CN102753496B - A kind of composition for the preparation of igneous rock crystal glass material, igneous rock crystal glass material and manufacture method thereof - Google Patents

A kind of composition for the preparation of igneous rock crystal glass material, igneous rock crystal glass material and manufacture method thereof Download PDF

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CN102753496B
CN102753496B CN201080049103.7A CN201080049103A CN102753496B CN 102753496 B CN102753496 B CN 102753496B CN 201080049103 A CN201080049103 A CN 201080049103A CN 102753496 B CN102753496 B CN 102753496B
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ore
volcanic rock
glass
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CN102753496A (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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  • 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 kind of preparation method of igneous rock crystal glass material comprises following processing step: ore reduction, broken ore pre-treatment, auxiliary material mixing, compound melting and finished product preparation.Described ore is volcanic rock.Broken ore pre-treatment adopts the method for washing or acid washing and water washing; Spent pickling acid is the hydrochloric acid of mass concentration 1 ~ 50%, nitric acid or sulfuric acid, and it is 0.5 ~ 24 hour that soak time is stirred in pickling; Auxiliary material is SiO 2, Al 2o 3, MgO, B 2o 3, ZrO 2, La 2o 3and Y 2o 3in at least one, auxiliary material add-on is 1 ~ 30% of ore quality; The smelting temperature of compound is ore melting temperature+50 DEG C ~ ore boiling temperature-50 DEG C, the non-strong oxidizing atmosphere of fusing environment.The igneous rock crystal glass material additionally providing a kind of composition for the preparation of volcanic rock glass material and obtain by described method.The method does not use fusing assistant and Strong oxdiative melting atmosphere, does not adopt Annealing Crystallization technique.The conforming product rate obtained is high, excellent property, beautiful appearance, and suitability is wide, and cost is lower.

Description

A kind of composition for the preparation of igneous rock crystal glass material, igneous rock crystal glass material and manufacture method thereof
Technical field
The present invention relates to mineral glass material preparation technology, be specially a kind of acidity, neutrality, alkalescence or hyperalkaline volcanic rock of utilizing and prepare the method for crystal glass material and the formula of use.
Background technology
Glass is a kind of non-crystalline solids, is formed by melt supercooled.Earth lava cools rapidly, just become volcanic rock (Igneous rocks) ore body of vitreous state, be commonly called as crystal or agate (as obsidian crystal Obsidian, black agate fire jade), Slow cooling just forms the common volcanic rock ore of non-glass state.People call crystal (or agate) natural volcanic rock glass, and to be different from simple glass, the mineral material prepared of the present invention's volcanic rock is also referred to as crystal glass (or agate) accordingly.
Volcanic rock accounts for 95% of earth's lithosphere, about has more than 700 kind.As the volcanic rock of earth skeleton, natural have the features such as intensity is high, stable chemical performance.The main skeleton component of volcanic rock is silicon-dioxide, aluminum oxide and ferric oxide, number (namely acid-basicity is strong and weak) volcanic rock according to dioxide-containing silica is divided into four large classes successively: 1. acidity (Felsic), dioxide-containing silica > 65%, as grouan, ryolite, dacite, perlite and obsidian etc.; 2. neutrality (Intermediate), dioxide-containing silica 52-65%, as diorite, andesite and basaltic andesite etc.; 3. alkalescence (Mafic), dioxide-containing silica 45-52%, as basalt, gabbro and diabase etc.; 4. hyperalkaline (Ultramafic), dioxide-containing silica < 45%, as peridotites and komatiite etc., one is micro-association jewel.The glass-ceramic of tradition volcanic rock cast product mainly basalt glass crystallization, Castingother product is rare in market.No. WO2003016232, patent reports a kind of after perlite powder or swelling perlite powder (a kind of acidic rock product) middle interpolation 15% caustic soda and limestone flux, casts the method for foam thermal insulation glass material.Because this material heat-insulating property and cost are all not as good as the swelling perlite powder as raw material, thus fail to promote.
1914, the glass annealing of France Francois Ribbe first found minerals, to before 500 DEG C, reheats 800 DEG C, is incubated 0.5-1.5 hour in the lehr, a large amount of crystallite can be generated in glass, thus improve intensity and the toughness (US1108007) of glass.1933, US1893382 patent reported the processing condition of production glass-ceramic under oxidation and reducing atmosphere further.1956, Dr.Stooky again this technological expansion to simple glass field (US2920971).1969, No. US3557575, patent is first the stupalith that this basalt glass is made, be called basalt glass pottery (Basaltic glass-ceramic), and suggestion melting under oxidizing atmosphere, anneal under non-strong oxidizing atmosphere, so far basalt glass ceramic process finalizes the design almost.Within 1956, glass-ceramic production technique is introduced into China, and its product is also referred to as devitrified glass (Devitrified glass), and mineral glass pottery is then called as cast stone (Cast stone).
