CN112851123B - A kind of method for preparing enstatite/spinel complex glass-ceramic with nickel iron slag - Google Patents
A kind of method for preparing enstatite/spinel complex glass-ceramic with nickel iron slag Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 96
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 66
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 51
- 239000011029 spinel Substances 0.000 title claims abstract description 51
- 229910052634 enstatite Inorganic materials 0.000 title claims abstract description 45
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000002425 crystallisation Methods 0.000 claims abstract description 31
- 230000008025 crystallization Effects 0.000 claims abstract description 30
- 239000010881 fly ash Substances 0.000 claims abstract description 17
- 229910000863 Ferronickel Inorganic materials 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 31
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000006121 base glass Substances 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims 2
- 239000013078 crystal Substances 0.000 abstract description 15
- 238000005728 strengthening Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 10
- 239000011521 glass Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910020068 MgAl Inorganic materials 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000003750 conditioning effect Effects 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 11
- 239000000395 magnesium oxide Substances 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 229910052611 pyroxene Inorganic materials 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052839 forsterite Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052661 anorthite Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910016006 MoSi Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910052637 diopside Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
本发明公开了一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法。以镍铁渣为原料，以粉煤灰为调质剂，通过优化镍铁渣与粉煤灰配比，并通过控制微晶玻璃(700‑1000℃)的析晶温度，诱导镍铁渣组分定向转变，制备出以顽火辉石为主晶相，尖晶石(MgFe2O4、MgAl2O4、MgCr2O4)为强化相的微晶玻璃，从而提高微晶玻璃综合性能。本发明所制备的顽火辉石/尖晶石复相微晶玻璃的密度为3.02‑3.09g/cm3，耐酸≥99.95％，耐碱≥99.51％，抗折强度为72‑116MPa，莫氏硬度为8‑9。本发明具有工艺简单，生产成本低，环境友好的特点。利用镍铁渣制备得到的辉石‑尖晶石复相微晶玻璃具有化学稳定性好、抗折强度高等诸多优点，具有良好的应用前景。The invention discloses a method for preparing enstatite/spinel complex crystallized glass by using nickel-iron slag. Using ferronickel slag as raw material and fly ash as conditioning agent, by optimizing the ratio of ferronickel slag and fly ash, and by controlling the crystallization temperature of glass-ceramic (700-1000℃), the ferronickel slag group is induced. The crystallized glass with enstatite as the main crystal phase and spinel (MgFe 2 O 4 , MgAl 2 O 4 , MgCr 2 O 4 ) as the strengthening phase is prepared, thereby improving the comprehensive performance of the glass-ceramic . The enstatite/spinel complex phase glass-ceramic prepared by the invention has a density of 3.02-3.09g/cm 3 , acid resistance ≥99.95%, alkali resistance ≥99.51%, flexural strength of 72-116MPa, Mohs resistance Hardness is 8‑9. The invention has the characteristics of simple process, low production cost and environmental friendliness. The pyroxene-spinel complex glass-ceramic prepared by using nickel-iron slag has many advantages such as good chemical stability and high flexural strength, and has a good application prospect.
Description
技术领域technical field
本发明涉及一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，属于玻璃陶瓷技术领域。The invention relates to a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag, and belongs to the technical field of glass ceramics.
技术背景technical background
随着不锈钢行业的飞速发展，所需镍铁的冶炼规模迅猛增长，镍铁冶炼渣排放量随之迅速增加。根据有关统计，我国镍铁渣年排放量约3000万吨，成为继铁渣、钢渣、赤泥后的第四大冶炼渣。目前，我国渣堆存量已超过2亿吨，利用率仅在10％左右，不仅占用大量土地，还造成了严重的环境污染。因此如何高效、合理、经济的处理镍铁渣逐渐成为镍铁冶炼行业所面临的一个严峻问题。With the rapid development of the stainless steel industry, the required smelting scale of ferronickel has grown rapidly, and the discharge of ferronickel smelting slag has also increased rapidly. According to relevant statistics, the annual discharge of ferronickel slag in my country is about 30 million tons, making it the fourth largest smelting slag after iron slag, steel slag and red mud. At present, the stockpile of slag in my country has exceeded 200 million tons, and the utilization rate is only about 10%, which not only occupies a large amount of land, but also causes serious environmental pollution. Therefore, how to deal with ferronickel slag efficiently, reasonably and economically has gradually become a serious problem faced by the ferronickel smelting industry.
