CN103553342B - Industrial protection glass-ceramic sheet material and preparation method thereof - Google Patents
Industrial protection glass-ceramic sheet material and preparation method thereof Download PDFInfo
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- CN103553342B CN103553342B CN201310467890.2A CN201310467890A CN103553342B CN 103553342 B CN103553342 B CN 103553342B CN 201310467890 A CN201310467890 A CN 201310467890A CN 103553342 B CN103553342 B CN 103553342B
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 44
- 239000011521 glass Substances 0.000 claims abstract description 32
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 30
- 238000002425 crystallisation Methods 0.000 claims abstract description 27
- 230000008025 crystallization Effects 0.000 claims abstract description 27
- 239000005357 flat glass Substances 0.000 claims abstract description 25
- 238000000137 annealing Methods 0.000 claims abstract description 20
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910004261 CaF 2 Inorganic materials 0.000 claims abstract description 14
- 150000007514 bases Chemical class 0.000 claims abstract description 13
- 238000003490 calendering Methods 0.000 claims abstract description 9
- 238000007493 shaping process Methods 0.000 claims abstract description 8
- 238000005520 cutting process Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052700 potassium Inorganic materials 0.000 claims description 23
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 18
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 claims description 12
- 230000007797 corrosion Effects 0.000 claims description 12
- 239000010436 fluorite Substances 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 239000004576 sand Substances 0.000 claims description 12
- 239000006004 Quartz sand Substances 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 238000010899 nucleation Methods 0.000 claims description 6
- 230000006911 nucleation Effects 0.000 claims description 6
- 239000011734 sodium Substances 0.000 description 27
- 239000003245 coal Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- -1 electric power Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910000617 Mangalloy Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000006132 parent glass Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
1), preparation raw material the invention discloses a kind of industrial protection glass-ceramic sheet material and preparation method thereof, preparation method comprises the following steps:: by CaO-MgO-Al
2o
3-SiO
2system requirement, makes the basic compound composition in raw material reach following weight percent: SiO
250 ~ 55%, MgO8 ~ 10%, CaO12 ~ 14%, Al
2o
38 ~ 10%, FeO3 ~ 5%, Na
2o+K
2o2 ~ 4%, CaF
26 ~ 8%, TiO
23%; 2), by raw material mix, through founding and homogenizing, obtain glass metal; 3), glass metal continuous calendering shaping, annealing; 4), sheet glass direct-on-line after annealing is sent into nucleus crystallization stove and carry out coring and Crystallizing treatment successively; 5), by the glass ceramic board cutting on line after coring and crystallization, be cooled to room temperature after, obtain industrial protection glass-ceramic sheet material.
Description
Technical field
The present invention relates to industrial protection field of material technology, particularly relate to a kind of wear-resistant, corrosion resistant glass-ceramic sheet material and preparation method thereof.
Background technology
The industry such as iron and steel, coal, electric power, chemical industry, papermaking, building materials is pillar industries of China, and the processes such as the starting material of these industries and the conveying of product, storage all need to protect relevant device and device.Such as, the blast furnace blending bunker, sintering silo, feeding machine, apparatus for making pearl ball etc. of steel industry; Under the waste bin of coal industry, medium bucket, scrapper conveyor, bucket elevator, chute, sieve, the inside such as funnel needs to increase one deck abrasion-proof backing block; The coal receiving bunker, coal bunker, storehouse, stokehold, dry coal grid, tippler, dragveyer, water treatment etc. of power industry; Chemical industry needs protection against corrosion ground, pump foundation etc.; The various feed bin inwall of cement producing line, pipeline etc. of building material industry; The vacuum water-absorbing panel, profiled sheeting, Wiper blade etc. of paper industry all need anti-wear component.Along with technology upgrading and the structural adjustment of China's pillar industries such as iron and steel, coal, electric power, chemical industry, papermaking, building materials, the process such as conveying, storage of high rigidity, corrodibility starting material and product proposes more harsh requirement to protective material, produces huge demand to industrial protection material.
Conventional protective material has the special material such as manganese steel, polymer, cast stone.Although manganese steel material intensity is high, good toughness, not corrosion-resistant; Macromolecular material erosion resistance, impact resistance is good, but wear-resisting, resistance to elevated temperatures is poor; Cast stone material is corrosion-resistant, wear resisting property good, but machining difficulty is large, and apparatus of load is large.Therefore, the more superior industrial protection material of over-all properties is urgently developed, to meet technology upgrading and the structural adjustment of the relevant industries such as iron and steel, coal, electric power, papermaking, building materials.The wear resistant corrosion resistant glass-ceramic sheet material of exploitation high technology content, high added value, it has pottery and glass dual property concurrently, and the protective material such as alternative existing manganese steel, polymer, cast stone, as industrial protection material.
