800 degree of forsterite refractory fibresTechnical field
The present invention relates to technical field of refractory materials, particularly relate to a kind of 800 degree of forsterite refractory fibres.
Background technology
The central institute of nineteen forty-one Babcock & Wilcox Co. (B&W) of the U.S. (Babcock & WilcoxCo.), finds, with the stream stock of compressed air spraying kaolin melt, to obtain the fiber that a kind of shape is similar with asbestos.China manufactures experimently pottery refractory fibre from early 1970s, the starting material such as general employing flint clay, kaolin, quartz sand, aluminum oxide are by electric arc or resistance furnace melt production fiber, main component is Al2O3 and SiO2, and be successfully used to industrial furnace, and be widely used in the various industrial circles such as metallurgy, machinery, oil, chemical industry, electronics and light industry.In addition, in the top science such as aerospace and nuclear power technology, have also been obtained application.World's Main Developed Countries all competitively develops ceramic fiber industry, and current World Ceramic fiber gross annual output amount is own breaks through 300,000 tons.
The advantage of ceramic fiber is that use temperature is high, applied at elevated temperature performance is good, but its maximum defect is non-degradable, harmful, this type of refractory fibre diameter is mostly below 6 μm, and self property is crisp in addition, easy fracture produces fibre dust, very easily be inhaled in human body, thus affect HUMAN HEALTH, bring out inflammation in respiratory system even canceration.And certain harm is caused to environment.
Since 20th century the nineties, along with people are to health, the pay attention to day by day of environmental protection, particularly developed country in line with the product design concept that people-oriented, and by the guide effect of some high-level policies.Therefore, international cancer research association, according to the hazard rating of ceramic fiber to HUMAN HEALTH, is divided into possibility carcinogen classfication, has been subject to increasing use restriction in some developed countries.
European and American developed countries achieved significant achievement in the substitute-biodegradable refractory fibre exploitation of ceramic fiber in recent years, increasing biodegradable refractory fibre is made to start to come into the market, with the sizable impact to traditional ceramics processbearing astrocyte of its noticeable environmental protection concept.
Along with the reinforcement of Environmental Protection in China law enforcement dynamics and the needs of accession to WTO, within 1998, be organized in Beijing by unit consolidations such as the hi tech and new material domain expert council of the Ministry of Science and Technology 863, National Natural Science Foundation of China and held the symposial of Eco-environmental Issues in China investigation of materials strategy.Result is thought, in order to make China's economy realize Sustainable development, taking into account again and adhering to development research type material to the Harmony aspect of ecotope while being required to meet the use properties of material.Exploitation and popularization have the bio-soluble refractory fibre of independent intellectual property right for this reason, have important practical significance to realizing China's refractory ceramic fibre material industry Sustainable development.
Soluble ceramic fiber in the market has a variety of, as the CMS system refractory fibre of the JM909 glass fibre of the Manville company of the U.S., the FIBROX300 of the Fibrox technology company in Taiwan, the ThemralRefractorys company of Britain.Wherein more typical solubility refractory fibre composition is Isofrax and Insulfrax of UnitfraxCorpNiagraFallsN.Y development.These two kinds of fiber applications are heat insulation at 980 DEG C-1260 DEG C.Isofrax fiber is primarily of MgO (19%-26%) and SiO2 (72%-77%).Insulfrax fiber main component CaO (32%), MgO (3%), SiO2 (65%).
In the process exploring bio-soluble ceramic fiber, a lot of national patent of all having applied for oneself in soluble ceramic fiber composition.Combine the U.S., the German various patents at soluble ceramic fiber composition, with following composition (percentage) for feature: SiO245-65%, MgO0-20%, CaO15-40%, K2O+Na2O0-6% or SiO230-40%, Al2O316-25%, MgO0-15%, K2O+Na2O0-5%, P2O50-0.8%.Combine the various patents of Britain at soluble ceramic fiber composition, all with following composition (percentage) for feature: SiO240-67%, MgO0-12%, CaO20-45%, B2O30-15%, P2O50-5%.
In view of above-mentioned technical problem and background material, the present invention aims to provide a kind of alternative ceramic series refractory material, and, both can be dissolved in human body fluid, and can also decompose, discharge, reduce harm to human body, improve the security of producing and using; There is again the ecological solubility refractory fibre of 1050 degree of Calucium Silicate powder of sufficiently high resistance to elevated temperatures and structural strength.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of alternative pottery system refractory fibre, and, both can be dissolved in human body fluid, and can also decompose, discharge, reduce the harm to human body, improve the security of producing and using; There is again 1050 degree of Calucium Silicate powder ecological solubility environmental protection refractory fibre of sufficiently high resistance to elevated temperatures and structural strength.
