastes or calcite waste material；Institute
Stating auxiliary material is quartz sand or silica or soda ash or aluminum oxide or zinc oxide or brium carbonate or potassium carbonate or magnesia or fluorite
Or at least four material in sodium nitrate；Described fining agent of fluxing is CeO2、Na2O、Al2O3、SiO2、CaO、Li2O、NH4NO3、
NaNO3Or Na2SO4In at least any one.
Both the above method of the present invention all produces the high-strength wearable complex phase polycrystalline work of high added value with calcium base waste material for raw material
Journey plate, after complex phase polycrystalline project plate blank flat is come out of the stove, uses above method can make the building dress of different colours and specification
Decoratice board, have uniqueness high temperature abrasion resistance, strongly high temperature resistance impact, resistance to strong corrosion, resist burst the performances such as impact, be fabricated to
Water slag groove liner, abrasion-proof pipe goods, distributor chute and various abrasion-proof backing block, can be widely applied to coal, iron and steel, ore dressing,
The industries such as electric power.The product made carries out determining thickness, corase grind, fine polishing, cutting, chamfered edge, obtains different specification size and glossiness
Finished product.
Compared with existing Ordinary microcrystalline plate, the method have the advantages that
1, high intensity, wear-resistant, excellent physical and mechanical property and chemical stability:
The physical and mechanical property of the complex phase polycrystalline project plate of the present invention is excellent, density 2.5-2.8g/cm3, Mohs' hardness 6-
8, rupture strength 30.0-103.5MPa, compression strength 70.0-903.0MPa, wearability 0.063-0.15g/cm2。
2, in institutional framework, crystallite dimension is little, crystalline content is high:
The institutional framework of the calcium base waste material complex phase polycrystalline engineering material of the present invention is made up of glass phase and crystalline phase, wherein crystalline phase
By cuspidine, cacoclasite, wollastonite, fluorine alkali wollastonite, akermanite, alkali wollastonite, forsterite, diopside, not
Carry out one or more crystal composition in stone, leucite, quartz, there is fabulous high-strength wearable, simultaneously by adjusting
Crystalline content (crystallization rate) in processing parameter regulation and control complex phase polycrystalline material and crystallite dimension, also make in calcium base waste material simultaneously
Trace element play in terms of regulation and control crystallization rate, crystallite dimension and complex phase polycrystalline material physical and mechanical property and chemical stability
Crucial effect.
3, high-valued comprehensive utilization calcium base waste material:
It is possible not only to reduce the production cost of complex phase polycrystalline material, it is also possible to alleviate the solid waste pollution to environment.
Heretofore described calcium base waste material account for calcium base waste material, auxiliary material, flux fining agent and the 10.0 of water gross mass～
25.0wt%, auxiliary material accounts for calcium base waste material, auxiliary material, flux fining agent and the 65.0-73.0wt% of water gross mass, fluxes
Fining agent accounts for calcium base waste material, auxiliary material, fining agent and the 2.0 of water gross mass～10.0wt% of fluxing.
CeO in heretofore described fining agent of fluxing2、Na2O、Al2O3、SiO2、CaO、Li2O、NH4NO3、NaNO3With
Na2SO4Mass ratio be 0～5 0～28 0～6 0～10 0～11 0～4 1～5 0～7 0～13.
In heretofore described calcium base waste material, CaO accounts for the 45.0～55% of calcium base waste material gross mass, SiO2Account for calcium base waste material total
The 0.01～1.5% of quality, Al2O3Accounting for the 0.01～2.0% of calcium base waste material gross mass, MgO accounts for the 0.01 of calcium base waste material gross mass
～2.0%, Fe2O3Account for the 0.01～2.0% of calcium base waste material gross mass.
Quartz sand, silica, soda ash, aluminum oxide, zinc oxide, brium carbonate, potassium carbonate, oxygen in heretofore described auxiliary material
Change magnesium, the mass ratio of fluorite and sodium nitrate be 40～98 8～35 0～5 0～4 0～5 5～17 0～7 7～14 0～
17。
It addition, the particle diameter of calcium base waste material of the present invention and auxiliary material is less than 2mm.
