CN102753496A - Composition used to produce igneous rock crystal glass material, igneous rock crystal glass material and production method thereof - Google Patents

Composition used to produce igneous rock crystal glass material, igneous rock crystal glass material and production method thereof Download PDF

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CN102753496A
CN102753496A CN2010800491037A CN201080049103A CN102753496A CN 102753496 A CN102753496 A CN 102753496A CN 2010800491037 A CN2010800491037 A CN 2010800491037A CN 201080049103 A CN201080049103 A CN 201080049103A CN 102753496 A CN102753496 A CN 102753496A
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igneous rock
igneous
ore
crystal glass
glass
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CN102753496B (en
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刘华武
杨宗彬
戴洪明
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Tianjin Dingshang Technology Co ltd
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Tianjin Dingshang Technology Co ltd
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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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C03C1/022—Purification of silica sand or other minerals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • 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
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

Abstract

A method for producing igneous rock crystal glass material comprises the following process steps: crushing ore, pre-treating crushed ore, mixing supplementary material, melting mixed material and preparing the finished product. Said ore is the igneous rock. Pre-treating crushed ore involves water-washing or acid-washing plus water-washing, in which the acid used in acid-washing is hydrochloric acid, nitric acid or sulfuric acid with the mass concentration of 1-50%. Stirring and dipping in acid is performed for 0.5-24 hours. Said supplementary material is at least one of SiO2, Al2O3, MgO, B2O3, ZrO2, La2O3 and Y2O3, the addition amount of which is 1-30% of the mass of crushed ore. Melting temperature is between the melting point of the ore plus 50 and the boiling point of the ore minus 50 . Melting atmosphere is non-strong oxidizing atmosphere. A composition used to produce the igneous rock crystal glass material and an igneous rock crystal glass material produced by said method are provided. The method does not use the flux and strong oxidizing melting atmosphere, and the annealing crystallization process is omitted. The product obtained has high qualified rate, excellent performance, good appearance, good applicability and low cost.

Description

Composition used to produce igneous rock crystal glass material, igneous rock crystal glass material and production method thereof
It is a kind of be used to preparing the composition of igneous rock crystal glass material, igneous rock crystal glass material and
Its manufacture method
Technical field
The present invention relates to mineral glass material preparation technology, specially a kind of formula for preparing the method for crystal glass material using acid, neutral, alkalescence or hyperalkaline igneous rock and using.Background technology
Glass is a kind of non-crystalline solids, is formed by melt supercooled.Earth lava is cooled down rapidly, is just turned into igneous rock (Igneous rocks) ore body of glassy state, is commonly called as crystal or agate（Such as obsidian crystal Obsidian, black agate fire jade), Slow cooling just forms the common igneous rock ore of non-glass state.Natural igneous rock glass is called crystal by people（Or agate）, to be different from simple glass, the mineral material also referred to as crystal glass that the present invention is prepared with igneous rock accordingly（Or agate）.
Igneous rock accounts for the 95% of earth's lithosphere, there are about more than 700 kind.As the igneous rock of earth skeleton, the features such as naturally there is high intensity, stable chemical performance.The main skeleton component of igneous rock is silica, aluminum oxide and iron oxide, the number according to dioxide-containing silica（I.e. acid-base property is strong and weak）Igneous rock is divided into four major classes：1. it is acid（), Felsic dioxide-containing silica>65%, such as granite, rhyolite, dacite, perlite and obsidian etc.；2. it is neutral（Intermediate), dioxide-containing silica 52-65%, such as diabase, andesite and basaltic andesite；3. alkalescence（Mafic), dioxide-containing silica 45-52%, such as basalt, gabbro and diabase；4. hyperalkaline（), Ultramafic dioxide-containing silica<45%, such as peridotite and komatiite, usually micro association jewel.Traditional igneous rock cast product is mainly the glass ceramics of basalt glass crystallization, and other cast articles are rare in market.Patent WO2003016232 reports one kind in crushed crude pearlite or swelling perlite powder（A kind of acidic igneous rock product）After 15% caustic soda of middle addition and limestone flux, the method for foam thermal insulation glass material is cast.Because the material heat-insulating property and cost are not as good as the swelling perlite powder as raw material, thus fail to promote.