For solving the problems of the technologies described above, the invention provides a kind of Calucium Silicate powder ecological solubility environmental protection refractory fibre, wherein, mass percent is as follows: SiO250-70%, CaO20-40%, ZrO20.5-1.0%, P2o50.1-0.5%, other foreign matter contents are not higher than 5%.
Or mass percent is as follows: SiO250-60%, CaO20-30%, ZrO20.5-0.8%, P2o50.1-0.3%, other foreign matter contents are not higher than 5%.
Or, the following SiO of mass percent260-70%, CaO30-40%, ZrO20.8-1.0%, P2o50.3-0.5%, other foreign matter contents are not higher than 5%.
Or mass percent is as follows: SiO255-65%, CaO25-35%, ZrO20.6-0.9%, P2o50.2-0.4%, other foreign matter contents are not higher than 5%.
Or mass percent is as follows: SiO258-62%, CaO32-36%, ZrO20.7-0.8%, P2o50.3-0.4%, other foreign matter contents are not higher than 5%.
Maximum operating temperature of the present invention is 1050 degrees Celsius.
Object to better implement the present invention, the invention also discloses the manufacture method of a kind of 1050 degree of Calucium Silicate powder ecological solubility environmental protection refractory fibre, as follows:
1, raw material mixing: form by above-mentioned percent mass, by wollastonite, quartz sand, zircon sand and P2o5for raw material is prepared burden, stirrer is mixed;
2, melting: the raw material mixed is placed in resistance furnace, through 1500 ~ 2000 DEG C of meltings;
3, silk is got rid of cotton with collection: use tumbling machine by fused solution by getting rid of a mode, more cotton through condensers collection, obtained product of the present invention.
The present invention alternative pottery system refractory fibre, and, both can be dissolved in human body fluid, and can also decompose, discharge, reduce the harm to human body, improve the security of producing and using; Have again sufficiently high resistance to elevated temperatures and structural strength, maximum operation (service) temperature of the present invention reaches 800 degrees Celsius.
Embodiment
Quartz sand: common quartz sand, i.e. SiO2>=90-99%Fe2o3≤ 0.060.02%, refractoriness 1750 DEG C.
One in olivine group, rhombic system, chemical formula Mg2SiO4, the normal hopcalite containing 2FeOSiO2 and a small amount of Na, K and Al.
Embodiment
Embodiment 1
With the forsterite of 80%, the quartz sand of 20% for raw material, mix, the raw material mixed is placed in resistance furnace, through 1500 ~ 2000 DEG C of meltings; Fused solution is by getting rid of a mode, cotton through condensers collection, and the obtained cellucotton base needing thickness, then through acupuncture, 500 ~ 650 DEG C of thermal treatments, eventually pass cutting, and clot forms ecological solubility environmental protection refractory fiber blanket.
Embodiment 2
With the forsterite of 85%, the quartz sand of 15% for raw material, mix, the raw material mixed is placed in resistance furnace, through 1500 ~ 2000 DEG C of meltings; Fused solution is by getting rid of a mode, cotton through condensers collection, and the obtained cellucotton base needing thickness, then through acupuncture, 500 ~ 650 DEG C of thermal treatments, eventually pass cutting, and clot forms ecological solubility environmental protection refractory fiber blanket.
Embodiment 3
With the forsterite of 75%, the quartz sand of 25% for raw material, mix, the raw material mixed is placed in resistance furnace, through 1500 ~ 2000 DEG C of meltings; Fused solution is by getting rid of a mode, cotton through condensers collection, and the obtained cellucotton base needing thickness, then through acupuncture, 500 ~ 650 DEG C of thermal treatments, eventually pass cutting, and clot forms ecological solubility environmental protection refractory fiber blanket.
Embodiment 4
With the forsterite of 70%, the quartz sand of 30% for raw material, mix, the raw material mixed is placed in resistance furnace, through 1500 ~ 2000 DEG C of meltings; Fused solution is by getting rid of a mode, cotton through condensers collection, and the obtained cellucotton base needing thickness, then through acupuncture, 500 ~ 650 DEG C of thermal treatments, eventually pass cutting, and clot forms ecological solubility environmental protection refractory fiber blanket.