The temperature of described melting furnaces is 1400～1560 DEG C (preferably 1420～1520 DEG C), and the fusing time in melting furnaces is
1.0～10.0h(preferably 2.0～8.0h).
The high-temperature fusant that temperature is 1100～1200 DEG C can be made amorphous state soleplate by rolling roll calendar.
Amorphous state soleplate also can be further broken up into amorphous state shivering material.
Also the high-temperature fusant that temperature is 1250～1350 DEG C can be poured into preheated die for molding, obtain amorphous state
Soleplate.
Also can make the amorphous state basis grain of different-grain diameter by high-temperature fusant that temperature is 1300～1350 DEG C through shrend
Material, is dried, treats die-filling use after classification.
The method of crystallization has two kinds:
One is: by amorphous state soleplate through 400～650 DEG C of annealing 2.0～8.0h, then then at 650～950 DEG C of crystallization
1.0～9.0h, finally then at 25～600 DEG C of annealing 2.0～8.0h.
Two are: by after die-filling for amorphous state basis pellet in shuttle kiln, with the speed of 5～20 DEG C/min be warming up to 1050～
1180 DEG C, insulation 0～2.5h shakeouts surface, is then down to 600～950 DEG C with the speed of 3～15 DEG C/min, insulation 1.0～
4.0h Crystallizing treatment, is cooled to 200～700 DEG C with the speed of 2～10 DEG C/min the most again, insulation 1.0～8.0h annealing, system
Become complex phase polycrystalline project plate blank flat.
Detailed description of the invention
Specifically describing the present invention with embodiment below, the present invention should not be limited by the examples.
In following example: in calcium base waste material, CaO accounts for the 45.0～55% of calcium base waste material gross mass, SiO2Account for calcium base waste material
The 0.01～1.5% of gross mass, Al2O3Accounting for the 0.01～2.0% of calcium base waste material gross mass, MgO accounts for calcium base waste material gross mass
0.01～2.0%, Fe2O3Account for the 0.01～2.0% of calcium base waste material gross mass.
Embodiment 1:
Calcium base waste material and various mineral auxiliary material are pulverized, then cross 40 mesh sieves, weigh 10.0～25.0 kilograms of calcium base waste materials,
50.0～67.0 kilograms of quartz sands or Cab-O-sil (SiO2), 8.0～14.0 kilograms of soda ash (Na2CO3), 0.0-4.0 kg of alumina
(Al2O3), 0～3.0 kilogram of zinc oxide (ZnO), 9.0～16.0 kg of potassium carbonate (K2CO3), 9.0～15.0 kilograms of fluorites
(CaF2), 3.0～5.0 kilograms of sodium nitrate (NaNO3), 1.0～3.0 kilograms of ammonium nitrate (NH4NO3).By calcium base waste material, assist former
Material and fining agent of fluxing are sufficiently mixed, and add the water of raw material gross weight 4.0% in mixed process, and stirring 10min mixing is all
Even, basis of formation batch.
Sending in melting furnaces by basis batch through conveyer belt or unit batch can, fusion temperature controls to melt at 1460～1490 DEG C
Changing 2.0～6.0h, qualified high-temperature fusant is made in homogenized, clarification.The high-temperature fusant of clarification enters melting furnaces work through dog-hole
Portion, temperature is down to 1120～1180 DEG C, and high-temperature fusant is by pressing roll calendar (calendering formation speed 12.0～25.0m/h)
Make basis amorphous plate.
The basic amorphous plate shaped enters roller kilns, initially enters basis amorphous plate plate annealing warm area, at 450～650 DEG C
In warm area, basis amorphous plate plate annealing 2.0～3.0h, subsequently into 650～850 DEG C of warm areas, crystallization 5.0～7.0h, finally enters
600～25 DEG C of warm areas, complex phase polycrystalline project plate annealing 4.0～6.0h.