1914, French Francois Ribbe have found that mineral glass is annealed to before 500 °C first, are reheated to 800 °C, are incubated 0.5-1.5 hours in the lehr, a large amount of crystallites can be generated in glass, so as to improve the intensity and toughness (US1108007) of glass.1933, US1893382 patents further reported the process conditions that glass ceramics is produced under oxidation and reducing atmosphere.1956, this technology was expanded to simple glass field by Dr. Stooky again（US2920971 ) .1969, patent US3557575 was first this ceramic material being made of basalt glass, referred to as basalt glass ceramics（Basaltic glass-ceramic), and advise the melting under oxidizing atmosphere, annealed under non-strong oxidizing atmosphere, so far basalt glass ceramic process finalizes the design almost.Glass ceramics production technology is introduced into China within 1956, and its product is also referred to as devitrified glass（Devitrified glass), mineral glass ceramics are then referred to as cast stone（Cast stone). The fusion temperature of basalt ore is 1350-1500 °C (CN1789187,2004), as Fe in ore composition2O3/FeO>When 0.5, glass casting just can generate crystallite under specific annealing conditions, as glass ceramics, and the nucleus of its crystalline solid is mainly the Fe in melt203And FeO.Usual igneous rock ore Fe203/ FeO ratios are less than 0.5, therefore melting needs to use oxidizing atmosphere so that FeO is converted into Fe203.Fe can be made by generally founding in atmosphere2O3/FeO>0.5, oxidant such as NH can also be further added in the feed4N03Or Mn02Realize this target（Cheng Jinshu etc., " devitrified glass ", Chemical Industry Press, Beijing, 2006).In order to reduce cost, basalt glass ceramics generally utilize basalt, or basalt and industrial residue are main material, through high melt, casting or calendering formation, then glass nucleation crystallization is formed, the leading indicator for characterizing its mechanical property is bending strength, typically between 30-80MPa.
Prepare traditional high Fe203/ FeO ratios（>0.5), the igneous rock glass of high tendency towards devitrification, and its technique of crystallization into glass ceramics have following defect：
1. cost is high：One typical basalt glass ceramic production technology is to be incubated 4 hours at 650 °C after ammonium nitrate of the addition 4% as oxidant, glass smelting, 880 °C of insulations, 1 hour production crystallite, and then re-annealing is to room temperature（Cheng Jinshu etc., " devitrified glass ", Chemical Industry Press, Beijing, 2006).The insulating process of 5 hours of the technique, increases energy consumption at double.
2. waste product is more：Basalt glass is interval as temperature drop viscosity can increase sharply in shaping（I.e. material property short, quick solidifying）, melt forming is interval in addition and crystallization is interval closely, crystallization devitrification is particularly easy to, as granulated slag shape waste material.And the basalt glass of high tendency towards devitrification, it is more easy to crystallization and scraps.Crystallization area is crossed so must be cooled down rapidly during glass casting（Crystallization ceiling temperature is about at 1260-1270 °C or so）Avoid crystallization devitrification.The thermal coefficient of expansion of basalt glass is big, and rapid cooling again can be because thermal stress is excessive and cracks, even scrap, so as to cause waste product during into glass.Basalt glass complicated components, content fluctuation are more difficult to control into brilliant process also much larger than simple glass than Ordinary microcrystalline glass.Annealing crystallization process, it is easy to produce waste product again.Chinese building material net reports a large amount of glass ceramics enterprises qualification rate all below 60%, it has also become the bottleneck of industry development.In addition glass ceramic board hardness is high, and the warpage after paving is difficult to flatten, many coarse wool pores occur after polishing, there is no method to handle at present, building materials market is difficult to receive（Chinese building material net report, www.bmlink.com/news/).And traditional basalt casting, it is easier to crystallization, it is easier to burst, crystallize and control more difficult, its glass ceramics qualification rate is lower.The plain such as earthenware of basalt glass ceramics outward appearance, market is more limited to compared with simple glass ceramics, is mainly used in anticorrosion pipeline.
3. quality deterioration：In order to reduce viscosity and fusing point, people add the fluxing agents such as lime stone, sodium carbonate, cullet and fluorite in basalt ore（Cheng Jinshu etc., " devitrified glass ", Chemical Industry Press, Beijing, 2006;Li Ping, Ou Zhi, " correctly recognizing basalt fibre, glass fibre ", 2008 (3)： 35-41；US4009015,1977), while tendency towards devitrification is improved, also bring many negative effects.Calcium ion in lime stone can increase glass while tendency towards devitrification is increased Fragility, shortening strip, raising burst tendency.Sodium ion in sodium carbonate then destroys glass microstructure, reduction heat endurance, chemical stability and mechanical strength.Cullet can improve cost, reduction intensity, increase fragility.Fluorite key component is CaF2, air is polluted after fluorine compounds volatilization, glass industry is it is not recommended that use.Traditional basalt glass ceramic process generates crystallite, it is desirable to Fe2O3/FeO>0.5, and using melting in atmosphere or use strong oxidizing atmosphere（Add oxidant or input oxygen）To improve this ratio.But discovered in recent years basalt glass Fe203/ FeO ratios are smaller, and the mechanical property of material is better on the contrary（Li Ping, Ou Zhi, correctly recognize basalt fibre, glass fibre, 2008 (3)： 35-41； US4009015, 1977).The raising for the mechanical property that crystallite is brought, by Fe203/ FeO ratios increase and major part is offset.
4. limitation is big：The high Fe of tradition203The preparation method of/FeO ratios, high tendency towards devitrification basalt glass and glass ceramics, its additive for improving crystal forming rate deteriorates some physicochemical properties of material, the improved space of material property is limited, while not also being suitable for acid and intermediate igneous rocks ore.Because acid and neutral ore middle skeleton material Si02And A1203Ratio greatly improve, so as to improve the viscosity of melt, also reduce material and be inclined into crystalline substance.