The temperature of fusion of basalt ore is 1350-1500 DEG C (CN1789187,2004), as Fe in ore composition 2o 3during/FeO > 0.5, glass foundry goods just can generate crystallite under specific annealing conditions, becomes glass-ceramic, the nucleus of its xln Fe mainly in melt 2o 3and FeO.Usual volcanic rock ore Fe 2o 3/ FeO ratio is less than 0.5, and therefore melting needs to adopt oxidizing atmosphere, makes FeO be converted into Fe 2o 3.Usually found in atmosphere and can make Fe 2o 3/ FeO > 0.5, also can add oxygenant as NH further in the feed 4nO 3or MnO 2realize this goal (Cheng Jinshu etc., " devitrified glass ", Chemical Industry Press, Beijing, 2006).In order to reduce costs, basalt glass pottery utilizes basalt usually, or basalt and industrial residue are main raw material, through high melt, casting or calendering formation, then glass nucleation crystallization formed, the leading indicator characterizing its mechanical property is flexural strength, and one is between 30-80MPa.
Prepare traditional high Fe 2o 3the volcanic rock glass of/FeO ratio (> 0.5), high tendency towards devitrification, and crystallization becomes the technique of glass-ceramic to have following defect:
1. cost is high: a typical basalt glass ceramic production technology is the ammonium nitrate of interpolation 4% as oxygenant, 650 DEG C of insulations 4 hours after glass smelting, 880 DEG C of insulations produce crystallite in 1 hour, and then be annealed to room temperature (Cheng Jinshu etc., " devitrified glass ", Chemical Industry Press, Beijing, 2006).This technique insulating process of 5 hours, increases production energy consumption at double.
2. waste product is many: basalt glass is along with temperature decline viscosity can increase sharply (namely material property is short, quick solidifying) between shaping area, and melt forming interval and crystallization interval are closely in addition, and easy especially crystallization devitrification, becomes granulated slag shape waste material.And the basalt glass of high tendency towards devitrification, easier crystallization is scrapped.Cross crystallization district (crystallization ceiling temperature is about about 1260-1270 DEG C) avoid crystallization devitrification so must cool rapidly during glass casting.The thermal expansivity of basalt glass is large, and in the process becoming glass, cooling can crack because thermal stresses is excessive again, even scrap rapidly, thus causes waste product.The fluctuation of basalt glass complicated components, content, also much larger than simple glass, becomes the control more difficult than Ordinary microcrystalline glass of brilliant process.Annealing crystallization process, is easy to again produce waste product.Chinese building material net reports that a large amount of glass-ceramic enterprises qualification rate is all below 60%, has become the bottleneck of industry development.In addition glass ceramic board hardness is high, and the warpage after paving is difficult to leveling, there will be many coarse wool pores, there is no method process at present after polishing, and building materials market is difficult to accept (Chinese building material net is reported, www.bmlink.com/news/).And traditional basalt foundry goods, easier crystallization, more easily burst, crystallization control more difficult, its glass-ceramic qualification rate is lower.Basalt glass pottery outward appearance is plain as earthenware, and market comparatively simple glass pottery is limited to more, is mainly used in anticorrosion pipeline.
3. quality badness: in order to reduce viscosity and fusing point, people add fusing assistant (Cheng Jinshu etc., " devitrified glass ", Chemical Industry Press, Beijing, 2006 such as Wingdale, sodium carbonate, glass cullet and fluorite in basalt ore; Li Ping, Ou Zhi, " being correctly familiar with basalt fibre, glass fibre ", 2008 (3): 35-41; US4009015,1977), while raising tendency towards devitrification, also bring a lot of negative impact.Calcium ion in Wingdale increase glass fragility, shortening material property, raising can burst tendency while increase tendency towards devitrification.Sodium ion in sodium carbonate then destroys glass microtexture, reduces thermostability, chemical stability and physical strength.Glass cullet can raise the cost, reduce intensity, increase fragility.Fluorite main ingredient is CaF 2, fluorine cpd volatilization after stain air, glass industry has not advised using.Tradition basalt glass ceramic process generates crystallite, requires Fe 2o 3/ FeO > 0.5, and utilize melting in atmosphere or adopt strong oxidizing atmosphere (namely adding oxygenant or input oxygen) to improve this ratio.But discovered in recent years basalt glass Fe 2o 3/ FeO ratio is less, on the contrary the mechanical property of material better (Li Ping, Ou Zhi, be correctly familiar with basalt fibre, glass fibre, 2008 (3): 35-41; US4009015,1977).The raising of the mechanical property that crystallite brings, by Fe 2o 3/ FeO ratio increases and major part is offset.
4. limitation is large: traditional high Fe 2o 3the preparation method of/FeO ratio, high tendency towards devitrification basalt glass and glass-ceramic, its additive improving crystal forming rate deteriorates some physicochemical properties of material, limits the space that material property improves, and is not also suitable for acid and intermediate igneous rocks ore simultaneously.Because framework material SiO in acid and neutral ore 2and Al 2o 3ratio greatly improve, thus improve the viscosity of melt, also reduce material and become brilliant tendency.