目前，镍铁渣的处理方式主要以堆存和填埋为主，其资研究方向主要集中于井下充填、建材原料、合成聚合物、制备耐火纤维、回收有价金属、制备隔热砖等方面。与铁渣、钢渣相比，镍铁渣中氧化镁、氧化硅含量高(二者含量之和占75wt％左右)，同时含有氧化亚铁(5-10wt％)、氧化铝(2-5wt％)以及有害重金属元素(如Cr等)，化学成分复杂，活性低，导致其在井下充填、建材原料、合成聚合物等方面镍铁渣的使用量小，附加价值低，在制备耐火纤维、回收有价金属方面流程长、操作困难。At present, the treatment methods of ferronickel slag are mainly stockpiling and landfilling, and its research direction mainly focuses on underground filling, building materials, synthetic polymers, preparation of refractory fibers, recovery of valuable metals, preparation of thermal insulation bricks, etc. . Compared with iron slag and steel slag, the content of magnesium oxide and silicon oxide in nickel-iron slag is high (the sum of the two content accounts for about 75wt%), and it also contains ferrous oxide (5-10wt%), alumina (2-5wt%) ) and harmful heavy metal elements (such as Cr, etc.), with complex chemical composition and low activity, resulting in a small amount of nickel-iron slag used in underground filling, building materials, synthetic polymers, etc., and low added value, in the preparation of refractory fibers, recycling In terms of valuable metals, the process is long and the operation is difficult.
制备微晶玻璃是一种冶金渣高效利用的方法。微晶玻璃具有玻璃、陶瓷和天然石材的优点，力学性能出色、化学稳定性高、耐磨性好，同时其制备原料来源广泛。因此，微晶玻璃，特别是CaO-Al2O3-SiO2 (CAS)、CaO-MgO-Al2O3-SiO2(CMAS)系微晶玻璃，已成为一种具有广阔市场应用前景的新型建筑装饰材料。CAS、CMAS系微晶玻璃主晶相有：透辉石、辉石类、硅灰石、钙长石等，此类晶相具有优异的力学性能、化学稳定性及耐磨性，但其莫氏硬度不高(5-6)。因此，在日常使用中微晶玻璃容易产生划痕，影响其使用寿命与装饰效果。同时，由于镍铁渣中含有较高的MgO，随着镍铁渣配入量的提高，氧化镁的含量会高于20wt％，在基础玻璃热处理过程中易生成镁橄榄石相，会导致微晶玻璃力学性能严重下降。The preparation of glass-ceramic is a method for efficient utilization of metallurgical slag. Glass-ceramic has the advantages of glass, ceramics and natural stone, excellent mechanical properties, high chemical stability, good wear resistance, and its preparation raw materials are widely sourced. Therefore, glass-ceramics, especially CaO-Al 2 O 3 -SiO 2 (CAS), CaO-MgO-Al 2 O 3 -SiO 2 (CMAS) series glass-ceramics, have become a kind of glass-ceramic with broad market application prospects. New building decoration materials. The main crystalline phases of CAS and CMAS glass-ceramics are: diopside, pyroxene, wollastonite, anorthite, etc. These crystalline phases have excellent mechanical properties, chemical stability and wear resistance, but their The hardness is not high (5-6). Therefore, the glass-ceramic is prone to scratches in daily use, which affects its service life and decorative effect. At the same time, due to the high content of MgO in the nickel-iron slag, with the increase of the amount of nickel-iron slag, the content of magnesium oxide will be higher than 20wt%. The mechanical properties of crystallized glass are seriously degraded.
专利201711326806.X公开了一种利用镍铁渣制备得到的建筑陶瓷的制备方法。以镍铁渣为原料，石英、富硅铝原料、钙质原料为添加剂，按质量百分比混合后，经过研磨、制粒成型、焙烧得到镍铁渣陶瓷。该方法中制备的镍铁渣陶瓷材料含有钙长石、尖晶石、橄榄石等晶，力学性能优良(抗折强度85-180MPa)，吸水率0.3-7.5％。但是该工艺资源化利用率不高(～60％)，随着镍铁渣配加量的增加，会不同程度的导致抗折强度与吸水率降低。Patent 201711326806.X discloses a preparation method of architectural ceramics prepared by using nickel-iron slag. Using nickel-iron slag as raw material, quartz, silicon-rich aluminum raw material and calcium raw material as additives, after mixing according to mass percentage, the nickel-iron slag ceramics are obtained by grinding, granulating, forming and roasting. The nickel-iron slag ceramic material prepared by the method contains anorthite, spinel, olivine and other crystals, and has excellent mechanical properties (flexural strength of 85-180 MPa) and a water absorption rate of 0.3-7.5%. However, the resource utilization rate of this process is not high (~60%). With the increase of nickel-iron slag dosage, the flexural strength and water absorption rate will be reduced to varying degrees.
