CN103073307A - 1,050-DEG C calcium silicate ecological soluble environment-friendly refractory fibre - Google Patents
1,050-DEG C calcium silicate ecological soluble environment-friendly refractory fibre Download PDFInfo
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- CN103073307A CN103073307A CN2012105683689A CN201210568368A CN103073307A CN 103073307 A CN103073307 A CN 103073307A CN 2012105683689 A CN2012105683689 A CN 2012105683689A CN 201210568368 A CN201210568368 A CN 201210568368A CN 103073307 A CN103073307 A CN 103073307A
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Abstract
The invention discloses a 1,050-DEG C calcium silicate ecological soluble environment-friendly refractory fibre, which comprises the following materials by mass percent: 50-70 percent of SiO2, 20-40 percent of CaO, 0.5-1.0 percent of ZrO2, 0.1-0.5 percent of P2O5, and impurities less than 5 percent. The refractory fibre provided by the invention can replace ceramic refractory fibre, is soluble in human body fluid, and can also be decomposed and emitted, to reduce the damage for human body and to improve the production and use safety. Besides, the refractory fibre has sufficiently high high-temperature resistance and structural strength, and has a long-time working temperature reaching 1,050 DEG C.
Description
Technical field
The present invention relates to technical field of refractory materials, relate in particular to the ecological solubility environmental protection of a kind of 1050 degree Calucium Silicate powder refractory fibre.
Background technology
Nineteen forty-one (the Babcock﹠amp of U.S. Babcock ﹠ Wilcox Co. (B﹠W); Wilcox Co.) central institute finds to obtain a kind of shape fiber similar with asbestos with the stream thigh of compressed air spraying kaolin melt.China manufactures experimently the pottery refractory fibre since early 1970s, the general starting material such as flint clay, kaolin, quartz sand, aluminum oxide that adopt are by electric arc or resistance furnace melt production fiber, main component is Al2O3 and SiO2, and be successfully used to industrial furnace, and in the various industrial circles such as metallurgy, machinery, oil, chemical industry, electronics and light industry, be widely used.In addition, in the top science technology such as aerospace and nuclear power, also obtained application.World's Main Developed Countries all competitively develops ceramic fiber industry, and world's ceramic fiber gross annual output amount is own at present breaks through 300,000 tons.
The advantage of ceramic fiber is that use temperature is high, the applied at elevated temperature performance is good, but its maximum defective is non-degradable, harmful, this type of refractory fibre diameter is mostly below 6 μ m, and self property is crisp in addition, easily fracture produces fibre dust, very easily be inhaled in the human body, thereby affect HUMAN HEALTH, bring out inflammation in respiratory system even canceration.And environment caused certain harm.
Since 20th century the nineties, along with people to health, the pay attention to day by day of environmental protection, particularly developed country be in line with the product design concept that people-oriented, and the guide effect by some high-level policies.Therefore, international cancer research association is divided into the possibility carcinogen classfication according to the hazard rating of ceramic fiber to HUMAN HEALTH with it, has been subject to increasing use restriction in some developed countries.
European and American developed countries were obtaining significant achievement aspect the substitute of ceramic fiber-biodegradable refractory fibre exploitation in recent years, so that increasing biodegradable refractory fibre begins to come into the market, with its noticeable environmental protection concept the traditional ceramics fiber has been formed sizable impact.
Along with the needs of reinforcement and the accession to WTO of Environmental Protection in China law enforcement dynamics, 1998 by the Eco-environmental Issues in China investigation of materials strategy symposial that has been organized in Held In Beijing of the unit consolidations such as the 863 hi tech and new material domain expert councils of the Ministry of Science and Technology, National Natural Science Foundation of China.The result thinks, realizes Sustainable development in order to make China's economy, takes into account again when requiring to satisfy the use properties of material the development research type material is adhered in the Harmony aspect of ecotope.Exploitation and the bio-soluble refractory fibre that popularization has independent intellectual property right have important practical significance to realizing China's refractory ceramic fibre material industry Sustainable development for this reason.
Soluble ceramic fiber in the market has a variety of, such as the CMS system refractory fibre of the Themral Refractorys company of the FIBROX300 of the Fibrox technology company in the JM909 glass fibre of the Manville company of the U.S., Taiwan, Britain.Wherein more typical solubility refractory fibre composition is Isofrax and the Insulfrax of UnitfraxCorp Niagra Falls N.Y development.These two kinds of fiber applications are heat insulation at 980 ℃-1260 ℃.The Isofrax fiber is mainly by MgO (19%-26%) and SiO2 (72%-77%).Insulfrax fiber main component CaO (32%), MgO (3%), SiO2 (65%).