Although glass-ceramic technique can improve the intensity of simple glass, for basalt glass pottery, the raising of intensity first by localized cracks or devitrification offset, then by fusing assistant, the destruction of glass properties to be offset, then also by Fe 2o 3/ FeO ratio increases offset, and loses and is greater than.The major cause causing strength of glass to decline is the flaw of glass itself, particularly the crackle on surface, after removal surface layer of glass, tensile strength can improve more than 10 times (Loewenstein, " continuous glass fibre manufacturing process ", China Standards Press, 2008).And cause the major cause of basalt glass surface crack to be exactly the high stress gradients that chilling and high thermal expansion coefficient cause and the strength of glass reduced by conventional art.In recent years, Ceramics Enterprises is being endeavoured to develop glass-ceramic (i.e. devitrified glass) product always.But " even to this day; how to capture the many difficulties of surface porosity, improve the quality of products, increase varieties and designs, reduce production cost; remain the critical point (Chinese building material net, www.bmlink.com/news/message/160393.html) being difficult to together go beyond." basalt glass ceramic industry, face the predicament of the market shrink especially.
Summary of the invention
For the deficiency that prior art exists, the technical problem that quasi-solution of the present invention is determined is: provide a kind of igneous rock crystal glass material and manufacture method and auxiliary material thereof to add scheme, this manufacture method and formula adopt anti-crystallization and optimize modification technology.Do not use fusing assistant and the Strong oxdiative melting atmosphere of deteriorated material property and raising devitrification of glass tendency, do not adopt basalt glass Annealing Crystallization technique, product qualified rate is high, product performance are excellent, beautiful appearance, suitability is wide, and cost is lower.
The technical scheme that the present invention solve the technical problem is, designs a kind of manufacture method of igneous rock crystal glass material, and this manufacture method comprises following processing step successively: ore pre-treatment, auxiliary material mixing, compound melting and finished product preparation; Described ore is volcanic rock, can carry out fragmentation according to the size of ore particles, and the broken ore particle diameter after ore reduction is 0.1-5mm; Described broken ore pre-treatment adopts the method for washing or acid washing and water washing; Spent pickling acid is the hydrochloric acid of mass concentration 1 ~ 50%, nitric acid or sulfuric acid, and it is 0.5 ~ 24 hour that soak time is stirred in pickling; The auxiliary material of described auxiliary material hybrid technique is SiO 2, Al 2o 3, MgO, B 2o 3, ZrO 2, La 2o 3and Y 2o 3in at least one, the add-on of auxiliary material is 1 ~ 30% of broken ore quality; The smelting temperature of described compound melting technology is ore melting temperature+50 DEG C ~ ore boiling temperature-50 DEG C, melting environment is non-strong oxidizing atmosphere, comprises reducing atmosphere, nitriding atmosphere, vacuum environment, enclosed environment and at least one in atmosphere in melting; Described finished product preparation technology comprises die casting, calendering or blow molding, or makes powder after the fragmentation of melt Quench.
In the preparation process in accordance with the present invention, the formula of use is made up of volcanic rock and auxiliary material, and add that quality is volcanic rock quality 1 ~ 30% of described auxiliary material, described volcanic rock carries out pre-treatment by washing or acid washing and water washing, and described auxiliary material is SiO 2, Al 2o 3, MgO, B 2o 3, ZrO 2, La 2o 3and Y 2o 3in at least one.
Utilize method of the present invention to prepare volcanic rock crystal material, comprise following component according to mass percent: SiO 245-90%, Al 2o 35-25%, Fe 2o 31-15%, FeO1-15%, MgO1-15%, CaO1-15%, Na 2o1-15%, K 2o1-15%, TiO 20-5%, B 2o 30-5%, ZrO 20-5%, La 2o 30-5%, Y 2o 30-5%.
Compared with prior art, manufacture method of the present invention is because have employed anti-crystallization composition and engineering, do not re-use and improve tendency towards devitrification, the fusing assistant reducing mechanical property and Strong oxdiative melting atmosphere (input oxygen or use oxygenant), thus have glass Slow cooling can be allowed shaping, reduce the feature of thermograde and thermal stresses gradient; Because have employed the auxiliary material reducing thermal expansivity, no longer adopt the fusing assistant increasing thermal expansivity, thus have the advantages that to reduce glass heat stress intensity; Because have employed the composition and engineering of reinforcing glass intensity, thus improve glass self crack resistance.These three measures of the present invention substantially increase yield rate and the mechanical property of material, no longer need to adopt crystallization to be the modified measures of glass-ceramic, therefore also improve outward appearance, reduce energy consumption.The bending strength of the embodiment of the present invention 1 gained sample is about the twice of existing market basalt glass pottery.
Igneous rock crystal glass and traditional basalt deep processed product have form, outward appearance, component, the scope of application, yield rate 5 big-difference: 1 traditional ore foundry goods the finished product are potteries that mineral glass is made, and the finished product of the present invention are glass; 2 glass-ceramic basalt outward appearances are as stone, tile fragment, and crystal glass outward appearance of the present invention is as morion, black agate; 3 traditional glass-ceramic basalts adopt high crystallization formula, with the addition of the auxiliary material utilizing crystallization, improve Fe simultaneously by oxidizing atmosphere 2o 3/ FeO ratio.The present invention adopts anti-crystallization auxiliary material, and resistance to fracture auxiliary material have employed simultaneously and do not improve or reduce Fe 2o 3the melting atmosphere of/FeO, the component of product differs widely; 4 traditional basalt deep processing methods are only applicable to alkaline igneous rocks, and this technology is applicable to whole acidity, neutrality, alkalescence and hyperalkaline volcanic rock, and resource utilization is improved greatly; 5 traditional cast stones coolings then become powder too slowly, then burst too soon, and scrap rate is high, and volcanic rock crystal can slow cooling shaping, substantially without waste product.