The patent report of current existing wear-resisting, corrosion-resistant crystallizing glass sheet material is specific as follows:
1, patent CN102491641 discloses a kind of Wear-resistant crystallized glass plate and preparation method thereof, and it mainly adopts slag to be raw material, utilizes sintering process to prepare decoration wear-resistant glass-ceramics.
2, patent CN102826758 discloses industrial wear resistant corrosion resistant crystallizing glass sheet material and preparation method thereof, and it mainly adopts chromium slag, flyash, gold tailings to be raw material, utilizes fusion process to prepare Wear-resistant crystallized glass plate.
3, patent CN100528781C discloses a kind of devitrified glass prepared containing magnetite mine tailing, and the weight percent of its composition is: SiO
2be 55 ~ 65, Al
2o
3be 4 ~ 10, CaO be 10 ~ 20, MgO be 3 ~ 7, TiO
2be 4 ~ 7, Fe
2o
3be 4.0 ~ 9.5, ZrO2 be 0 ~ 1.5, K
2o-Na
2o is 4 ~ 9.
Although above-mentioned patent all informs the method preparing wear-resisting, corrosion-resistant microcrystal glass material, but all do not inform the thing phase composite of parent glass system and crystallite phase, also do not adopt continuous calendering moulding process aborning, and the performance of the microcrystal glass material of final preparation is also not enough to for industrial protection.In addition, the solid waste such as some and iron tailings, flyash, gold tailings, coal gangue, red mud are also had to be that raw material prepares the Patents of microcrystal glass material openly, these patents mainly to maximally utilise for the purpose of solid waste, can't more consideration Structure of Glass Ceramics, performance with and uses thereof.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of wear-resisting, corrosion resistant industrial protection glass-ceramic sheet material and preparation method thereof.
In order to solve the problems of the technologies described above, the invention provides a kind of industrial protection glass-ceramic sheet material, comprising the composition of following weight content:
SiO
250 ~ 55%, MgO8 ~ 10%, CaO12 ~ 14%, Al
2o
38 ~ 10%, FeO3 ~ 5%, Na
2o+K
2o2 ~ 4%, CaF
26 ~ 8% and TiO
23%.
The present invention also provides a kind of preparation method of industrial protection glass-ceramic sheet material simultaneously, comprises the following steps:
1), preparation raw material:
By CaO-MgO-Al
2o
3-SiO
2system requires (carrying out material composition coupling during batching), makes the basic compound composition in raw material reach following weight percent:
SiO
250～55%、MgO8～10%、CaO12～14%、Al
2O
38～10%、FeO3～5%、Na
2O+K
2O2～4%、CaF
26～8%，TiO
23%；
Remarks illustrate: at Na
2o+K
2o(and Na
2o and K
2the mixture of O composition) in, Na
2o, K
2o can mix this according to the proportion relation of any part by weight;
Select the mixture of iron tailings, rhombspar, quartz sand, potassium felspar sand, fluorite and titanium dioxide as raw material, make chemical composition contained in described raw material meet above-mentioned weight percent;
2), by raw material mix, be placed in glass melter and be heated to 1480 ~ 1500 DEG C and found 2 ~ 3 hours, insert in settling pond and homogenize 1 ~ 2 hour in 1500 ~ 1550 DEG C, obtain clarifying uniform glass metal;
Remarks illustrate: in Homogenization, generally without the need to stirring;
3), glass metal is through the shaping sheet glass preparing 1 ~ 2 cm thick of continuous calendering, the sheet glass direct-on-line of forming is annealed, annealing temperature 480 ~ 520 DEG C (being preferably 500 DEG C), soaking time is 0.5 hour, sheet glass after obtaining annealing (in black or brown);
4), by sheet glass direct-on-line after annealing send into nucleus crystallization stove and carry out coring and Crystallizing treatment successively, nucleation temperature 720 ~ 750 DEG C, soaking time is 1 ~ 2 hour; Crystallization temperature 950 ~ 980 DEG C, soaking time is 1 ~ 2 hour, obtains the glass ceramic board after coring and crystallization (in black or brown);
Remarks illustrate: coring and crystallization are the different stepss of nucleus crystallization stove, but carry out in same body of heater;
5), by the glass ceramic board cutting on line after coring and crystallization, be cooled to room temperature after, obtain industrial protection glass-ceramic sheet material.