Although glass ceramics technique can improve the intensity of simple glass, for basalt glass ceramics, the raising of intensity is first offset by localized crackses or devitrification, then the destruction of glass properties is offset by fluxing agent, then also by Fe203The increase of/FeO ratios is offset, and is lost and is more than.The main cause for causing strength of glass to decline is the flaw of glass in itself, the particularly crackle on surface, and after surface layer of glass is removed, tensile strength can improve more than 10 times（Loewenstein, " continuous glass fibre manufacturing process ", China Standards Press, 2008).And it is exactly high stress gradients and the strength of glass reduced by conventional art caused by chilling and high thermal expansion coefficient to cause the main cause of basalt glass face crack.In recent years, Ceramics Enterprises are being endeavoured to develop glass ceramics always（That is devitrified glass）Product." but even to this day, how to capture the difficulty more than surface pores, improve product quality, increase varieties and designs, reduce production cost, be still the critical point for being difficult to go beyond together（Chinese building material net, www.bmlink.com/news/ message/ 160393.html)." basalt glass ceramic industry even more faces the predicament of the market shrink.The content of the invention
In view of the deficienciess of the prior art, the technical problem that the present invention is intended to solve is：A kind of igneous rock crystal glass material and its manufacture method and auxiliary material addition scheme are provided, the manufacture method and formula are using anti-crystallization and optimization modification technology.Without using deterioration material property and the fluxing agent and Strong oxdiative melting atmosphere of raising devitrification of glass tendency, basalt glass Annealing Crystallization technique is not used, product qualified rate is high, properties of product are excellent, and beautiful appearance, applicability is wide, and cost is relatively low.
The technical scheme that the present invention solves the technical problem is to design a kind of manufacture method of igneous rock crystal glass material, and the manufacture method is comprised the following steps that successively：It is prepared by ore pretreatment, auxiliary material mixing, compound melting and finished product；The ore is igneous rock, can be crushed according to the size of ore particles, the broken ore particle diameter after ore reduction is 0.1-5mm; The broken ore pretreatment is using washing or the method for acid washing and water washing；Spent pickling acid is hydrochloric acid, nitric acid or the sulfuric acid of mass concentration 1 50%, and pickling stirring soak time is 0.5 24 hours；The auxiliary material of the auxiliary material hybrid technique is Si02、 A1203、 MgO、 B203、 Zr02、 La203And Y203At least one of, the addition of auxiliary material is the 1 30% of broken ore quality；The smelting temperature of the compound smelting technology is one 50 °C of ore boiling temperature of+50 °C of ore melting temperature, melting environment is non-strong oxidizing atmosphere, including reducing atmosphere, nitriding atmosphere, vacuum environment, enclosed environment and at least one of melting in atmosphere；The finished product preparation technology includes die casting, calendering or blow molding, or melt Quench it is broken after powder is made.
In the preparation process in accordance with the present invention, the formula used is made up of igneous rock and auxiliary material, and the addition quality of the auxiliary material is the 1 30% of igneous rock quality, and the igneous rock is pre-processed by washing or acid washing and water washing, and the auxiliary material is Si02、 A1203、 MgO、 B203、 Zr02、 La203And Y203At least one of.
Igneous rock crystal material is prepared using the method for the present invention, includes following components according to mass percent： Si02 45-90%、 A1203 5-25%, Fe203l-15%、 FeO 1-15%, MgO 1-15%, CaO 1-15%, Na20 1-15%, K20 1-15%, Ti02 0-5%, B203 0-5%, Zr020-5%, La2030-5%, Y2O3 0-5%。
Compared with prior art, manufacture method of the present invention does not use because employing anti-crystallization formula and technique and improves tendency towards devitrification, reduces the fluxing agent and Strong oxdiative melting atmosphere of mechanical property（Input oxygen uses oxidant）, so that having can allow glass Slow cooling to be molded, the characteristics of reducing thermograde and thermal stress gradient；Because employing the auxiliary material of reduction thermal coefficient of expansion, no longer using the fluxing agent of increase thermal coefficient of expansion, so that the characteristics of there is reduction glass heat stress intensity；Because employing the formula and technique of reinforcing glass intensity, so as to improve glass itself anti-crack ability.These three measures of the invention substantially increase the yield rate and mechanical property of material, it is no longer necessary to use crystallization for the modified measures of glass ceramics, therefore also improve outward appearance, reduce energy consumption.The bending strength of the gained sample of the embodiment of the present invention 1 is about twice of existing market basalt glass ceramics.