Accompanying drawing explanation
Fig. 1 is the manufacturing approach craft schematic flow sheet of igneous rock crystal glass material of the present invention;
Fig. 2 is the continuous filament yarn photo figure that the modification intermediate igneous rocks crystal glass material of manufacture method (embodiment 1) gained of igneous rock crystal glass material of the present invention manufactures;
Fig. 3 is the photo figure (3a is natural obsidian crystal bangle, and 3b is volcanic rock crystal slab goods) of the alkaline igneous rocks crystal glass material product of manufacture method (embodiment 2) gained of igneous rock crystal glass material of the present invention;
Fig. 4 is acidic rock crystal glass material (crystal) the powder photo figure of manufacture method (embodiment 3) gained of igneous rock crystal glass material of the present invention;
Fig. 5 is that the modification intermediate igneous rocks crystal glass material sample of manufacture method (embodiment 1) gained of igneous rock crystal glass material of the present invention has no obvious crystallization X-RAY test curve figure;
Fig. 6 is manufacture method embodiment 1 gained sample thermal expansivity test curve figure (unit: 10 of the present invention -6/ DEG C);
Fig. 7 is manufacture method embodiment 1 gained sample permittivity ε ' of the present invention, dielectric loss ε " test curve figure;
Fig. 8 is manufacture method embodiment 1 gained sample permeability μ ' of the present invention, magnetic loss μ " test curve figure.
Embodiment
The present invention is described further below in conjunction with embodiment and accompanying drawing thereof:
The manufacture method of the igneous rock crystal glass material of the present invention's design (is called for short manufacture method, see Fig. 1-8), this manufacture method comprises following processing step successively: ore reduction 1, broken ore pre-treatment 2, auxiliary material mixing 3, compound melting 4 and finished product prepare 5 (see Fig. 1); Described ore is volcanic rock, and broken ore particle size range is 0.1-5mm; Described broken ore pre-treatment adopts the method for washing or acid washing and water washing; Described pickling be hydrochloric acid, nitric acid or sulfuric acid with acid, the mass concentration of Acidwash solution is 1 ~ 50%, pickling stir soak time be 0.5 ~ 24 hour; The auxiliary material of described auxiliary material hybrid technique is SiO 2, Al 2o 3, MgO, B 2o 3, ZrO 2, La 2o 3and Y 2o 3in at least one, the add-on of auxiliary material is 1 ~ 30% of ore quality; The smelting temperature of described compound melting technology is ore melting temperature t melt+ 50 DEG C ~ ore boiling temperature t boil-50 DEG C, melting environment adopts non-strong oxidizing atmosphere (namely do not input oxygen, do not add oxygenant), comprises reducing atmosphere, nitriding atmosphere, vacuum environment, enclosed environment and at least one in atmosphere in melting; Described finished product preparation technology comprises die casting, calendering or blow molding, or makes powder after the fragmentation of melt Quench.
Volcanic rock described in manufacture method of the present invention comprises the large class volcanic rock of acidity, neutrality, alkalescence and hyperalkaline whole four.In ore reduction technique, the particle diameter of ore reduction one be designed to 0.1-5mm.Broken ore particle greatly not only melts slowly, and because fusing not exclusively forms calculus in finished product, powdery auxiliary material also easily may be made simultaneously to be leaked to bottom by the space between broken ore, cause batch mixing irregular, affect quality product in auxiliary material hybrid technique.Although broken ore is less, melt faster, energy consumption is lower, and meticulous stone flour easily flies upward, lumps, and causes dust and incomplete mixing.The particle diameter of broken ore of the present invention at more than 0.1mm, tank furnace with broken ore particle diameter at more than 0.25mm.Preferable particle size of the present invention is less than the stone field waste material broken ore of 5mm, and its price is lower, melting less energy intensive, particularly can omit ore reduction technique, raise the efficiency further, reduce costs; Or/and select particle diameter slightly larger than the stone field waste material broken ore of 5mm, pulverize easily, also can raise the efficiency, reduce costs.
Manufacture method of the present invention, in pretreatment technology, adopts washing or acid washing and water washing pre-treatment broken ore.The object of pickling is adopted to be more effectively remove impurity and remove the alkalimetal oxide destroying glass structure.Described pickling be hydrochloric acid, nitric acid or sulfuric acid with acid, the mass concentration of acid solution is 1 ~ 50%, pickling stir soak time be 0.5 ~ 24 hour.One employing clear water of pretreatment technology in the basalt deep processing preparation method of prior art rinses or alkali cleaning, and object is to retain basaltic basic component (CN101263090,2008).In order to reduce tendency towards devitrification, present invention employs the pretreatment process of suitable pickling, to reduce the content of alkaline matter in ore and Nucleating Agent.Volatile matter and other impurity can also be removed while pickling, improve melt viscosity, play the effect being lowered into brilliant tendency and improving material physicochemical property.