发明内容SUMMARY OF THE INVENTION
针对现有技术的不足，本发明旨在提供一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，通过优化镍铁渣与粉煤灰配比，并通过控制微晶玻璃的析晶温度，诱导镍铁渣组分定向转变，获得了密度为3.08g/cm3，耐酸99.97％，耐碱99.70％，抗折强度为116MPa，莫氏硬度为8-9的顽火辉石/尖晶石复相微晶玻璃，大幅提高了镍铁渣的利用率。Aiming at the deficiencies of the prior art, the present invention aims to provide a method for preparing enstatite/spinel complex glass-ceramic with nickel-iron slag, by optimizing the ratio of nickel-iron slag and fly ash, and by controlling The crystallization temperature of glass-ceramics induces the directional transformation of nickel-iron slag components, and obtains a density of 3.08g/cm 3 , acid resistance of 99.97%, alkali resistance of 99.70%, flexural strength of 116MPa, and Mohs hardness of 8-9. Enstatite/spinel complex phase glass-ceramic greatly improves the utilization rate of nickel-iron slag.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，包括如下步骤：将镍铁渣与粉煤灰混合，获得混合料，混合料熔融，获得熔体，将熔体浇铸成型后，进行退火处理获得基础玻璃；将基础玻璃进行结晶处理，即得顽火辉石/尖晶石复相微晶玻璃；The present invention provides a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag, comprising the following steps: mixing nickel-iron slag and fly ash to obtain a mixture, and melting the mixture to obtain a melt , after the melt is cast and formed, the base glass is obtained by annealing treatment; the base glass is crystallized to obtain enstatite/spinel complex phase glass-ceramic;
所述混合料中，镍铁渣的质量分数为65％～80％；In the mixture, the mass fraction of nickel-iron slag is 65% to 80%;
所述镍铁渣中含有Cr2O3；The nickel-iron slag contains Cr 2 O 3 ;
所述混合料中Cr2O3的质量分数为1.3-1.7wt％。The mass fraction of Cr 2 O 3 in the mixture is 1.3-1.7 wt %.
本发明的制备方法通过采用含有Cr2O3的镍铁渣作为原料，与粉煤灰互配，控制镍铁渣的质量分数为65％～80％，可制得顽火辉石/尖晶石复相微晶玻璃，本发明中的镍铁渣中的Cr2O3,可以作为天然的形核剂，促进微晶玻璃析晶，而且MgCr2O4能够减少辉石相的结晶壁垒，促进其析晶。In the preparation method of the invention, enstatite/spinel can be prepared by using nickel-iron slag containing Cr 2 O 3 as a raw material, mixing with fly ash, and controlling the mass fraction of nickel-iron slag to be 65% to 80%. Stone complex phase glass-ceramic, Cr 2 O 3 in the nickel-iron slag in the present invention can be used as a natural nucleating agent to promote the crystallization of glass-ceramic, and MgCr 2 O 4 can reduce the crystallization barrier of pyroxene phase, promote its crystallization.
在本发明中，混合料中Cr2O3的质量分数需要有效控制，若含量过大，也会导致形核结晶过度，影响产品的综合性能。In the present invention, the mass fraction of Cr 2 O 3 in the mixture needs to be effectively controlled. If the content is too large, it will also lead to excessive nucleation and crystallization and affect the comprehensive performance of the product.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，所述混合料中，按质量百分比计，其化学成份组成如下：The present invention is a method for preparing enstatite/spinel complex glass-ceramic with nickel-iron slag. In the mixture, in terms of mass percentage, its chemical composition is as follows:
SiO2 49.2-51.0wt％；Al2O3 8.5-13.5wt％；MgO 18.5-23.5wt％；Fe2O3 10-12wt％；CaO 3.0-4.0％wt％；Cr2O3 1.35-1.70wt％。 SiO2 49.2-51.0wt%; Al2O3 8.5-13.5wt%; MgO 18.5-23.5wt%; Fe2O3 10-12wt %; CaO 3.0-4.0%wt%; Cr2O3 1.35-1.70wt % %.