Room temperature generally refers to 10 ~ 30 DEG C.
Improvement as the preparation method of industrial protection glass-ceramic sheet material of the present invention: by CaO-MgO-Al
2o
3-SiO
2system requirement, makes the basic compound composition in raw material reach following weight percent:
SiO
250%, MgO10%, CaO14%, Al
2o
38%, FeO3%, Na
2o+K
2o4%(and Na
2o is 0.5%, K
2o is 3.5%), CaF
28%, TiO
23%.
Industrial protection glass-ceramic sheet material of the present invention, Essential Chemistry composition meets CaO-MgO-Al
2o
3-SiO
2system, after mating chemical composition, final material composition reaches following weight percent: SiO
250 ~ 55%, MgO8 ~ 10%, CaO12 ~ 14%, Al
2o
38 ~ 10%, FeO3 ~ 5%, Na
2o+K
2o2 ~ 4%, CaF
26 ~ 8%, TiO
23%.
In the present invention, the iron tailings that iron tailings such as can select Inner Mongol Iron And Steel Company to produce, its main component is: SiO
218.3%, MgO3.4%, CaO16.1%, Al
2o
31.2%, FeO24.7%, Na
2o1.0%, K
2o0.78%.
The rhombspar that rhombspar such as can select ore field, Guangxi to produce, its main component CaO30.4%, MgO21.7%.
Quartz sand is conventional city's purchased items, and the content of its SiO2 is 99.5%, that is, foreign matter content can be ignored.
The potassium felspar sand that potassium felspar sand such as can select ore field, Hebei to produce, its main component is K
2o is 11.4 ~ 15.5%, Na
2o is 1.7 ~ 3.9%, SiO
264.1%, Al
2o
318.5%.
The fluorite that fluorite such as can select District, Xinyang Area, Henan Province to produce, its CaF
2content be 90 ~ 97%.
Titanium dioxide is commercial, and TiO2 is 99.9%.That is, foreign matter content can be ignored.
Certainly, the slightly distinguishing iron tailings of other component content, rhombspar, quartz sand, potassium felspar sand, fluorite and titanium dioxide can also be selected.
In the present invention, first according to the weight percentage of the basic compound composition in raw material, and then according to component content in selected iron tailings, rhombspar, quartz sand, potassium felspar sand, fluorite and titanium dioxide, extrapolate the weight part of required iron tailings, rhombspar, quartz sand, potassium felspar sand, fluorite and titanium dioxide.
Generally speaking, raw material can by iron tailings 40 ~ 50 parts, rhombspar 5 ~ 10 parts, quartz sand 30 ~ 40 parts, potassium felspar sand 5 ~ 10 parts, and 6 ~ 8 parts, fluorite and titanium dioxide 3 parts composition, described part is weight part.
Compared with prior art, the present invention has following characteristics:
1), glass ceramic body is CaO-MgO-Al
2o
3-SiO
2system, can obtain trichroite (for principal crystalline phase), thus make glass-ceramic have superior mechanical property and corrosion resistance nature, also have good hot expansibility; As shown in Figure 1.
2), accurate material composition coupling, what ensure glass founds feature, guarantees that glass metal can meet the requirement of on-line continuous calendering formation;
3), adopt Calcium Fluoride (Fluorspan) and oxide compound Nucleating Agent composition Composite Nucleation Agents, breach traditional C aO-MgO-Al
2o
3-SiO
2system is difficult to the technical barrier of overall crystallization, realizes the overall crystallization of trichroite;
4), integrated raw material, fusing, shaping, coring, crystallization, the online manufacturing process such as processing, the constant product quality of wear resistant corrosion resistant glass-ceramic sheet material is guaranteed in automatic production, realizes industrial large-scale production.