Manufacture method of the present invention, in auxiliary material hybrid technique, according to product design needs, adds auxiliary material SiO in the ratio of broken ore quality 1 ~ 30% 2, Al 2o 3, MgO, B 2o 3, ZrO 2, La 2o 3and Y 2o 3in at least one, to improve the devitrification resistance energy of glass material, mechanical property, corrosion resistance nature and thermal stability.Al in auxiliary material 2o 3, MgO and ZnO be anti-crystallization component, it can make the silicon-oxy tetrahedron of fracture reconnect, thus crystallization ability is declined; And the Al in auxiliary material 2o 3, B 2o 3and Ga 2o 3the extra-network ion that can reduce strength of electric field larger gathers, thus reduces tendency towards devitrification, wherein Al 2o 3anti-crystallization effect is the most remarkable, for embodiment is preferred.Basalt is a kind of common alkali volcanic rock, and basalt glass contains a large amount of alkalimetal oxide, and thermal expansivity is higher, easily causes bursting, and therefore adding auxiliary material can be SiO 2, Al 2o 3, ZrO 2, B 2o 3, MgO, ZnO 3in at least one, and remove alkalimetal oxide with pickling, reduce thermal expansivity, improve its thermal stability.Recent study finds, in glass material composition, introduce La 2o 3, Y 2o 3and/or TiO 2effectively can improve glass modulus, increase the toughness of glass, and introduce SiO 2, Al 2o 3and/or B 2o 3the intensity of glass can be improved.ZrO in auxiliary material 2, SnO 2and La 2o 3for important alkaline-resisting modification auxiliary material, particularly ZrO 2there is good chemical stability, both alkaline-resisting also acidproof, but addition is no more than 5% of broken ore quality, otherwise can tendency towards devitrification be increased; ZrO in auxiliary material 2, Al 2o 3, ZnO is important acidproof modification auxiliary material, but acidic rock ore one be rich in Al 2o 3, be a kind of acid resisting material of excellence, one does not need additionally to add acidproof auxiliary material.During technological operation, after the auxiliary material added fully mixes in mixer, drop in smelting furnace.
Manufacture method of the present invention is in compound melting technology, and smelting temperature is between the melting temperature and boiling temperature of volcanic rock.Ore is at t meltstart fusing, temperature is higher, melts faster, simultaneously larger to the corrosion of body of heater.Reach t boillarger volatilization and ineffective energy consumption also can be caused to increase, and likely cause melt to overflow.Therefore should between ore melt temperature and boiling temperature between smelting zone, i.e. ore melting temperature t melt+ 50 DEG C ~ ore boiling temperature t boil-50 DEG C.
In the compound melting technology of manufacture method of the present invention, melting atmosphere adopts non-strong oxidizing atmosphere, comprise reducing atmosphere, nitriding atmosphere, vacuum environment, enclosed environment and at least one in atmosphere in melting, but do not comprise input oxygen or/and add the atmosphere of oxygenant.Reducing atmosphere refers to inputting hydrogen, carbon monoxide or rare gas element, or use reductive agent as powdered carbon (or carbohydrate powder of oxidable one-tenth carbon dust), soluble tartrate, glass putty, antimony powder or aluminium powder, or the electrode, the crucible that use graphite to make, or use two or more described method simultaneously.Reducing atmosphere can Fe 2o 3be converted into FeO, thus reduce Fe 2o 3the ratio of/FeO, reaches the object stoping crystallization, can also improve the mechanical property of material simultaneously.The embodiment of the present invention adopts the carbon dust adding ore quality 1 ~ 3%, or/and use plumbago crucible, or/and use Graphite Electrodes, realizes reducing atmosphere.
Described nitriding atmosphere refers to input nitrogen N 2or ammonia NH 3, or add nitride, as Si 3n 4, AlN, Li 3n etc., or both use simultaneously.The present invention suitably employs nitriding atmosphere (see embodiment 3) first in the preparation of volcanic rock mineral glass.This nitriding atmosphere does not all adopt (because nitriding atmosphere can stop basalt glass ceramic junction crystallization, also can increase the difficulty that basalt becomes silk) in traditional volcanic rock melting technology.The nitriding atmosphere technique that the present invention adopts is blown into nitrogen 2 ~ 16 hours, or/and add the Si of ore quality 1 ~ 3% 3n 4, AlN and Li 3at least one in N, realizes nitriding atmosphere.After oxygen in glass material is replaced by nitrogen, can oxynitride glass be formed, improve Young's modulus, the corrosion-resistant and wear resisting property of glass.
Described vacuum environment, enclosed environment or in atmosphere melting because do not input oxygen, and do not add oxygenant, also belong to non-strong oxidizing atmosphere, therefore can not increase substantially Fe 2o 3/ FeO ratio.Crystallization is not easy (as low Fe at glass 2o 3/ FeO ratio, low iron content, pickling pre-treatment, add anti-crystallization component) and do not worry glass rupture when (as thinner in finished product or be powder) when, described three kinds of melting environment can adopt flexibly according to smelting furnace situation, such as, pan furnace can adopt enclosed environment, plumbago crucible can adopt vacuum environment, tank furnace can melting in atmosphere.