Igneous rock crystal glass and traditional basalt deep processed product have form, outward appearance, component, the scope of application, the big difference of yield rate 5：1 traditional ore casting final products are the ceramics that mineral glass is made, and final products of the present invention are glass；2 glass-ceramic basalt outward appearances are such as stone, tile fragment, and the crystal glass outward appearance of the present invention is such as morion, black agate；3 traditional glass-ceramic basalts use high crystallization formula, the auxiliary material using crystallization are with the addition of, while improving Fe by oxidizing atmosphere203/ Fe0 ratios.The present invention uses anti-crystallization auxiliary material, and resistance to fracture auxiliary material does not improve or reduced Fe while employing203/ Fe0 melting atmosphere, the component of product differs widely；4 traditional basalt deep working methods are only applicable to alkaline igneous rocks, and this technology is applied to all acid, neutral, alkalescence and hyperalkaline igneous rock so that resource utilization is greatly improved；5 traditional cast stone coolings are then then burst very much soon into powder, too slowly, and percent defective is high, and igneous rock crystal can be molded with slow cooling, substantially without waste product. Brief description of the drawings
Fig. 1 is the manufacturing approach craft schematic flow sheet of igneous rock crystal glass material of the present invention；
Fig. 2 is the manufacture method of igneous rock crystal glass material of the present invention（Embodiment 1) obtained by modification intermediate igneous rocks crystal glass material manufacture continuous filament yarn photo figure；
Fig. 3 is the manufacture method of igneous rock crystal glass material of the present invention（Embodiment 2) obtained by alkaline igneous rocks crystal glass material product photo figure（3a is natural obsidian crystal bangle, and 3b is igneous rock crystal slab products）；
Fig. 4 is the manufacture method of igneous rock crystal glass material of the present invention（Embodiment 3) obtained by acidic igneous rock crystal glass material（Crystal）Powder photo figure；
Fig. 5 is the manufacture method of igneous rock crystal glass material of the present invention（Embodiment 1) obtained by modification intermediate igneous rocks crystal glass material sample have no obvious crystallization X-RAY test curve figures；
Fig. 6 is the gained sample thermal coefficient of expansion test curve figure of manufacture method embodiment 1 of the present invention（Unit： 10-6/°C );Fig. 7 is the gained sample permittivity ε ' of manufacture method embodiment 1 of the present invention, dielectric loss ε " test curve figures；Fig. 8 is the gained sample permeability μ ' of manufacture method embodiment 1 of the present invention, magnetic loss μ " test curve figures.Embodiment
The present invention is further discussed below with reference to embodiment and its accompanying drawing：
The manufacture method for the igneous rock crystal glass material that the present invention is designed（Abbreviation manufacture method, the manufacture method are comprised the following steps that referring to Fig. 11 8) successively：Ore reduction 1, broken ore pretreatment 2, auxiliary material mixing 3, compound melting 4 and finished product prepare 5 (referring to Fig. 1);The ore is igneous rock, and broken ore particle size range is 0.1-5mm;Described broken ore pretreatment is using washing or the method for acid washing and water washing；The pickling is hydrochloric acid, nitric acid or sulfuric acid with acid, and the mass concentration of Acidwash solution is 1 50%, and pickling stirring soak time is 0.5 24 hours；The auxiliary material of the auxiliary material hybrid technique is Si02、 A1203、 MgO、 B203、 Zr02、 La203And Y203At least one of, the addition of auxiliary material is the 1 30% of ore quality；The smelting temperature of the compound smelting technology is ore melting temperature tmelt+ 50 °C of ore boiling temperature tboil- 50 °C, melting environment uses non-strong oxidizing atmosphere（Oxygen is not inputted, without oxidant）, including reducing atmosphere, nitriding atmosphere, vacuum environment, enclosed environment and at least one of melting in atmosphere；The finished product preparation technology includes die casting, calendering or blow molding, or melt Quench it is broken after make powder.
Igneous rock described in manufacture method of the present invention includes acid, neutral, alkalescence and hyperalkaline all four major class igneous rock.In ore reduction technique, the particle diameter of ore reduction is typically designed as 0.1-5mm.Broken ore particle not only melts greatly slow, and probably due to fusing not exclusively forms calculus in finished product, while it is broken in auxiliary material hybrid technique to pass through also easily powdery auxiliary material Space between ore is leaked to bottom, causes batch mixing not hook, and influences product quality.Although broken ore is smaller, melt faster, energy consumption is lower, and meticulous stone flour easily flies upward, lumpd, cause dust and mixing not to hook.The particle diameter of broken ore of the present invention is in more than 0.1mm, and tank furnace is with broken ore particle diameter in more than 0.25mm.Preferable particle size of the present invention is less than 5mm stone waste material broken ore, and its price is relatively low, and melting less energy intensive particularly can omit ore reduction technique, further improve efficiency, reduce cost；Or/and the selection particle diameter stone slightly larger than 5mm waste material broken ore, crush easy, can also improve efficiency, reduce cost.
Manufacture method of the present invention pre-processes broken ore in pretreating process using washing or acid washing and water washing.It is the alkali metal oxide for more effectively going the removal of impurity and removing destruction glass structure using the purpose of pickling.The pickling is hydrochloric acid, nitric acid or sulfuric acid with acid, and the mass concentration of acid solution is 1 50%, and pickling stirring soak time is 0.5 24 hours.Pretreating process in the basalt deep processing preparation method of prior art is typically rinsed or alkali cleaning using clear water, it is therefore intended that retain basaltic basic component（CN101263090, 2008).In order to reduce tendency towards devitrification, present invention employs the preprocess method of appropriate pickling, to reduce the content of alkaline matter and Nucleating Agent in ore.Volatile materials and other impurities can also be removed while pickling, melt viscosity is improved, the effect for reducing into brilliant tendency and improving material physicochemical property is played.