进一步的优选，所述混合料中，SiO2与Al2O3的质量分数之和为 57.7-64.5wt％。Further preferably, in the mixture, the sum of the mass fractions of SiO 2 and Al 2 O 3 is 57.7-64.5 wt %.
进一步的优选，所述混合料中，MgO与Fe2O3的质量分数之和大于28wt％。Further preferably, in the mixture, the sum of the mass fractions of MgO and Fe 2 O 3 is greater than 28 wt %.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，所述镍铁渣中，MgO的质量分数≥25wt％。The present invention is a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag, wherein in the nickel-iron slag, the mass fraction of MgO is greater than or equal to 25wt%.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，所述镍铁渣中86％及以上的粒径<0.074mm。The present invention is a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag, wherein 86% and above of the nickel-iron slag has a particle size of less than 0.074 mm.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，所述粉煤灰颗粒粒径中86％及以上的粒径<0.074mm。The present invention is a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag, wherein the particle size of 86% and above of the particle size of the fly ash is less than 0.074 mm.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，所述混合料中，镍铁渣的质量分数为70％～75％。The present invention is a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag. In the mixture, the mass fraction of nickel-iron slag is 70% to 75%.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，The present invention is a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag,
所述熔融的温度为1500-1550℃，熔融的时间为1-3h。The melting temperature is 1500-1550° C., and the melting time is 1-3 h.
在实际操作过程中，将混合料置于马弗炉中加热熔融，其中马弗炉采用高温MoSi棒马弗炉。In the actual operation process, the mixture is heated and melted in a muffle furnace, wherein the muffle furnace adopts a high-temperature MoSi rod muffle furnace.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，The present invention is a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag,
所述熔体的温度为1500-1550℃。The temperature of the melt is 1500-1550°C.
在本发明的实际操作过程中，熔体出炉的温度为1550℃，即不经冷却直接进行浇铸成型。In the actual operation process of the present invention, the temperature at which the melt is released from the furnace is 1550° C., that is, the casting is directly performed without cooling.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，The present invention is a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag,
所述浇铸成型所用模具为预热200-500℃的不锈钢模具。The mold used for the casting is a stainless steel mold preheated at 200-500°C.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，The present invention is a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag,
所述退火处理的温度为600-650℃，退火处理的时间为0.5-2h。The temperature of the annealing treatment is 600-650° C., and the time of the annealing treatment is 0.5-2 h.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，所述结晶处理的温度为864-907℃，结晶处理的时间为1-3h，升温速度为4-9℃/min，优选为4-6℃/min。The present invention is a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag. -9°C/min, preferably 4-6°C/min.
本发明中，通过控制升温速度，采用一步结晶法，获得了顽火辉石/尖晶石复相微晶玻璃，在本发明中，尖晶石的析晶温度为700-900℃，顽火辉石的析晶温度800-1000℃，然而发明人意外的发现，通过控制结晶温度在尖晶石和顽火辉石在析晶温度中间，利用尖晶石能够促进辉石相的析出，可以成功的制备获得以顽火辉石为主晶相，尖晶石为强化相的复相微晶玻璃，同时避免镁橄榄石的析出。In the present invention, the enstatite/spinel complex phase glass-ceramic is obtained by controlling the heating rate and adopting a one-step crystallization method. The crystallization temperature of pyroxene is 800-1000°C. However, the inventor unexpectedly found that by controlling the crystallization temperature between the crystallization temperature of spinel and enstatite, the use of spinel can promote the precipitation of pyroxene phase, which can be successful. The preparation of the multi-phase glass-ceramic with enstatite as the main crystal phase and spinel as the strengthening phase is obtained, and the precipitation of forsterite is avoided at the same time.
因而在本发明中，结晶处理的温度，升温速度均是需要有效控制的，若升温速度过快会导致结晶形核不充分，而且会导致较大的收缩率。而若结晶温度过低会导致结晶生长不完全，导致材料性能下降。结晶温度过高会导致形核过分生长，晶相会相互连接在一起，得不到理想的复相结构，导致性能下降，同时温度高了能耗也会变高。Therefore, in the present invention, the temperature of the crystallization treatment and the heating rate need to be effectively controlled. If the heating rate is too fast, the crystal nucleation will be insufficient, and the shrinkage rate will be larger. However, if the crystallization temperature is too low, the crystal growth will be incomplete, resulting in a decrease in material properties. If the crystallization temperature is too high, the nucleation will be excessively grown, and the crystal phases will be connected to each other, and the ideal complex phase structure will not be obtained, resulting in a decrease in performance. At the same time, the energy consumption will increase when the temperature is high.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，所述结晶处理的气氛为空气气氛。The present invention is a method for preparing enstatite/spinel complex glass-ceramic by using nickel-iron slag, and the atmosphere of the crystallization treatment is air atmosphere.