In the finished product preparation technology of manufacture method of the present invention, as required, utilize die casting, roll or be blow molded into shaping after melt homogenize, clarification can be adopted, make glass devices, also the melt after clarification can be poured into chilling in water scraps after (swash broken), makes powder.
The method wide adaptability, in material composition fluctuation situation, can ensure that quality product is relatively stable, and comparatively basalt glass pottery (i.e. cast stone) is abundanter for product category simultaneously.The modification intermediate igneous rocks continuous filament yarn of manufacture method of the present invention (such as embodiment 1) gained is black gray expandable (see Fig. 2), is different from golden yellow or red-brown basalt (i.e. alkaline igneous rocks) glass fibre of tradition.Cast(ing) surface prepared by manufacture method of the present invention (such as embodiment 2) without coarse wool pore, outward appearance and natural obsidian crystal (Obsidian), the same luxurious beauty (see Fig. 3) of black agate (Fire iade).Acidic rock (perlite) powder prepared by manufacture method of the present invention (such as embodiment 3) can see Fig. 4.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below.Specific embodiment only for further describing the present invention, does not form limiting to the claimed invention.
Embodiment 1
The present embodiment adopts intermediate igneous rocks (andesite basalt) for raw material manufacture intermediate igneous rocks crystal glass, realize the preparation of anti-crystallization technique and neutral mineral glass, and detect mechanics, calorifics, the electromagnetism fundamental property of conventional igneous rock crystal glass material.
The andesite basalt ore main ingredient of table 1. embodiment 1 intermediate igneous rocks
Adopt intermediate igneous rocks (andesite basalt) ore described in table 1, be broken for the particle of below particle diameter 5mm, then stir in 20% quality is than the sulphuric acid soln of concentration immersion 0.5 little time, rinse 0.5 hour in clear water.Add the SiO of ore quality 1% 2, 2% ZrO 2with 3% A1 2o 3, after Homogeneous phase mixing auxiliary material and broken ore, drop in the closed kiln of heated by natural gas, be slowly warmed up to 1500 DEG C from 800 DEG C, remain on 1500 DEG C until melt completely; Clarify one hour, then in one hour, furnace temperature is evenly reduced to 1000 DEG C, slowly cross crystallization district (detection shows to have no obvious crystallization, see Fig. 5); Melt casts in the cast iron die being preheating to 600 DEG C and is shaped to sheet material, and product is without to burst or crystallization scraps generation.
In this batch of sample ore component, containing a large amount of Nucleating Agent, Fe simultaneously 2o 3/ FeO=1.13 > > 0.5, but adopting pickling, adding a small amount of Al 2o 3(reduce tendency towards devitrification, gain in strength) and SiO 2, ZrO 2after (improve viscosity, gain in strength, reduce thermal expansivity), crystallization negligible (see Fig. 5), illustrates that the measure of the anti-crystallization of the present invention is feasible, easy.
Flexural strength is the most weak mechanical property of volcanic rock glass and glass-ceramic, is therefore used to the improvement characterizing mechanical property.Basalt glass pottery salable product flexural strength one be not less than 65MPa, mean value about about 67MPa (see Xiao state equality, " application of 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, and 1990 (3): 13,1990).The flexural strength of the embodiment of the present invention 1 modification igneous rock crystal glass is 131.19MPa, is about the twice of parabasalt glass-ceramic flexural strength.If adopt electrical heat tracing mould, but not adopt plain cast iron die casting, and extend annealing time, igneous rock crystal glass flexural strength also can be significantly improved.Embodiment 1 illustrates, abandons traditional glass ceramic process and adopts manufacture method of the present invention, and not only technique is simple, reduces energy consumption, extends the space that volcanic rock mechanical castings is improved, and also improves product appearance, improve quality.
Table 2. embodiment 1 intermediate igneous rocks crystal glass data of mechanical
Thermal expansivity is the leading indicator weighing thermal stability, and test shows that temperature T is 100,300,500,700 DEG C time, and embodiment 1 sample thermal expansivity is respectively 6.0688,6.6979,7.1705,7.4581 (10 -6/ DEG C, see Fig. 6), show that thermal expansivity increases with the raising of temperature T.Its equation of linear regression is:
Thermal expansivity (10 -6/ DEG C)=0.0023T+5.9207 (R 2=0.9736, T ∈ 100-700 DEG C) (formula 1)
Usually volume specific resistance is greater than 10 9the material of Ω 2.cm, is called insulating material, and embodiment 1 volcanic rock glass volume specific resistance is 0.4-3.8 × 10 12therefore Ω .cm is a kind of good insulating material (see table 3).When current displacement angle tangent is greater than 0.01, be called dielectric loss material (Liu Shunhua etc., " electromagnetic wave shielding and absorbing material ", Chemical Industry Press, 2006), test shows that the current displacement angle of embodiment 1 gained volcanic rock glass is all greater than 0.01, is a kind of weak dielectric loss material (see table 3).