Manufacture method of the present invention, according to product design needs, auxiliary material Si0 is added in the ratio of broken ore quality 1 30% in auxiliary material hybrid technique2、 A1203、 MgO、 B203、 Zr02、 La203And Y203At least one of, to improve devitrification resistance energy, mechanical property, decay resistance and the thermal stability of glass material.A1 in auxiliary material203, MgO and ZnO be anti-crystallization component, it can be such that the silicon-oxy tetrahedron of fracture reconnects, so that the decline of crystallization ability；And the A1 in auxiliary material203、 B203And Ga203The larger extra-network ion accumulation of electric-field intensity can be reduced, so that tendency towards devitrification is reduced, wherein A1203Anti- crystallization effect is the most notable, is that embodiment is preferred.Basalt is a kind of common alkali igneous rock, and basalt glass contains a large amount of alkali metal oxides, and thermal coefficient of expansion is higher, easily causes and bursts, therefore addition auxiliary material can be Si02、 A1203、 Zr02、 B203、 MgO、 Zn03At least one of, and alkali metal oxide is removed with pickling, thermal coefficient of expansion is reduced, its thermal stability is improved.Recent study is found, La is introduced in glass material composition203、 Y203And/or Ti02Glass modulus can be effectively improved, increases the toughness of glass, and introduces Si02、 A1203And/or B203The intensity of glass can be improved.Zr0 in auxiliary material2、 Sn02And La203For important alkaline-resisting modified auxiliary material, particularly Zr02There is good chemical stability, it is both alkaline-resisting or acidproof, but otherwise addition can increase tendency towards devitrification no more than the 5% of broken ore quality；Zr0 in auxiliary material2、 A1203, ZnO be important acidproof modified auxiliary material, but acidic igneous rock ore typically be rich in A1203, it has been a kind of excellent acid resisting material, typically need not have additionally added acidproof auxiliary material.During technological operation, after the auxiliary material added is sufficiently mixed in batch mixer, in input smelting furnace.
Manufacture method of the present invention is in compound smelting technology, and smelting temperature is between the melting temperature and boiling temperature of igneous rock.Ore is in tmdtStart fusing, temperature is higher, melt faster, while the corrosion to body of heater is bigger.Reach tb∞1Also Larger volatilization and ineffective energy consumption increase can be caused, and it is possible to cause melt to overflow.Therefore melting interval should be between ore melt temperature and boiling temperature, i.e. ore melting temperature tmelt+ 50 °C of ore boiling temperature tb<Ml-5(TC。
In the compound smelting technology of manufacture method of the present invention, melting atmosphere uses non-strong oxidizing atmosphere, including reducing atmosphere, nitriding atmosphere, vacuum environment, enclosed environment and at least one of melting in atmosphere, but do not include input oxygen or/and add the atmosphere of oxidant.Reducing atmosphere refers to inputting hydrogen, carbon monoxide or inert gas, or uses reducing agent such as powdered carbon (or the oxidable carbohydrate powder into carbon dust）, potassium tartrate, glass putty, antimony powder or aluminium powder, or electrode, the crucible made using graphite, or two or more methods describeds are used simultaneously.Reducing atmosphere can be Fe203FeO is converted into, so as to reduce Fe203/ FeO ratio, reaches the purpose for preventing crystallization, while the mechanical property of material can also be improved.The embodiment of the present invention uses the carbon dust of addition ore quality 1 3%, or/and uses graphite crucible, or/and uses graphite electrode, realizes reducing atmosphere.
Described nitriding atmosphere refers to input nitrogen N2Or ammonia NH3, or addition nitride, such as Si3N4, A1N, Li3N etc., or both use simultaneously.The present invention has suitably used nitriding atmosphere in the preparation of igneous rock mineral glass first（Referring to embodiment 3).This nitriding atmosphere is not used in traditional igneous rock smelting technology（Because nitriding atmosphere can prevent basalt glass ceramics crystallization, it can also increase basalt into the difficulty of silk）.The nitriding atmosphere technique that the present invention is used is to be blown into nitrogen 2 16 hours, or/and adds the Si of ore quality 1 3%3N4, A1N and Li3At least one of N, realizes nitriding atmosphere.After oxygen in glass material is replaced by nitrogen, oxynitride glass can be formed, modulus of elasticity, the corrosion-resistant and anti-wear performance of glass is improved.
Described vacuum environment, enclosed environment or in atmosphere melting because without input oxygen, and without oxidant, fall within non-strong oxidizing atmosphere, therefore Fe will not be increased substantially203/ FeO ratios.It is not easy crystallization in glass（Such as low Fe203/ FeO ratios, low iron content, pickling pre-process, have added anti-crystallization component）In the case of glass rupture is not concerned about（As finished product is relatively thin or is powder）In the case of, three kinds of melting environment can flexibly be used according to smelting furnace situation, for example, pan furnace can use vacuum environment, tank furnace can melting in atmosphere using enclosed environment, graphite crucible.
In the finished product preparation technology of manufacture method of the present invention, as needed, can using melt hookizations, clarify after using die casting, roll or be blow molded into shaping, glass devices are made, the melt after clarification can also be poured into chilling in water and scraped（Swash broken）Afterwards, powder is made.