本发明一种用镍铁渣制备顽火辉石/尖晶石复相微晶玻璃的方法，所述顽火辉石/尖晶石复相微晶玻璃的密度为3.02-3.09g/cm3，耐酸≥ 99.95％，耐碱≥99.51％，抗折强度为72-116MPa，莫氏硬度为8-9。The present invention is a method for preparing enstatite/spinel complex phase glass-ceramic by using nickel-iron slag, and the density of the enstatite/spinel complex phase glass-ceramic is 3.02-3.09g/cm 3 , acid resistance ≥ 99.95%, alkali resistance ≥ 99.51%, flexural strength of 72-116MPa, Mohs hardness of 8-9.
原理与优势Principles and Advantages
由于镍铁渣具有镁高、铁高的特性，对于制备顽火辉石相微晶玻璃，从目标组成上来说，单独利用镍铁渣制备难以实现，一般需要配加一定量的调质剂改善原料化学组成体系，而且辉石相微晶玻璃莫氏硬度不高，在平时使用过程中易产生划痕，影响其使用寿命与装饰效果。同时，随着镍铁渣使用配比的提高，过量的氧化镁在析晶过程中会生成镁橄榄石，导致微晶玻璃的力学性能显著下降(如抗折强度)，极大限制了镍铁渣在制备微晶玻璃方面的利。目前，镍铁渣制备微晶玻璃的使用配比一般在30-50wt％，使得镍铁渣无法最大化的进行资源利用，同时导致微晶玻璃的成本上升。Since nickel-iron slag has the characteristics of high magnesium and iron, for the preparation of enstatite phase glass-ceramics, it is difficult to prepare by using nickel-iron slag alone in terms of target composition. Generally, it is necessary to add a certain amount of conditioner to improve the raw material chemistry. The composition system, and the Mohs hardness of the pyroxene phase glass-ceramics is not high, so it is prone to scratches during normal use, affecting its service life and decorative effect. At the same time, with the increase of the ratio of nickel-iron slag, excess magnesium oxide will generate forsterite during the crystallization process, resulting in a significant decrease in the mechanical properties of glass-ceramics (such as flexural strength), which greatly limits the nickel-iron slag. The advantages of slag in the preparation of glass-ceramic. At present, the ratio of nickel-iron slag to prepare glass-ceramics is generally 30-50 wt%, which makes the nickel-iron slag unable to maximize resource utilization, and at the same time leads to an increase in the cost of glass-ceramics.
本发明通过采用含有Cr2O3的镍铁渣作为原料，与粉煤灰互配，在镍铁渣的质量配比高达65％～80％的情况下，却获得了性能优异的，顽火辉石/尖晶石复相微晶玻璃，避免了镁橄榄石析出。The invention adopts the nickel-iron slag containing Cr 2 O 3 as the raw material and mixes it with the fly ash. Under the condition that the mass ratio of the nickel-iron slag is as high as 65% to 80%, it obtains excellent performance, recalcitrant fire Pyroxene/spinel complex phase glass-ceramic, avoiding forsterite precipitation.
本发明中，一方面通过控制镍铁渣与粉煤灰的互配，使得混合料中MgO的含量小于25wt％，另一方面通过采用通过控制升温速度，采用一步结晶法，将温度控制在尖晶石和顽火辉石析晶温度中间，加上尖晶石能够促进辉石相的析出，以此避免了镁橄榄石析出。In the present invention, on the one hand, the content of MgO in the mixture is less than 25 wt% by controlling the interaction of nickel-iron slag and fly ash; Between the crystallization temperature of spar and enstatite, adding spinel can promote the precipitation of pyroxene phase, thus avoiding the precipitation of forsterite.