After high-strength wearable complex phase polycrystalline project plate blank flat is come out of the stove, carry out determining thickness, corase grind, fine polishing to it, cut, fall
Rib, obtains the finished product of different specification size and glossiness.
Embodiment 2
Calcium base waste material and various mineral auxiliary material are pulverized, then cross 40 mesh sieves, weigh 10.0～25.0 kilograms of calcium base waste materials,
50.0～67.0 kilograms of quartz sands or Cab-O-sil (SiO2), 8.0～14.0 kilograms of soda ash (Na2CO3), 0.0-4.0 kg of alumina
(Al2O3), 0～3.0 kilogram of zinc oxide (ZnO), 9.0～16.0 kg of potassium carbonate (K2CO3), 9.0～15.0 kilograms of fluorites
(CaF2), 3.0～5.0 kilograms of sodium nitrate (NaNO3), 1.0～3.0 kilograms of ammonium nitrate (NH4NO3).By calcium base waste material, assist former
Material and fining agent of fluxing are sufficiently mixed, and add raw material gross weight 3.0～the water of 4.0%, and stirring 10～15min mixes, shape
Become basis batch.
Sending in melting furnaces by basis batch through conveyer belt or unit batch can, fusion temperature controls to melt at 1470～1530 DEG C
Changing 2.0～6.0h, qualified high-temperature fusant is made in homogenized, clarification.The high-temperature fusant of clarification enters melting furnaces work through dog-hole
Portion, temperature is down to 1250-1300 DEG C, and high-temperature fusant is poured into preheated die for molding, obtains basic non-crystal block.
The non-crystal block in basis of castable is sent in shuttle kiln or tunnel cave or roller kilns, with 5 DEG C/min in shuttle kiln
Speed be warming up to 650～950 DEG C insulation 6.0h crystallization, be then cooled to 200～700 DEG C of insulations with the speed of 3 DEG C/min
6.0h anneals, and eliminates the various stress that complex phase polycrystalline project plate produces in heat treatment process, cools down with stove.
After high-strength wearable complex phase polycrystalline project plate blank flat is come out of the stove, carry out determining thickness, corase grind, fine polishing to it, cut, fall
Rib, obtains the finished product of different specification size and glossiness.
Embodiment 3
Calcium base waste material and various mineral auxiliary material are pulverized, then cross 40 mesh sieves, weigh 10.0～25.0 kilograms of calcium base waste materials,
50.0～67.0 kilograms of quartz sands or Cab-O-sil (SiO2), 8.0～14.0 kilograms of soda ash (Na2CO3), 0.0～4.0 kilogram of oxidation
Aluminium (Al2O3), 0～3.0 kilogram of zinc oxide (ZnO), 9.0～16.0 kg of potassium carbonate (K2CO3), 9.0～15.0 kilograms of fluorites
(CaF2), 3.0～5.0 kilograms of sodium nitrate (NaNO3), 1.0～3.0 kilograms of ammonium nitrate (NH4NO3).By calcium base waste material, assist former
Material and fining agent of fluxing are sufficiently mixed, and add raw material gross weight 3.0～the water of 4.0%, and stirring 10～15min mixes, shape
Become basis batch.
Sending in melting furnaces by basis batch through conveyer belt or unit batch can, fusion temperature controls to melt at 1470～1530 DEG C
Changing 2.0～6.0h, qualified high-temperature fusant is made in homogenized, clarification.The high-temperature fusant of clarification enters melting furnaces work through dog-hole
Portion, temperature is down to 1320～1350 DEG C (to ensure the epigranular of shrend amorphous particle), through stream material mouth or the hole shape stream of rising as high as the banks
Material mouth enters in circulating water chennel, and shrend becomes the basic amorphous pellet of different-grain diameter, is dried, treats die-filling use after classification.