This method wide adaptability, in the case of material composition fluctuation, it is ensured that product quality is stablized relatively, while product category is compared with basalt glass ceramics（That is cast stone）More enrich.Manufacture method of the present invention（Such as embodiment 1) obtained by modification intermediate igneous rocks continuous filament yarn be black gray expandable（Referring to Fig. 2), different from traditional golden yellow or brownish red basalt（That is alkaline igneous rocks) glass fibre.Manufacture method of the present invention（Such as embodiment 2) prepare cast(ing) surface without coarse wool pore, outward appearance and natural obsidian crystal（Obsidian), black agate（Firejade) same luxurious beauty（Referring to Fig. 3).Manufacture method of the present invention（Example Such as embodiment 3) acidic igneous rock for preparing（Perlite）Powder can be found in Fig. 4.
The present invention does not address part and is applied to prior art.
The specific embodiment of the present invention is given below.Specific embodiment is only used for that the present invention is further described, and does not constitute limiting to the claimed invention.
Embodiment 1
The present embodiment uses intermediate igneous rocks（Andesite basalt）Intermediate igneous rocks crystal glass is manufactured for raw material, the preparation of anti-crystallization technique and neutral mineral glass is realized, and detects the mechanics, calorifics, electromagnetism basic performance of conventional igneous rock crystal glass material.
The andesite basalt ore key component of the intermediate igneous rocks of 1. embodiment of table 1
Using intermediate igneous rocks described in table 1（Andesite basalt）Ore, is broken for below particle diameter 5mm particle, and then stirring immersion 0.5 hour in the sulfuric acid solution of 20% mass concentration ratio, is rinsed 0.5 hour in clear water.Add the Si0 of ore quality 1%2, 2% Zr02With 3% A1203, hook after mixed accessories and broken ore, in the closing kiln for putting into heated by natural gas, slowly 1500 °C be warming up to from 800 °C, be maintained at 1500 °C until being completely melt；Clarification one hour, then hooks furnace temperature within a hour and is reduced to 1000 °C, slowly cross crystallization area（Detection shows to have no obvious crystallization, referring to Fig. 5);Melt, which casts in be preheating in 600 °C of cast iron die, is shaped to sheet material, and product is without bursting or crystallization scraps generation.
In this batch of sample ore component, containing a large amount of Nucleating Agents, while Fe2O3/ FeO=1.13 0.5, but using pickling, a small amount of A1 of addition203(reduction tendency towards devitrification, increase intensity）Standing grain B Si02、 Zr02(improve viscosity, increase intensity, reduction thermal coefficient of expansion）Afterwards, crystallization can be ignored（See Fig. 5), the measure for illustrating anti-crystallization of the invention is feasible, easy.
Bending strength is igneous rock glass and glass ceramics a most weak mechanical property, therefore is used for the improvement that characterizes mechanical property.Basalt glass ceramics certified products bending strength is typically no less than 65MPa, and average value is about in 67MPa or so（Referring to Xiao state equality, " application of the glass-ceramic basalt technology in blast furnace slag flushing ditch ", Shandong is metallurgical, 25 (6)： 68-69, 2003；Xu Zhaoheng, " manufacture of cast stone ", today is scientific and technological, 1990 (3)：13,1990).The bending strength that the embodiment of the present invention 1 is modified igneous rock crystal glass is 131.19MPa, is approximately twice of parabasalt glass ceramics bending strength.If using electrical heat tracing mould, rather than using plain cast iron die casting, and extend annealing time, igneous rock crystal glass bending strength can also be significantly improved.Embodiment 1 illustrates, abandons traditional glass ceramic process and uses manufacture method of the present invention, not only Technique is simple, reduces energy consumption, extends the space of igneous rock mechanical castings improvement, and also improves product appearance, improves quality.
The intermediate igneous rocks crystal glass data of mechanical of 2. embodiment of table 1
Thermal coefficient of expansion is the leading indicator for weighing thermal stability, test show temperature T 100,300,500,700 °C when, the sample thermal coefficient of expansion of embodiment 1 be respectively 6.0688,6.6979,7.1705,7.4581 (10 "6/ °C, referring to Fig. 6), show that thermal coefficient of expansion increases with temperature T raising.Its equation of linear regression is：
Thermal coefficient of expansion（10-6/°C ) =0.0023T+5.9207 (R2L00-700 °C of=0.9736, Te) (formula 1) generally by specific insulation be more than 109Q.cm material, referred to as insulating materials, and the igneous rock glass specific insulation of embodiment 1 is 0.4-3.8xl012Q.cm, therefore be a kind of good insulating materials（Referring to table 3).When current displacement angle tangent is more than 0.01, dielectric loss material is called（Liu Shunhua etc., " electromagnetic wave shielding and absorbing material ", Chemical Industry Press, 2006), test shows that the current displacement angle of the gained igneous rock glass of embodiment 1 is all higher than 0.01, is a kind of weak dielectric loss material（Referring to table 3).