另外，本发明中，采用含有Cr2O3的镍铁渣作为原料，镍铁渣中含有Cr2O3,可以作为天然的形核剂，促进微晶玻璃析晶，而且MgCr2O4能够减少辉石相的结晶壁垒，促进其析晶。通过上述思路，通过优化组分及控制析晶，诱导镍铁渣组分实现定向转化，获得以顽火辉石为主晶相，尖晶石为强化相的复相微晶玻璃，其性能优异，达到国标标准。In addition, in the present invention, the nickel-iron slag containing Cr 2 O 3 is used as the raw material, and the nickel-iron slag contains Cr 2 O 3 , which can be used as a natural nucleating agent to promote the crystallization of glass-ceramics, and MgCr 2 O 4 can Reduce the crystallization barrier of pyroxene phase and promote its crystallization. Through the above ideas, by optimizing the composition and controlling the crystallization, the nickel-iron slag composition is induced to achieve directional transformation, and a multiphase glass-ceramic with enstatite as the main crystal phase and spinel as the strengthening phase is obtained, and its performance is excellent. , up to the national standard.
本发明“以废治废”，环境友好，镍铁渣的利用率在75％左右，不仅可以很好地解决镍铁渣大量堆存带来的环境问题，而且制备得到的微晶玻璃性能优良。同时在本发明过程中，Cr2O3可以固化在尖晶石中，可以减小镍铁渣中的铬对环境带来的不利影响，总的说来，本发明具有良好的经济效益及社会效益。The present invention is environmentally friendly, and the utilization rate of nickel-iron slag is about 75%, which can not only solve the environmental problems caused by a large amount of nickel-iron slag, but also the prepared glass-ceramic has excellent performance . At the same time, in the process of the present invention, Cr 2 O 3 can be solidified in the spinel, which can reduce the adverse effect of chromium in the nickel-iron slag on the environment. In general, the present invention has good economic benefits and social benefits benefit.
本发明具有工艺简单，生产成本低，环境友好的特点。利用镍铁渣制备得到的辉石-尖晶石复相微晶玻璃具有化学稳定性好、抗折强度高等诸多优点，具有良好的应用前景。The invention has the characteristics of simple process, low production cost and environmental friendliness. The pyroxene-spinel complex glass-ceramic prepared by using nickel-iron slag has many advantages such as good chemical stability and high flexural strength, and has a good application prospect.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步的详细说明，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例，基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The present invention will be further described in detail below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, those of ordinary skill in the art will All other embodiments obtained under the premise of creative work fall within the protection scope of the present invention.
为避免重复，现将本具体实施方式所涉及的原料统一描述如下，具体实施例中不再赘述：In order to avoid repetition, the raw materials involved in this specific embodiment are now described uniformly as follows, and will not be repeated in the specific examples:
所述镍铁渣按质量百分比计其成分如下：Described ferronickel slag measures its composition by mass percentage as follows:
SiO2含量为48.25wt％，MgO含量为28.32wt％，Fe2O3含量为 13.92wt％，Al2O3含量2.27wt％，CaO含量为3.71wt％，Cr2O3含量为2.09wt％，余量为杂质。The SiO2 content was 48.25wt%, the MgO content was 28.32wt%, the Fe2O3 content was 13.92wt%, the Al2O3 content was 2.27wt %, the CaO content was 3.71wt %, and the Cr2O3 content was 2.09wt % , the remainder is impurities.
所述粉煤灰按质量百分比计其成分如下：The fly ash has the following components in terms of mass percentage:
SiO2含量为53.49wt％，MgO含量为0.49wt％，Fe2O3含量为 2.92wt％，Al2O3含量33.77wt％，CaO含量为3.89wt％，余量为杂质。The SiO2 content was 53.49wt%, the MgO content was 0.49wt%, the Fe2O3 content was 2.92wt %, the Al2O3 content was 33.77wt %, the CaO content was 3.89wt%, and the balance was impurities.
所述的镍铁渣的粒径为86％小于0.074mm。The particle size of the nickel-iron slag is 86% smaller than 0.074mm.
所述的粉煤灰的粒径为86％小于0.074mm。The particle size of the fly ash is 86% smaller than 0.074mm.
所述微晶玻璃性能中化学稳定性测试(耐酸、耐碱)其测试方法如下：The chemical stability test (acid resistance, alkali resistance) in the performance of the glass-ceramic is as follows:
化学稳定性测试参照标准JC/T2283-2014，将微晶玻璃样品置于 20％H2SO4和20％NaOH溶液中水浴加热至沸腾状态，加热时间为 1h。化学稳定性：C＝(m1-m2)/m1×100％，其中m1为未腐蚀前样品质量，m2为腐蚀后样品质量。The chemical stability test refers to the standard JC/T2283-2014, and the glass-ceramic sample is placed in a 20% H 2 SO 4 and 20% NaOH solution and heated to a boiling state in a water bath for 1 h. Chemical stability: C=(m 1 -m 2 )/m 1 ×100%, where m 1 is the mass of the sample before corrosion, and m 2 is the mass of the sample after corrosion.