Industrial protection glass-ceramic sheet material of the present invention and production method thereof are that contriver obtains after long-term experimental study and production practice.Glass-ceramic sheet material of the present invention, its principal crystalline phase and paracrystalline phase are trichroite, and crystal shape is bar-shaped, minor axis shape, and bending strength is 100 ~ 150MPa or higher, impelling strength>=3.0kJ/m
2, compressive strength>=800MPa, resistance to sulphuric acid soln (massfraction is 0.20)>=96.0%, resistance to sodium hydroxide solution (massfraction is 0.20)>=98.0%, abrasion loss≤0.055g/cm
2, kind is divided into black or amber glass pottery.The preparation method of glass-ceramic sheet material of the present invention, mainly for the production of industrial protection glass-ceramic panel, also may be used for manufacture and the production of architectural decorative glass ceramic.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is prepared CaO-MgO-Al
2o
3-SiO
2the XRD figure spectrum of system glass-ceramic.
Embodiment
The preparation method of embodiment 1, a kind of industrial protection glass-ceramic sheet material, carries out following steps successively:
1), by CaO-MgO-Al
2o
3-SiO
2system requires (carrying out material composition coupling during batching), makes the basic compound composition in raw material reach following weight percent:
SiO
255%, MgO8%, CaO13%, Al
2o
38%, FeO3%, Na
2o+K
2o3%(namely, Na
2o is 0.5%, K
2o is 2.5%), CaF
27%, TiO
23%.
Select iron tailings about 40 parts, rhombspar about 5 parts, quartz sand about 40 parts, potassium felspar sand about 5 parts, about 7 parts, fluorite, the mixture that titanium dioxide is about 3 parts as raw material, thus guarantees that chemical composition contained in raw material meets above-mentioned weight percent.
2), by raw material fully mix, be placed in glass melter and be heated to 1480 ~ 1500 DEG C and found 3 hours, to insert in settling pond 1500 ~ 1550 DEG C and homogenize 2 hours, obtain clarifying uniform glass metal.
3), glass metal is shaping through continuous calendering, prepare the sheet glass of 1 cm thick, annealed by the sheet glass direct-on-line of forming, annealing temperature 500 DEG C, soaking time is 0.5 hour, obtains sheet glass after the annealing of black or brown.
4), sheet glass direct-on-line after annealing is sent into nucleus crystallization stove and carry out coring and Crystallizing treatment successively, nucleation temperature 720 ~ 750 DEG C, soaking time is 2 hours, crystallization temperature 950 ~ 980 DEG C, soaking time is 2 hours, obtains the glass ceramic board after black or brown.
5), by the glass ceramic board cutting on line after coring and crystallization, after being cooled to room temperature, the industrial protection glass-ceramic sheet material of brown is obtained.
The preparation method of embodiment 2, a kind of industrial protection glass-ceramic sheet material, carries out following steps successively:
1), by CaO-MgO-Al
2o
3-SiO
2system requires (carrying out material composition coupling during batching), makes the basic compound composition in raw material reach following weight percent:
SiO
252%, MgO8%, CaO12%, Al
2o
310%, FeO5%, Na
2o+K
2o4%(and Na
2o is 1%, K
2o is 3%), CaF
26%, TiO
23%.
Select iron tailings about 50 parts, rhombspar about 5 parts, quartz sand about 30 parts, potassium felspar sand about 5 parts, about 7 parts, fluorite, the mixture that titanium dioxide is about 3 parts as raw material, thus guarantees that chemical composition contained in raw material meets above-mentioned weight percent.
2), by raw material fully mix, be placed in glass melter and be heated to 1480 ~ 1500 DEG C and found 3 hours, insert in settling pond and homogenize 2 hours in 1500 ~ 1550 DEG C, obtain clarifying uniform glass metal.
3), glass metal is shaping through continuous calendering, and prepare the sheet glass of 1 cm thick, annealed by the sheet glass direct-on-line of forming, annealing temperature 500 DEG C, soaking time is 0.5 hour, obtains sheet glass after the annealing of black or brown.
4), by sheet glass direct-on-line after annealing send into nucleus crystallization stove and carry out coring and Crystallizing treatment, nucleation temperature 720 ~ 750 DEG C, soaking time was at 2 hours, and crystallization temperature 950 ~ 980 DEG C, soaking time, at 2 hours, obtains the glass ceramic board of black or brown.
5), by the glass ceramic board cutting on line after coring and crystallization, after cooling, industrial protection glass-ceramic sheet material is obtained.
The preparation method of embodiment 3, a kind of industrial protection glass-ceramic sheet material, carries out following steps successively:
1), by CaO-MgO-Al
2o
3-SiO
2system requires (carrying out material composition coupling during batching), makes the basic compound composition in raw material reach following weight percent:
SiO
250%, MgO10%, CaO14%, Al
2o
38%, FeO3%, Na
2o+K
2o4%(and Na
2o is 0.5%, K
2o is 3.5%), CaF
28%, TiO
23%.