The intermediate igneous rocks crystal glass of 3. embodiment of table 1 basis electric property
Igneous rock glass is famous with its excellent heat-insulating property, and the sample of testing example 1 is found, its coefficient of heat conduction is 0.033 W.m^.K "1, belong to heat-insulating material.In addition to thermal and insulating performance is excellent, igneous rock deep processed product is also a kind of good heat-resisting sound-absorbing material（CN1884164,2006), therefore igneous rock glass has infrared stealthy, sonar hidden function concurrently.Electromagnetism detection finds that the dielectric constant and dielectric loss of the sample of embodiment 1 decline as frequency increases, and magnetic conductivity and magnetic loss are improved as frequency increases, and its electromagnetic performance quadratic fit curve is（Referring to Fig. 7-8):It is a kind of radar stealth material to illustrate the sample of embodiment 1, does not reflect radar wave, also the feature with micro suction ripple, be it is a kind of it is rare have that radar is stealthy, infrared stealthy three functions of stealthy, sonar material concurrently, military application prospect is wide.Described dielectric constant, dielectric loss, magnetic conductivity and magnetic loss calculation formula are as follows：
Permittivity ε '=- 0.0247 (GHz)2+0.1431(GHz)+7.6958 (R2=0.9987, GHze8.2-12.4) (formula 2);Dielectric loss s 〃=- 0.0133 (GHz)2+0.2269(GHz)-0.5974 (R2=0.9571, GHze 8.2-12.4) (formula 3);Magnetic conductivity '=0.0089 (GHz)2-0.1341(GHz)+1.3605 (R2=0.9985, GHze 8.2-12.4) (formula 4); Magnetic loss μ 〃=0.0026 (GHz)2-0.0481(GHz)+0.2388 (R2=0.9692, GHze 8.2-12.4) (formula 5).Embodiment 2
Embodiment 2 is to use alkaline igneous rocks ore（Basalt）The black crystal glass plate of preparation.Embodiment 2 is used to estimate least cost, while showing the minimum igneous rock crystal glass mechanical property lower limit of framework material.Sample will be used to prepare morion handicraft, that is, cut into mill after definite shape and be carved into type, or be put into mould, heat compressing.
The basalt ore key component of the alkaline igneous rocks of 4. embodiment of table 2
Basalt ore described in table 4, is the waste material below building stones factory particle diameter 5mm.Stirring immersion 8 hours, are rinsed 0.5 hour in clear water in the sulfuric acid solution of 20% mass ratio；Without any auxiliary material, quartz or corundum crucible are put into after drying, 1450 °C of meltings, clarification are heated in atmosphere；Heating into 600 °C of cast iron dies, be cast into after the glass plate that thickness is 10mm, be immediately placed in muffle furnace and anneal 8 hours, annealing ceiling temperature is 840 °C.
The alkaline igneous rocks crystal glass data of mechanical of 5. embodiment of table 2
Embodiment 3
The present embodiment sampling acidic igneous rock（Perlite）Ore prepares modified igneous rock powder.It realizes the preparation of acid mineral glass powder, examines product formula, reduction and the nitriding atmosphere technique for improving intensity.Dusty material will be used as the inserts of anticorrosive coating, and cement anticorrosion, insulation, the inserts of waterproof layer.
The perlite ore key component of the acidic igneous rock of 6. embodiment of table 3
Raw material is the crushed crude pearlite cleaned, adds ore quality（Yu Tong）1% Zr02With 1% La203, strengthen its anti-corrosion capability, while adding the B of ore quality 3%203Increase the strength of materials reduction coefficient of expansion；Protected using nitrogen（Nitrogen is blown into 10 hours, while adding the Si of ore quality 1%3N4) graphite crucible, be heated to 1800 °C of meltings.Melt flows into chilling in recirculated cooling water and scraped, and it is powder then to crush.Detection finds that the sample of embodiment 3 can be well combined with cement, is the higher cement base gel auxiliary material of activity（Referring to table 7). The sample of 7. embodiment of table 3 as cement inserts activity index
Embodiment 4
Embodiment 4 is to use alkaline igneous rocks ore（Basalt）The black crystal glass block of preparation.The present embodiment uses Non-energy-consumption annealing way, and the morion material of low cost can be provided for art glass, artistic crystal producer.