The basic amorphous pellet that shrend becomes according to different granularity layerings die-filling after send into shuttle kiln, or basis amorphous plate breaks
The different broken amorphous block of the size that is broken into according to different size layering die-filling after send into shuttle kiln, with 5～20 DEG C/
The speed of min is warming up to 1130～1190 DEG C of insulations and 0.5～1.5h shakeouts surface, then with the speed of 5 DEG C/min be down to 600～
970 DEG C of insulation 1.0～4.0h Crystallizing treatment, lower the temperature with the speed of 3 DEG C/min and move back at 200～700 DEG C of insulation 7.0h
Fire, makes big-pattern type or little pattern type complex phase polycrystalline project plate blank flat.
After high-strength wearable complex phase polycrystalline project plate blank flat is come out of the stove, carry out determining thickness, corase grind, fine polishing to it, cut, fall
Rib, obtains the finished product of different specification size and glossiness.
Claims (9)
1. the production method of a high-strength wearable complex phase polycrystalline project plate, it is characterised in that by calcium base waste material, auxiliary material, flux
Fining agent and water mix after put into melting furnaces, homogenized, clarification after formed high-temperature fusant, then by high-temperature fusant through calendering or
Basis amorphous plate is made in cast, and through Crystallizing treatment, basis amorphous plate is formed complex phase polycrystalline project plate blank flat；Described calcium base
Waste material is lime stone waste material or marble wastes or calcite waste material；Described auxiliary material is quartz sand or silica, soda ash, oxidation
At least four material in aluminium, zinc oxide, brium carbonate, potassium carbonate, magnesia, fluorite, sodium nitrate；Described fining agent of fluxing is
CeO2、Na2O、Al2O3、SiO2、CaO、Li2O、NH4NO3、NaNO3Or Na2SO4In at least any one；
Described calcium base waste material accounts for calcium base waste material, auxiliary material, fining agent and the 10.0 of water gross mass～25.0wt% of fluxing, auxiliary
Raw material accounts for calcium base waste material, auxiliary material, flux fining agent and the 65.0-73.0wt% of water gross mass, and fining agent of fluxing accounts for calcium base
Waste material, auxiliary material, fining agent and the 2.0 of water gross mass～10.0wt% of fluxing；
CeO in described fining agent of fluxing2、Na2O、Al2O3、SiO2、CaO、Li2O、NH4NO3、NaNO3And Na2SO4Mass ratio be 0
～5 0～28 0～6 0～10 0～11 0～4 1～5 0～7 0～13；
In described calcium base waste material, CaO accounts for the 45.0～55% of calcium base waste material gross mass, SiO2Account for calcium base waste material gross mass 0.01～
1.5%, Al2O3Accounting for the 0.01～2.0% of calcium base waste material gross mass, MgO accounts for the 0.01～2.0% of calcium base waste material gross mass, Fe2O3
Account for the 0.01～2.0% of calcium base waste material gross mass；
Quartz sand or silica in described auxiliary material, soda ash, aluminum oxide, zinc oxide, brium carbonate, potassium carbonate, magnesia, fluorite and
The mass ratio of sodium nitrate is 40～98 8～35 0～5 0～4 0～5 5～17 0～7 7～14 0～17.