Table 3. embodiment 1 intermediate igneous rocks crystal glass basis electric property
Volcanic rock glass is famous with the heat-insulating property of its excellence, and testing example 1 sample finds, its heat-conduction coefficient is 0.033W.m -1.K -1, belong to thermal insulation material.Except thermal and insulating performance excellence, volcanic rock deep processed product is also a kind of heat-resisting sound-absorbing material (CN1884164,2006) well, and therefore volcanic rock glass has infrared stealth, sonar hidden function concurrently.Electromagnetism detects and finds, the specific inductivity of embodiment 1 sample and dielectric loss increase along with frequency and decline, magnetic permeability and magnetic loss increase along with frequency and improve, its electromagnetic performance quadratic fit curve is (see Fig. 7-8): illustrate that embodiment 1 sample is a kind of radar stealth material, not reflected radar ripple, also have the feature that trace inhales ripple, be a kind of material having radar stealth, infrared stealth, stealthy three functions of sonar concurrently seldom, military application prospect is wide.Described specific inductivity, dielectric loss,
Magnetic permeability and magnetic loss calculation formula as follows:
DIELECTRIC CONSTANT ε '=-0.0247 (GHz) 2+ 0.1431 (GHz)+7.6958 (R 2=0.9987, GHz ∈ 8.2-12.4) (formula 2);
Dielectric loss ε "=-0.0133 (GHz) 2+ 0.2269 (GHz)-0.5974 (R 2=0.9571, GHz ∈ 8.2-12.4) (formula 3);
Magnetic permeability μ '=0.0089 (GHz) 2-0.1341 (GHz)+1.3605 (R 2=0.9985, GHz ∈ 8.2-12.4) (formula 4);
Magnetic loss μ "=0.0026 (GHz) 2-0.0481 (GHz)+0.2388 (R 2=0.9692, GHz ∈ 8.2-12.4) (formula 5).
Embodiment 2
Embodiment 2 is the black crystal glass plate adopting alkaline igneous rocks ore (basalt) to prepare.Embodiment 2, for estimating least cost, shows the igneous rock crystal glass mechanical property lower limit that framework material is minimum simultaneously.Sample will for the preparation of morion artwork, and after namely cutting into definite shape, mill is carved into type, or puts into mould, heating compression moulding.
The basalt ore main ingredient of table 4. embodiment 2 alkaline igneous rocks
Basalt ore described in table 4 is the waste material of building stones factory below particle diameter 5mm.In the sulphuric acid soln of 20% mass ratio, stir immersion 8 hours, rinse 0.5 hour in clear water; Do not add any auxiliary material, after drying, put into quartz or corundum crucible, be heated to 1450 DEG C of meltings, clarification in atmosphere; In burning heat in 600 DEG C of cast iron dies, being cast into thickness is after the sheet glass of 10mm, puts into muffle furnace immediately and anneals 8 hours, and annealing ceiling temperature is 840 DEG C.
Table 5. embodiment 2 alkaline igneous rocks crystal glass data of mechanical
Embodiment 3
The present embodiment sampling acidic rock (perlite) ore prepares modification volcanic rock powder.It achieve the preparation of acid mineral glass powder, examine the formula for a product of raising intensity, reduction and nitriding atmosphere technique.Powdered material will be used as the stopping composition of anticorrosive coating, and cement protection against corrosion, insulation, waterproof layer stopping composition.
The perlite ore main ingredient of table 6. embodiment 3 acidic rock
Raw material is cleaned perlite powder, adds the ZrO of ore quality (remaining same) 1% 2with 1% La 2o 3, strengthen its anti-corrosion capability, add the B of ore quality 3% simultaneously 2o 3increase the strength of materials and reduce the coefficient of expansion; Nitrogen protection is used (to be blown into nitrogen 10 hours, to add the Si of ore quality 1% simultaneously 3n 4) plumbago crucible, be heated to 1800 DEG C of meltings.Melt flows into chilling in recirculated cooling water and scraps, and then pulverizes as powder.Detecting and find, embodiment 3 sample energy and the good compound of cement, is active higher cement based gel subsidiary material (see table 7).
Table 7. embodiment 3 sample is as the activity index of cement stopping composition
Embodiment 4
Embodiment 4 is the black crystal glass block material adopting alkaline igneous rocks ore (basalt) to prepare.The present embodiment adopts Non-energy-consumption annealing way, can be art glass, morion material that artistic crystal producer provides low cost.
The basalt ore main ingredient of table 8. embodiment 4 alkaline igneous rocks
Basalt ore described in table 8 is the stone field waste material of particle diameter at below 5mm.In the sulphuric acid soln of 20% mass ratio, stir immersion 2 hours, rinse 0.5 hour in clear water; Dry the carbon dust of rear interpolation quality 1%, put into closed smelting furnace melting, clarification, smelting temperature is 1450 DEG C.Melt is imbedded in swelling perlite powder be cast into four stupefied posts in the mould of preheating after immediately, anneals 7 days and get final product.Adopt the ore delineation contrasts such as diamond, corundum, quartz to find, the Mohs' hardness of products obtained therefrom is 6.5, is better than the Mohs' hardness 5.5 of obsidian, suitable with the Mohs' hardness of common welding glass.