Select iron tailings about 40 parts, rhombspar about 10 parts, quartz sand about 31 parts, potassium felspar sand about 8 parts, about 8 parts, fluorite, the mixture that titanium dioxide is about 3 parts as raw material, thus guarantees that chemical composition contained in raw material meets above-mentioned weight percent.
2), by raw material fully mix, be placed in glass melter and be heated to 1480 ~ 1500 DEG C and found 3 hours, insert in settling pond and homogenize 2 hours in 1500 ~ 1550 DEG C, obtain clarifying uniform glass metal.
3), glass metal is shaping through continuous calendering, and prepare the sheet glass of 1 cm thick, annealed by the sheet glass direct-on-line of forming, annealing temperature 500 DEG C, soaking time is 0.5 hour, obtains sheet glass after the annealing of black or brown.
4), by sheet glass direct-on-line after annealing send into nucleus crystallization stove and carry out coring and Crystallizing treatment, nucleation temperature 720 ~ 750 DEG C, soaking time is 2 hours, crystallization temperature 950 ~ 980 DEG C, and soaking time, at 2 hours, obtains the glass ceramic board of black or brown.
5), by the glass ceramic board cutting on line after coring and crystallization, after cooling, industrial protection glass-ceramic sheet material is obtained.
The preparation method of embodiment 4, a kind of industrial protection glass-ceramic sheet material, carries out following steps successively:
1), by CaO-MgO-Al
2o
3-SiO
2system requires (carrying out material composition coupling during batching), makes the basic compound composition in raw material reach following weight percent:
SiO
252%, MgO9%, CaO12%, Al
2o
310%, FeO4%, Na
2o+K
2o3%(and Na
2o is 0.5%, K
2o is 2.5%), CaF
27%, TiO
23%.
Select iron tailings about 44 parts, rhombspar about 8 parts, quartz sand about 33 parts, potassium felspar sand about 6 parts, about 6 parts, fluorite, the mixture that titanium dioxide is about 3 parts as raw material, thus guarantees that chemical composition contained in raw material meets above-mentioned weight percent.
2), by raw material fully mix, be placed in glass melter and be heated to 1480 ~ 1500 DEG C and found 2 ~ 3 hours, insert in settling pond and homogenize 2 hours in 1500 ~ 1550 DEG C, obtain clarifying uniform glass metal.
3), glass metal is shaping through continuous calendering, prepare the sheet glass of 1 cm thick, annealed by the sheet glass direct-on-line of forming, annealing temperature 500 DEG C, soaking time is 0.5 hour, obtains sheet glass after the annealing of black or brown.
4), by sheet glass direct-on-line after annealing send into nucleus crystallization stove and carry out coring and Crystallizing treatment, nucleation temperature 720 ~ 750 DEG C, soaking time is 2 hours, crystallization temperature 950 ~ 980 DEG C, and soaking time is 2 hours, obtains the glass ceramic board of black or brown.
5), by the glass ceramic board cutting on line after coring and crystallization, after cooling, industrial protection glass-ceramic sheet material is obtained.
Experiment: performance test
Glass-ceramic sheet material to carry out stuctures and properties detection according to three-point bending method, anti-impact striking, x-ray diffractometer, resistance to acids and bases testing standard is obtained to embodiment 1 ~ 4, the results are shown in Table 1.
Table 1
Comparative example 1, for embodiment 3, make the basic compound composition in raw material into following weight percent:
SiO
252.5%, MgO6.5%, CaO10.5%, Al
2o
39%, FeO4%, Na
2o+K
2o4.5%(namely, Na
2o is 0.5%, K
2o is 4%), CaF
28.5%, TiO
24.5%.
And the number of thing used in corresponding change raw material.
All the other are equal to embodiment 3.
Comparative example 2, for embodiment 3, make the basic compound composition in raw material into following weight percent:
SiO
251.7%, MgO10.2%, CaO14.1%, Al
2o
38.1%, FeO3.2%, Na
2o+K
2o1.2%(namely, Na
2o is 0.9%, K
2o is 0.3%), CaF
28.3%, TiO
23.2%.
And the number of thing used in corresponding change raw material.
All the other are equal to embodiment 3.