2. the production method of a high-strength wearable complex phase polycrystalline project plate, it is characterised in that by calcium base waste material, auxiliary material, flux
Fining agent and water put into melting furnaces after mixing, form high-temperature fusant, then by high-temperature fusant through shrend system after homogenized, clarification
Become amorphous state pellet, amorphous state pellet is melted into complex phase polycrystalline project plate blank flat through sinter；Described calcium base waste material is stone
Lime stone waste material or marble wastes or calcite waste material；Described auxiliary material is quartz sand or silica, soda ash, aluminum oxide, oxidation
At least four material in zinc, brium carbonate, potassium carbonate, magnesia, fluorite, sodium nitrate；Described fining agent of fluxing is CeO2、Na2O、
Al2O3、SiO2、CaO、Li2O、NH4NO3、NaNO3Or Na2SO4In at least any one；
Described calcium base waste material accounts for calcium base waste material, auxiliary material, fining agent and the 10.0 of water gross mass～25.0wt% of fluxing, auxiliary
Raw material accounts for calcium base waste material, auxiliary material, flux fining agent and the 65.0-73.0wt% of water gross mass, and fining agent of fluxing accounts for calcium base
Waste material, auxiliary material, fining agent and the 2.0 of water gross mass～10.0wt% of fluxing；
CeO in described fining agent of fluxing2、Na2O、Al2O3、SiO2、CaO、Li2O、NH4NO3、NaNO3And Na2SO4Mass ratio be 0
～5 0～28 0～6 0～10 0～11 0～4 1～5 0～7 0～13；
In described calcium base waste material, CaO accounts for the 45.0～55% of calcium base waste material gross mass, SiO2Account for calcium base waste material gross mass 0.01～
1.5%, Al2O3Accounting for the 0.01～2.0% of calcium base waste material gross mass, MgO accounts for the 0.01～2.0% of calcium base waste material gross mass, Fe2O3
Account for the 0.01～2.0% of calcium base waste material gross mass；
Quartz sand or silica in described auxiliary material, soda ash, aluminum oxide, zinc oxide, brium carbonate, potassium carbonate, magnesia, fluorite and
The mass ratio of sodium nitrate is 40～98 8～35 0～5 0～4 0～5 5～17 0～7 7～14 0～17.
Production method the most according to claim 1 or claim 2, it is characterised in that the particle diameter of described calcium base waste material and auxiliary material is less than
2mm。
Production method the most according to claim 1 or claim 2, it is characterised in that the temperature of described melting furnaces is 1400～1560 DEG C,
Fusing time in melting furnaces is 1.0-10.0h.
Production method the most according to claim 1, it is characterised in that the high-temperature fusant that temperature is 1100～1200 DEG C is passed through
Basis amorphous plate is made in roll calendar calendering.
Production method the most according to claim 1, it is characterised in that by the high-temperature fusant cast that temperature is 1250～1350 DEG C
To preheated die for molding, obtain basis amorphous plate.
Production method the most according to claim 2, it is characterised in that the high-temperature fusant that temperature is 1300～1350 DEG C is passed through
Shrend, makes the amorphous state pellet of different-grain diameter, is dried, treats die-filling use after classification.
8. according to production method described in claim 5 or 6, it is characterised in that by basis amorphous plate through 400～650 DEG C of annealing 2.0
～8.0h, then then at 650～950 DEG C of crystallization 1.0～9.0h, finally then at 25～600 DEG C of annealing 2.0～8.0h.
Production method the most according to claim 7, it is characterised in that by after die-filling for amorphous state pellet in shuttle kiln, with 5～
The speed of 20 DEG C/min is warming up to 1050～1180 DEG C, and insulation 0～2.5h shakeouts surface, then with the speed of 3～15 DEG C/min
It is down to 600～950 DEG C, is incubated 1.0～4.0h Crystallizing treatment, is cooled to 200～700 with the speed of 2～10 DEG C/min the most again
DEG C, insulation 1.0～8.0h annealing, make complex phase polycrystalline project plate blank flat.
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| CN102942303A (en) * | 2012-10-29 | 2013-02-27 | 中国科学院过程工程研究所 | High-strength wear-resistant engineering microcrystalline glass prepared by using granite waste materials and preparation method thereof |
| CN103539357A (en) * | 2013-08-27 | 2014-01-29 | 中国科学院过程工程研究所 | Silicon-slag microcrystalline glass and preparation method thereof |
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| CN102942303A (en) * | 2012-10-29 | 2013-02-27 | 中国科学院过程工程研究所 | High-strength wear-resistant engineering microcrystalline glass prepared by using granite waste materials and preparation method thereof |
| CN103539357A (en) * | 2013-08-27 | 2014-01-29 | 中国科学院过程工程研究所 | Silicon-slag microcrystalline glass and preparation method thereof |
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