实施例1Example 1
将80wt％镍铁渣与20wt％粉煤灰混合均匀，将混合料在高温下熔融为玻璃液，熔融温度为1550℃，熔融时间为3h；随后出炉浇铸到预热至300℃的不锈钢模具冷却成型，并在650℃退火消除应力，退火时间2h；然后随炉冷，获得基础玻璃。Mix 80wt% nickel-iron slag and 20wt% fly ash uniformly, melt the mixture into glass liquid at high temperature, the melting temperature is 1550 ℃, and the melting time is 3h; then it is cast into a stainless steel mold preheated to 300 ℃ to cool Formed, and annealed at 650°C to relieve stress, annealing time was 2h; then cooled with furnace to obtain base glass.
将制备的基础玻璃放入马弗炉进行热处理。以5℃/min的速度升温到864℃形核，结晶时间为2h；随炉冷获得以顽火辉石相为主晶相，尖晶石相为强化相的微晶玻璃。The prepared base glass is put into a muffle furnace for heat treatment. The temperature was heated to 864°C at a rate of 5°C/min for nucleation, and the crystallization time was 2h; the crystallized glass with enstatite as the main crystal phase and spinel phase as the strengthening phase was obtained with furnace cooling.
本实施例1用镍铁渣制备的以顽火辉石为主晶相，尖晶石为强化相的微晶玻璃：密度3.09g/cm3，耐酸99.95％，耐碱99.51％，抗折强度78MPa，莫氏硬度8-9。In Example 1, the crystallized glass with enstatite as the main crystal phase and spinel as the strengthening phase prepared with nickel iron slag: density 3.09g/cm 3 , acid resistance 99.95%, alkali resistance 99.51%, flexural strength 78MPa, Mohs hardness 8-9.
实施例2Example 2
将75wt％镍铁渣与25wt％粉煤灰混合均匀，将混合料在高温下熔融为玻璃液，熔融温度为1550℃，熔融时间为3h；随后出炉浇铸到预热至200-500℃的不锈钢模具冷却成型，并在650℃退火消除应力，退火时间2h；然后随炉冷，获得基础玻璃。Mix 75wt% nickel-iron slag and 25wt% fly ash uniformly, melt the mixture into glass liquid at high temperature, the melting temperature is 1550℃, and the melting time is 3h; then cast into stainless steel preheated to 200-500℃ The mold is cooled and formed, and annealed at 650° C. to eliminate stress, and the annealing time is 2 hours; then, the base glass is obtained by cooling with the furnace.
将制备的基础玻璃放入马弗炉进行热处理。以5℃/min的速度升温到867℃结晶，结晶时间为2h；然后随炉冷，获得以顽火辉石相为主晶相，尖晶石相为强化相的微晶玻璃。The prepared base glass is put into a muffle furnace for heat treatment. The temperature was heated to 867°C for crystallization at a rate of 5°C/min, and the crystallization time was 2h; then cooled in the furnace to obtain a glass-ceramic with enstatite phase as the main crystal phase and spinel phase as the strengthening phase.
本实施例2用镍铁渣制备的以顽火辉石为主晶相，尖晶石为强化相的微晶玻璃：密度3.08g/cm3，耐酸99.97％，耐碱99.70％，抗折强度116MPa，莫氏硬度8-9。In Example 2, the glass-ceramic with enstatite as the main crystal phase and spinel as the strengthening phase prepared with nickel-iron slag: density 3.08g/cm 3 , acid resistance 99.97%, alkali resistance 99.70%, flexural strength 116MPa, Mohs hardness 8-9.
实施例3Example 3
将70wt％镍铁渣与30wt％粉煤灰混合均匀，将混合料在高温下熔融为玻璃液，熔融温度为1550℃，熔融时间为3h；随后出炉浇铸到预热至300℃的不锈钢模具冷却成型，并在650℃退火消除应力，退火时间2h；然后随炉冷，获得基础玻璃。Mix 70wt% nickel-iron slag and 30wt% fly ash uniformly, melt the mixture into glass liquid at high temperature, the melting temperature is 1550℃, and the melting time is 3h; then it is cast out of the furnace and cast into a stainless steel mold preheated to 300℃ to cool Formed, and annealed at 650°C to relieve stress, annealing time was 2h; then cooled with furnace to obtain base glass.