Embodiment 5
With the forsterite of 90%, the quartz sand of 10% for raw material, mix, the raw material mixed is placed in resistance furnace, through 1500 ~ 2000 DEG C of meltings; Fused solution is by getting rid of a mode, cotton through condensers collection, and the obtained cellucotton base needing thickness, then through acupuncture, 500 ~ 650 DEG C of thermal treatments, eventually pass cutting, and clot forms ecological solubility environmental protection refractory fiber blanket.
Embodiment 1-5 solubleness test result is as follows:
| SiO2 | CaO | Total meltage (ppm) | Resistance to temperature DEG C |
| Ecological soluble fiber 24h solubleness | 153 | 53 | 208 | 800 |
| Ecological soluble fiber 48h solubleness | 164 | 54 | 218 | 800 |
Biology performance is tested
(1) pulmonary toxicity test is carried out to animal.Hamster is placed in high density glass wool dust and tests.Namely mouse be exposed to can suck certain fiber after through dissecting mouse, find whether mouse has fibrosis lesion with it.
Table 1-1 is different, and organism affects fibrolysis
| Different organism | Mouse | People |
| Suck the size (D μm) of fiber | 0-5 | 0-10 |
| Scavenger cell size (μm) | 12 | 17 |
| Fibrolysis rate every day (%) | 0.01 | 0.00015 |
| Half-life (my god) | 70 | 460 |
According to oberdoset, epidemic research statistical study and the biometric analysis research in lab mouse simulation Bioexperiment are carried out to direct labor, it is different for demonstrating different bionts to the suction of the fiber of different size and fiber degraded in vivo, and identical biodegradability is also different.Pottery system refractory fibre Fibre diameter is less than 6 μm, and generally speaking, this fiber is insoluble to Human Lung liquid, easily causes human body to suffer from silicosis, to human body have carcinogenic may, wherein more is cancer between lung cancer and skin.
The corrosion resistance of mineral fibre to lung liquid is different, but people are the most it is of concern that mineral fibre is once by people's inspiration deep lung, how long can it exist in lung? research according to people such as Miller [i] shows: mineral fibre depends on the chemical stability of fiber in human lung depths lifetime length, namely it is to the corrosion resistance of lung liquid, and this plays very important effect in its potential biological action.The chemical stability of fiber, namely its dissolution rate in chemical solution, depends primarily on its chemical composition, surface-area and condition of surface.And different fibers changes difference in mouse lung.
Table 1-2 fiber various dissolving and index thereof in simulation human body fluid and oxalic acid
Table1-2FibersinvitroSolutionvalues
By to oxide dissolution experimental study, the performance point of dissolution rate can be three major types: Al2O3 can reduce dissolution rate greatly.B2O3, BaO, Na2O, CaO, MgO can make dissolution rate increase, and are the most especially with B2O3.SiO2 is little on dissolution rate impact.Because glass fibre is being jetted in forming process at wire drawing shaping, glass wool, virgin fibre is due to thermal stresses effect, tiny crack can be formed at glass periphery, in addition fiberglass surfacing contains some positively charged ions and has wetting ability, so the fiber surface in lung liquid is very easily moistened by lung immersion, lung liquid pH=7.4 is in slightly alkaline, and fiberglass surfacing tiny crack can expand, deepen under lung liquid corrodes.Be the increase in fiberglass surfacing on the one hand to amass; The tiny crack of fiber expands, deepens and fibre strength decline on the other hand, accelerates it by scavenger cell " dissolving ".Make a thorough investigation of research and calculate glass fibre constant of dissolution rate and be: 50 ~ 300ng/cm2h.
Based on above-mentioned materials, by embodiment 1-5 and pottery system refractory fibre, fibrous magnesium silicate, whether be dissolved in lung liquid about fiber and test with mouse, be compared as follows:
| Group | Whether be dissolved in lung liquid |
| Embodiment 1 | Be |
| Embodiment 2 | Be |
| Embodiment 3 | Be |
| Embodiment 4 | Be |
| Embodiment 5 | Be |
| Pottery system refractory fibre | No |
| Asbestos | No |
(2) lung carcinogenicity test is carried out to animal.Being chronically exposed to rat and each 10 examples of hamster necessarily to suck in fibre content air, cuts lung, sees and whether occur lung tumor, be compared as follows
| Group | Rat | Hamster |
| Embodiment 1 | Without lung tumor | Without lung tumor |
| Embodiment 2 | Without lung tumor | 1 example |
| Embodiment 3 | Without lung tumor | Without lung tumor |
| Embodiment 4 | 1 example | Without lung tumor |
| Embodiment 5 | Without lung tumor | Without lung tumor |
| Pottery system refractory fibre | There are 7 examples in 10 examples | There are 6 examples in 10 examples |
| Asbestos | There are 6 examples in 10 examples | There are 4 examples in 10 examples |
Through above-mentioned several table, can draw, embodiment 1-5 can be dissolved in lung liquid, not easily makes human body occur silicosis, occurs that the probability of lung tumor is low.