Embodiment 5
Embodiment 5 adopts alkaline igneous rocks ore (basalt) and adds the SiO of ore quality 3% 2, 1% ZrO 2, 0.8% Y 2o 3with 1% MgO, to improve the Young's modulus of basalt fibre.Ore stirs immersion 24 hours in the sulphuric acid soln of 20% mass ratio, rinses 0.5 hour in clear water.Compound is in 1500 DEG C of meltings, clarification, wire drawing, and gained fiber product Young's modulus is 98.21.It is as shown in the table that quantitative analysis records this fiber product component:
Table 9. embodiment 5 alkaline igneous rocks crystal fiber important component per-cent

Claims (11)

1. for the preparation of a composition for volcanic rock glass, it is characterized in that, described composition is made up of volcanic rock and auxiliary material, and described volcanic rock can be acid, neutral, alkaline or hyperalkaline volcanic rock building stones; Described auxiliary material is SiO 2, Al 2o 3, MgO, B 2o 3, ZrO 2, La 2o 3and Y 2o 3in at least one, add that quality is volcanic rock quality 1 ~ 30% of described auxiliary material.
2. the composition for the preparation of volcanic rock glass according to claim 1, is characterized in that, described composition is made up of intermediate igneous rocks and auxiliary material, and described auxiliary material is by SiO 2, Al 2o 3and ZrO 2composition, wherein SiO 2add-on be intermediate igneous rocks quality 1%, Al 2o 3add-on be intermediate igneous rocks quality 3%, ZrO 2add-on is 2% of intermediate igneous rocks quality.
3. the composition for the preparation of volcanic rock glass according to claim 1, is characterized in that, described composition is made up of acidic rock and auxiliary material, and described auxiliary material is by La 2o 3and ZrO 2composition, wherein ZrO 2add-on be acidic rock quality 1%, La 2o 3add-on is 1% of acidic rock quality.
4. the composition for the preparation of volcanic rock glass according to claim 1, is characterized in that, described composition is made up of alkaline igneous rocks and auxiliary material, and described auxiliary material is by SiO 2, ZrO 2, Y 2o 3with MgO composition, wherein SiO 2add-on is 3%, ZrO of alkaline igneous rocks 2add-on is 1%, Y of alkaline igneous rocks 2o 3add-on is 0.8%, MgO add-on of alkaline igneous rocks is 1% of alkaline igneous rocks.
5. a manufacture method for volcanic rock glass material, is characterized in that, carries out according to following processing step: first volcanic rock ore is carried out to pre-treatment, then carries out melting, finally carry out the preparation of finished product; The pre-treatment of described volcanic rock ore adopts the method for washing or acid washing and water washing; The smelting temperature of described melting technology is ore melting temperature+50 DEG C ~ ore boiling temperature-50 DEG C, and melting environment is non-strong oxidizing atmosphere; Described finished product preparation technology is die casting, calendering or blow molding, or makes powder after the fragmentation of melt Quench; Described non-strong oxidizing atmosphere is reducing atmosphere, nitriding atmosphere, vacuum environment or enclosed environment.
6. the manufacture method of a kind of volcanic rock glass material according to claim 5, is characterized in that, spent pickling acid is the hydrochloric acid of mass concentration 1 ~ 50%, nitric acid or sulfuric acid, and it is 0.5 ~ 24 hour that soak time is stirred in pickling.
7. the manufacture method of a kind of volcanic rock glass material according to claim 5, is characterized in that, described reducing atmosphere is the carbon dust adopting interpolation 1 ~ 3%, or/and use plumbago crucible, or/and use Graphite Electrodes.
8. the manufacture method of a kind of volcanic rock glass material according to claim 5, is characterized in that, described nitriding atmosphere adopts to be blown into nitrogen 2 ~ 16 hours, or/and add the Si of 1 ~ 3% 3n 4, AlN and Li 3at least one in N.
9. according to the manufacture method of a kind of volcanic rock glass material one of claim 5-8 Suo Shu, it is characterized in that, before pre-processing, being first crushed to ore particle diameter to volcanic rock ore is 0.1-5mm.
10. according to the manufacture method of a kind of volcanic rock glass material one of claim 5-8 Suo Shu, it is characterized in that, before carrying out melting, in pretreated volcanic rock ore, add auxiliary material mix, described auxiliary material is SiO 2, Al 2o 3, MgO, B 2o 3, ZrO 2, La 2o 3and Y 2o 3in at least one, the add-on of auxiliary material is 1 ~ 30% of broken ore quality.
Volcanic rock glass material prepared by 11. 1 kinds of methods according to claim 5, is characterized in that, comprise following component: SiO according to mass percent 245-90%, Al 2o 35-25%, Fe 2o 31-15%, FeO 1-15%, MgO 1-15%, CaO 1-15%, Na 2o 1-15%, K 2o 1-15%, TiO 20-5%, B 2o 30-5%, ZrO 20-5%, La 2o 30-5%, Y 2o 30-5%, each component sum is 100%.
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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
CN105366934A (en) * 2015-12-08 2016-03-02 四川航天拓鑫玄武岩实业有限公司 Pretreatment method used for preparing continuous volcanic fiber raw materials
CN109836118B (en) * 2017-11-27 2022-03-18 辽宁省轻工科学研究院有限公司 Preparation method of cast stone plate with andesite as main raw material
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