将制备的基础玻璃放入马弗炉进行热处理。以5℃/min的速度升温到883℃结晶，结晶时间为2h；然后随炉冷，获得以顽火辉石相为主晶相，尖晶石相为强化相的微晶玻璃。The prepared base glass is put into a muffle furnace for heat treatment. The temperature was heated to 883°C for crystallization at a rate of 5°C/min, and the crystallization time was 2h; then cooled in the furnace to obtain a glass-ceramic with enstatite phase as the main crystal phase and spinel phase as the strengthening phase.
本实施例3用镍铁渣制备的以顽火辉石为主晶相，尖晶石为强化相的微晶玻璃：密度3.06g/cm3，耐酸大于99.99％，耐碱99.74％，抗折强度101.5MPa，莫氏硬度8-9。In Example 3, the glass-ceramic with enstatite as the main crystal phase and spinel as the strengthening phase prepared by using nickel-iron slag: density 3.06g/cm 3 , acid resistance greater than 99.99%, alkali resistance 99.74%, folding resistance Strength 101.5MPa, Mohs hardness 8-9.
实施例4Example 4
将65wt％镍铁渣与35wt％粉煤灰混合均匀，将混合料在高温下熔融为玻璃液，熔融温度为1550℃，熔融时间为3h；随后出炉浇铸到200-500℃的不锈钢模具冷却成型，并在650℃退火消除应力，退火时间2h；然后随炉冷，获得基础玻璃。Mix 65wt% nickel-iron slag and 35wt% fly ash evenly, melt the mixture into glass liquid at high temperature, the melting temperature is 1550℃, and the melting time is 3h; then the stainless steel mold casted to 200-500℃ is cooled and formed , and annealed at 650 ℃ to eliminate stress, annealing time 2h; and then cooled with the furnace to obtain the base glass.
将制备的基础玻璃放入马弗炉进行热处理。以5℃/min的速度升温到907℃结晶，结晶时间为2h；然后随炉冷，获得以顽火辉石相为主晶相，尖晶石相为强化相的微晶玻璃。The prepared base glass is put into a muffle furnace for heat treatment. The temperature was heated to 907°C for crystallization at a rate of 5°C/min, and the crystallization time was 2h; then cooled in the furnace to obtain a glass-ceramic with enstatite phase as the main crystal phase and spinel phase as the strengthening phase.
本实施例4用镍铁渣制备的以辉石为主晶相，尖晶石为强化相的微晶玻璃：密度3.02g/cm3，耐酸大于99.99％，耐碱99.89％，抗折强度72MPa，莫氏硬度8-9。In Example 4, the glass-ceramic with pyroxene as the main crystal phase and spinel as the strengthening phase prepared by nickel-iron slag: density 3.02g/cm 3 , acid resistance greater than 99.99%, alkali resistance 99.89%, flexural strength 72MPa , Mohs hardness 8-9.
对比例1Comparative Example 1
其他条件与实施例1相同，仅是将90wt％镍铁渣与10wt％粉煤灰混合均匀。Other conditions are the same as in Example 1, except that 90wt% nickel-iron slag and 10wt% fly ash are uniformly mixed.
经检测，本对比例1镍铁渣制备的微晶玻璃：密度3.16g/cm3，耐酸99.84％，耐碱99.47％，抗折强度61MPa。After testing, the glass-ceramic prepared from nickel-iron slag in Comparative Example 1 has a density of 3.16 g/cm 3 , an acid resistance of 99.84%, an alkali resistance of 99.47%, and a flexural strength of 61 MPa.
对比例2Comparative Example 2
其他条件与实施例1相同，仅是以10℃/min速度升温到867℃结晶。Other conditions were the same as in Example 1, except that the temperature was raised to 867°C at a rate of 10°C/min for crystallization.
经检测，本对比例2镍铁渣制备的微晶玻璃：密度3.05g/cm3，耐酸99.75％，耐碱99.14％，抗折强度45MPa。After testing, the glass-ceramic prepared from nickel-iron slag in Comparative Example 2 has a density of 3.05 g/cm 3 , an acid resistance of 99.75%, an alkali resistance of 99.14%, and a flexural strength of 45 MPa.
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明，因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。It will be apparent to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, but that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention, therefore, no matter from In all respects, the embodiments should be considered as exemplary and non-restrictive, the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that All changes within the meaning and scope are included in the invention.
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方案。In addition, it should be understood that although this specification is described in terms of embodiments, not each embodiment only includes an independent technical solution, and this description in the specification is only for the sake of clarity, and those skilled in the art should take the specification as a whole , the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.
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