The basalt ore key component of the alkaline igneous rocks of 8. embodiment of table 4 Basalt ore described in table 8 is stone waste material of the particle diameter in below 5mm.Stirring immersion 2 hours, are rinsed 0.5 hour in clear water in the sulfuric acid solution of 20% mass ratio；The carbon dust of quality 1% is added after drying, the melting of closing smelting furnace, clarification is put into, smelting temperature is 1450 °C.Melt is embedded in swelling perlite powder immediately after being cast into four stupefied posts in warmed-up mould, and annealing is produced for 7 days.Find that the Mohs' hardness of products obtained therefrom is 6.5, better than the Mohs' hardness 5.5 of obsidian using the delineation contrast of the ores such as diamond, corundum, quartz, and the Mohs' hardness of common filter glass is suitable.Embodiment 5
Embodiment 5 uses alkaline igneous rocks ore（Basalt）And add the Si0 of ore quality 3%2, 1% Zr02, 0.8% Y203With 1% MgO, to improve the modulus of elasticity of basalt fibre.Ore stirs immersion 24 hours in the sulfuric acid solution of 20% mass ratio, is rinsed 0.5 hour in clear water.Compound is in 1500 °C of meltings, clarification, wire drawings, and gained fiber product modulus of elasticity is 98.21.It is as shown in the table that quantitative analysis measures the fiber product component：The alkaline igneous rocks crystal fiber important component percentage of 9. embodiment of table 5
Zr02 Y203 Si02 A1203 MgO CaO Na20 K20 Fe203+FeO Ti02
0.93 0.75 51.02 12.38 9.42 6.56 2.45 1.02 11.01 2.21

Claims (1)

  1. Claim
    1. a kind of composition for being used to prepare igneous rock crystal glass, it is characterised in that the composition is made up of igneous rock and auxiliary material, the igneous rock can be acid, neutral, alkalescence or hyperalkaline igneous rock building stones；The auxiliary material is Si02、 A1203、 MgO、 B203、 Zr02、 La203And Y203At least one of, the addition quality of the auxiliary material is the 1 30% of igneous rock quality.
    2. being used for according to claim 1 prepares the composition of igneous rock crystal glass, it is characterised in that the composition is made up of intermediate igneous rocks and auxiliary material, and the auxiliary material is by Si02、 A1203And Zr02Composition, wherein Si02Addition is the 1% of intermediate igneous rocks quality, A1203Addition is the 3% of intermediate igneous rocks quality, Zr02Addition is the 2% of intermediate igneous rocks quality.
    3. being used for according to claim 1 prepares the composition of igneous rock crystal glass, it is characterised in that the composition is made up of acidic igneous rock and auxiliary material, and the auxiliary material is by La203And Zr02Composition, wherein Zr02Addition is the 1% of acidic igneous rock quality, La203Addition is the 1% of acidic igneous rock quality.
    4. being used for according to claim 1 prepares the composition of igneous rock crystal glass, it is characterised in that the composition is made up of alkaline igneous rocks and auxiliary material, and the auxiliary material is by Si02、 Zr02、 Y203With MgO compositions, wherein Si02Addition is 3%, Zr0 of alkaline igneous rocks2Addition is 1%, Y of alkaline igneous rocks203Addition is that 0.8%, the MgO additions of alkaline igneous rocks are the 1% of alkaline igneous rocks.
    5. a kind of manufacture method of igneous rock crystal glass material, it is characterised in that carried out according to following processing steps：First igneous rock ore is pre-processed and then carried out melting, finally carry out the preparation of finished product；
    The pretreatment of the igneous rock ore is using washing or the method for acid washing and water washing；
    The smelting temperature of the smelting technology is one 50 °C of ore boiling temperature of+50 °C of ore melting temperature, and melting environment is non-strong oxidizing atmosphere；
    The finished product preparation technology is die casting, calendering or blow molding, or melt Quench it is broken after make powder.
    6. the manufacture method of a kind of igneous rock crystal glass material according to claim 5, it is characterised in that spent pickling acid is hydrochloric acid, nitric acid or the sulfuric acid of mass concentration 1 50%, and pickling stirring soak time is 0.5 24 hours.
    7. the manufacture method of a kind of igneous rock crystal glass material according to claim 5, it is characterised in that the non-strong oxidizing atmosphere is reducing atmosphere, nitriding atmosphere, vacuum environment, enclosed environment or air atmosphere.
    8. the manufacture method of a kind of igneous rock crystal glass material according to claim 7, it is characterised in that the reducing atmosphere is the carbon dust using addition 1 3%, or/and uses graphite crucible, or/and uses graphite electrode.
    9. the manufacture method of a kind of igneous rock crystal glass material according to claim 7, it is characterised in that described Nitriding atmosphere is to use to be blown into nitrogen 2 16 hours, or/and adds 1 3% Si3N4, A1N and Li3At least one of N.
    10. the manufacture method of a kind of igneous rock crystal glass material according to claim 5-9, it is characterised in that before pre-processing, be first crushed to ore particle diameter for 0.1-5mm to igneous rock ore.
    11. the manufacture method of a kind of igneous rock crystal glass material according to claim 5-10, it is characterised in that before melting is carried out, into pretreated igneous rock ore, addition auxiliary material, which is mixed, hooks, and the auxiliary material is Si02、 A1203、 MgO、 B203、 Zr02、 La203And Y203At least one of, the addition of auxiliary material is the 1 30% of igneous rock ore quality.
    12.-kind of the igneous rock crystal material prepared according to the method for claim 5, it is characterised in that include following components according to mass percent： Si02 45-90% A1203 5-25%, Fe203l-15%、 FeO 1-15%, MgO 1-15%, CaO 1-15%, Na20 1-15%, K20 1-15%, Ti02 0-5%, B2030-5%, Zr020-5%, La2030-5%, Y2030-5%。
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CN104973779B (en) * 2015-06-02 2019-01-01 安徽鑫泰玻璃科技有限公司 A kind of black glass production technology
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CN115140931A (en) * 2022-08-12 2022-10-04 烟台华正科信新材科技有限公司 Method for preparing basalt scales by adopting raw ores

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