In the process of exploring bio-soluble ceramic fiber, a lot of countries are in the patent of all having applied for oneself aspect the soluble ceramic fiber composition.Combine the U.S., German various patents at the soluble ceramic fiber composition, take following composition (by weight percentage ratio) as feature: SiO245-65%, MgO 0-20%, CaO15-40%, K2O+Na2O 0-6% or SiO230-40%, Al2O316-25%, MgO 0-15%, K2O+Na2O 0-5%, P2O50-0.8%.Combine Britain in the various patents of soluble ceramic fiber composition, all take following composition (by weight percentage ratio) as 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, can also decompose, discharge, reduce the harm to human body, improve the security of producing and using; The ecological solubility refractory fibre of 1050 degree Calucium Silicate powder that has again sufficiently high resistance to elevated temperatures and structural strength.
Summary of the invention
Technical problem to be solved by this invention is, it is refractory fibre that a kind of alternative pottery is provided, and, both can be dissolved in human body fluid, can also decompose, discharge, reduce the harm to human body, improve the security of producing and using; The ecological solubility environmental protection of the 1050 degree Calucium Silicate powder refractory fibre that has again sufficiently high resistance to elevated temperatures and structural strength.
For solving the problems of the technologies described above, the invention provides the ecological solubility environmental protection of a kind of Calucium Silicate powder refractory fibre, wherein, mass percent is as follows: SiO
250-70%, CaO 20-40%, ZrO
20.5-1.0%, P
2O
50.1-0.5%, other foreign matter contents are not higher than 5%.
Perhaps, mass percent is as follows: SiO
250-60%, CaO 20-30%, ZrO
20.5-0.8%, P
2O
50.1-0.3%, other foreign matter contents are not higher than 5%.
Perhaps, the following SiO of mass percent
260-70%, CaO 30-40%, ZrO
20.8-1.0%, P
2O
50.3-0.5%, other foreign matter contents are not higher than 5%.
Perhaps, mass percent is as follows: SiO
255-65%, CaO25-35%, ZrO
20.6-0.9%, P
2O
50.2-0.4%, other foreign matter contents are not higher than 5%.
Perhaps, mass percent is as follows: SiO
258-62%, CaO32-36%, ZrO
20.7-0.8%, P
2O
50.3-0.4%, other foreign matter contents are not higher than 5%.
Maximum operating temperature of the present invention is 1050 degrees centigrade.
Purpose the invention also discloses a kind of 1050 and spends the manufacture method of the ecological solubility environmental protection of Calucium Silicate powder refractory fibres to better implement the present invention, and is as follows:
1, raw material mixes: by above-mentioned quality percentage composition, with wollastonite, quartz sand, zircon sand and P
2O
5Prepare burden for raw material, stirrer mixes it;
2, melting: the raw material that mixes is placed resistance furnace, through 1500～2000 ℃ of meltings;
3, get rid of silk cotton with collection: use tumbling machine with fused solution by getting rid of a mode, cotton through the condensers collection again, make product of the present invention.
The alternative pottery of the present invention is refractory fibre, and, both can be dissolved in human body fluid, 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 1050 degrees centigrade.
Embodiment:
Wollastonite is CaSiO
3Or CaOSiO
2, contain SiO
251.75%, CaO48.25%.Iron content, manganese, magnesium; Quartz sand is common quartz sand, i.e. SiO
2〉=97.5%, Fe
2O
3≤ 0.04,1750 ℃ of refractoriness.Theoretical (wB%): the ZrO that forms of zircon sand (zircon)
267.1%, SiO
232.9%.
Embodiment 1
Wollastonite with 70%, 29% quartz sand, 0.5% zircon sand and 0.5% P
2O
5Be raw material, mix, the raw material that mixes is placed resistance furnace, through 1500～2000 ℃ of meltings; Fused solution is by getting rid of a mode, and is cotton through the condensers collection, makes product of the present invention.
Embodiment 2
Wollastonite with 60%, 39% quartz sand, 0.5% zircon sand and 0.5% P
2O
5Be raw material, mix, the raw material that mixes is placed resistance furnace, through 1500～2000 ℃ of meltings; Fused solution is by getting rid of a mode, and is cotton through the condensers collection, makes product of the present invention.
Embodiment 3
Wollastonite with 51%, 48% quartz sand, 0.5% zircon sand and 0.5% P
2O
5Be raw material, mix, the raw material that mixes is placed resistance furnace, through 1500～2000 ℃ of meltings; Fused solution is by getting rid of a mode, and is cotton through the condensers collection, makes product of the present invention.