Comparative example 3, for embodiment 3, make the basic compound composition in raw material into following weight percent:
SiO
252.5%, MgO11%, CaO16%, Al
2o
39%, FeO3.5%, Na
2o+K
2o4.5%(namely, Na
2o is 0.5%, K
2o is 4%), TiO
23.5%.
And the number of thing used in corresponding change raw material.
All the other are equal to embodiment 3.
Comparative example 4, for embodiment 3, make the basic compound composition in raw material into following weight percent:
SiO
251.5%, MgO10.5%, CaO14.5%, Al
2o
38.2%, FeO3.0%, Na2O+K
2o4.1%(namely, Na
2o is 0.6%, K
2o is 0.35%), CaF
28.2%.
And the number of thing used in corresponding change raw material.
All the other are equal to embodiment 3.
Comparative example 5, the technology contents of first informing according to CN100528781C prepare " SiO
2be 56%, Al
2o
3be 10%, CaO be 14%, MgO be 7%, TiO
2be 4%, Fe
2o
3be 4.0%, ZrO2 be 1%, K
2o-Na
2o is 4% " system.
Then be prepared according to the method described in embodiment 1.The glass-ceramic sheet material of above-mentioned comparative example 1 ~ 5 gained carries out the detection of stuctures and properties, in table 2.
Table 2
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (1)
1. the preparation method of wear-resisting, corrosion resistant industrial protection glass-ceramic sheet material, is characterized in that comprising the following steps:
1), preparation raw material:
By CaO-MgO-Al
2o
3-SiO
2system requirement, makes the basic compound composition in raw material reach following weight percent: SiO
250%, MgO 10%, CaO 14%, Al
2o
38%, FeO 3%, Na
2o+K
2o 4%, CaF
28%, TiO
23%;
Select the mixture of iron tailings, rhombspar, quartz sand, potassium felspar sand, fluorite and titanium dioxide as raw material, make chemical composition contained in described raw material meet above-mentioned weight percent;
2), by raw material mix, be placed in glass melter and be heated to 1480 ~ 1500 DEG C and found 2 ~ 3 hours, insert in settling pond and homogenize 1 ~ 2 hour in 1500 ~ 1550 DEG C, obtain clarifying uniform glass metal;
3), glass metal is shaping through continuous calendering, and prepare the sheet glass of 1 ~ 2 cm thick, annealed by the sheet glass direct-on-line of forming, annealing temperature 480 ~ 520 DEG C, soaking time is 0.5 hour, sheet glass after obtaining annealing;
4), by sheet glass direct-on-line after annealing send into nucleus crystallization stove and carry out coring and Crystallizing treatment successively, nucleation temperature 720 ~ 750 DEG C, soaking time is 1 ~ 2 hour; Crystallization temperature 950 ~ 980 DEG C, soaking time is 1 ~ 2 hour, obtains the glass ceramic board after coring and crystallization;
5), by the glass ceramic board cutting on line after coring and crystallization, be cooled to room temperature after, obtain industrial protection glass-ceramic sheet material.
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| CN1613806A (en) * | 2004-11-24 | 2005-05-11 | 沈阳建筑大学 | Microcrystallizing glass for construction and produced from metal flume and its production |
| CN101298366A (en) * | 2008-07-04 | 2008-11-05 | 沈阳建筑大学 | Metal tailings construction nucleated glass and one-step sintering preparation thereof |
| CN101718137A (en) * | 2009-11-19 | 2010-06-02 | 荥经县腾达石材开发有限责任公司 | Method for producing microcrystal glass decoration plate material with granite waste material |
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Patent Citations (4)
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|---|---|---|---|---|
| CN1263059A (en) * | 1999-01-29 | 2000-08-16 | 河北邢台晶牛玻璃股份有限公司 | Method for making microcrystalline board material by using iron milltailings |
| CN1613806A (en) * | 2004-11-24 | 2005-05-11 | 沈阳建筑大学 | Microcrystallizing glass for construction and produced from metal flume and its production |
| CN101298366A (en) * | 2008-07-04 | 2008-11-05 | 沈阳建筑大学 | Metal tailings construction nucleated glass and one-step sintering preparation thereof |
| CN101718137A (en) * | 2009-11-19 | 2010-06-02 | 荥经县腾达石材开发有限责任公司 | Method for producing microcrystal glass decoration plate material with granite waste material |
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| 含复合晶核剂CaO–MgO–Al2O3–SiO2 微晶玻璃析晶与性能;郭兴忠等;《硅酸盐学报》;20130430;第41卷(第4期);第480~485页 * |
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