The fiber crystallization ability of embodiment 1-5
Getting rid of in a process, soluble ceramic fiber raw material melt has tendency towards devitrification in various degree, and this tendency towards devitrification is referred to as crystallization property.
In the production of fiber, crystallization is definitely unallowed, and it will cause the fracture of fiber, and intensity reduces.Produce crystallization for avoiding getting rid of ceramic fiber in a process, mold temperature must higher than the recrystallization temperature of raw material.Measuring crystallization ceiling temperature is the key determining mold temperature.In the use procedure of soluble ceramic fiber, along with the increase of time and temperature, fiber occurs that crystallization may make filament contraction and destruction.
Glass is below its balance liquid liquidus temperature, and for crystallization phases, be in the steady state that is situated between, maximum system energy is higher, therefore the trend of oriented crystal transition.When glass generation crystallization changes, the change of system total energy is by the difference Δ G of glassy phase and crystalline phase two-phase free energy of chemistry, the interfacial energy U that the crystalline phase of precipitation and glassy phase are formedfwith strain energy Usthree part compositions.In the crystallization transition process of glass, Uf+ Us=Δ G, therefore mainly considers the change of system free energy of chemistry.The nucleus formed in glass, the transition process of glassy phase and crystalline phase near interface atom is depended in its growth.The vibrational frequency of atom be v its cross interface from glassy phase and proceed to crystalline phase and need activation energy.
It is v that atom crosses from glassy phase the frequency that interface proceeds to crystalline phase1in=vexp [-E/ (RT)] formula, R is gas law constant, and T is thermodynamic temperature, and v is atomic vibration frequency.System free energy decline Δ G is caused due to the migration of atom.For reverse procedure, namely atom proceeds to glassy phase from crystalline phase needs to cross potential barrier (E+ Δ G), and jump frequency is v2=vexp [(E+ Δ G)/(RT)] is so the clean jump frequency of atom from glassy phase to crystalline phase is v1-v2.If nucleating surface grows one deck atom, phase interface migration distance be all then nucleus along one-dimensional square to growth velocity:
U＝λ(v1-v2)＝λvexp(-E/(RT){1-exp[-ΔG/(RT)]}(1)
Make k0=v{1-exp [-Δ G/ (RT)] } (2)
Then formula (1) can be write as U=λ k0[exp (-E/ (RT)], E is devitrification of glass activation energy.K0be commonly referred to as frequency factor, and be considered to have nothing to do with temperature T, and in fact this only has and just strictly sets up under isothermal conditions.For non-isothermal process, from formula (2), k0relevant with T, the k tried to achieve with diverse ways0value differ an order of magnitude sometimes.Only in certain temperature range, the rising of temperature causes v to increase cancelling out each other with the reduction of the free energy difference Δ G of glassy phase and crystalline phase just can being similar to during a part regarding constant as.
The present invention, through after Overheating Treatment, no longer includes crystallization and occurs.As can be seen from above phenomenon, thermal treatment of the present invention can improve the performance of goods to a certain extent.After thermal treatment to a certain degree, the devitrification resistance of refractory fibre can be able to increase significantly.Phosphorus be added in the performance improving fiber to a certain extent, reduce the tendency towards devitrification of system.The content of phosphorus unicorn of the present invention, further can improve the flowing property after raw materials melt, improves the success ratio of blown fibre.And can be further large-scale commercial production and establish solid basis.
In sum, the present invention alternative pottery system refractory fibre, and, both can be dissolved in human body fluid, and can also decompose, discharge, reduce the harm to human body, improve the security of producing and using; Have again sufficiently high resistance to elevated temperatures and structural strength, maximum operation (service) temperature of the present invention reaches 800 degrees Celsius.