Embodiment 4
Wollastonite with 55%, 43.5% quartz sand, 1.0% zircon sand and 0.5% P
2O
5Be raw material, mix, the raw material that mixes is placed resistance furnace, through 1500～2000 ℃ of meltings; Fused solution is by getting rid of a mode, and is cotton through the condensers collection, makes product of the present invention.
Embodiment 5
Wollastonite with 65%, 34.4% quartz sand, 0.5% zircon sand and 0.1% P
2O
5Be raw material, mix, the raw material that mixes is placed resistance furnace, through 1500～2000 ℃ of meltings; Fused solution is by getting rid of a mode, and is cotton through the condensers collection, makes product of the present invention.
Embodiment 1-5 solubleness test result is as follows:
| ? | SiO 2 | CaO | ZrO 2 | Total meltage (ppm) | Heatproof degree ℃ |
| Ecological soluble fiber 24h solubleness | 153 | 53 | 9 | 215 | 1050 |
| Ecological soluble fiber 48h solubleness | 164 | 54 | 10 | 228 | 1050 |
The biology performance experiment
(1) animal is carried out the pulmonary toxicity test.Hamster is placed in the high density glass wool dust tests.Namely mouse is exposed to and sucks certain fiber by mouse is dissected, find whether mouse has fibrosis lesion with it.
Table 1-1 is different, and organism affects fibrolysis
| Different organisms | Mouse | The people |
| Suck the size (D μ m) of fiber | 0-5 | 0-10 |
| Scavenger cell size (μ m) | 12 | 17 |
| Fibrolysis rate every day (%) | 0.01 | 0.00015 |
| Half-life (my god) | 70 | 460 |
The direct labor is carried out the epidemic research statistical study and in the biometrics analysis and research of laboratory mouse simulation Bioexperiment according to oberdoset, proved that different bionts is different to suction and the fiber degraded in vivo of the fiber of different size, identical biodegradability is also different.Pottery be the refractory fibre Fibre diameter less than 6 μ m, 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.
Mineral fibre is different to the corrosion resistance of lung liquid, but what people were concerned about the most is that mineral fibre is in case by people's inspiration deep lung, how long can it exist in lung? according to Miller[i] etc. studies show that of people: mineral fibre depends on the chemical stability of fiber in human lung depths lifetime length, be its to the corrosion resistance of lung liquid, 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 different in the mouse lung.
Table 1-2 fiber various dissolvings and index thereof in simulation human body fluid and oxalic acid
Table?1-2Fibers?in?vitro?Soluti?onvalues
By to the 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, especially with B2O3 for.SiO2 is little on the dissolution rate impact.Because glass fibre is in wire drawing shaping, glass wool are being jetted forming process, virgin fibre is because the thermal stresses effect, can form tiny crack at the glass periphery, fiberglass surfacing contains some positively charged ions and has wetting ability in addition, infiltrated by lung liquid so the fiber surface in lung liquid is very easy, lung liquid pH=7.4 is slightly alkalescence, and the fiberglass surfacing tiny crack can enlarge, deepen under lung liquid corrode.To have increased fiberglass surfacing to amass on the one hand; The on the other hand tiny crack expansion of fiber, intensification and fibre strength descend, and accelerate it by scavenger cell " dissolving ".Make a thorough investigation of research and calculate the glass fibre constant of dissolution rate and be: 50～300ng/cm2h.
Based on above-mentioned materials, be refractory fibre, fibrous magnesium silicate with embodiment 1-5 and pottery, whether be dissolved in lung liquid about fiber and do experiment 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 is refractory fibre | No |
| Asbestos | No |
(2) animal is carried out the lung carcinogenicity test.Necessarily can suck in the fibre content air rat and each 10 routine long-term exposure of hamster, cut lung, see lung tumor whether occurs, 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 is refractory fibre | 7 examples appear in 10 examples | 6 examples appear in 10 examples |
| Asbestos | 6 examples appear in 10 examples | 4 examples appear in 10 examples |
Through above-mentioned several tables, can draw, embodiment 1-5 can be dissolved in lung liquid, is difficult for making human body silicosis to occur, and the probability that lung tumor occurs is low.
The fiber crystallization ability of embodiment 1-5
In getting rid of a process, the 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, strength decreased.Ceramic fiber produces crystallization in the process in order to avoid getting rid of, and mold temperature must be higher than the recrystallization temperature of raw material.Measuring the crystallization ceiling temperature is the key that determines mold temperature.In the use procedure of soluble ceramic fiber, along with the increase of time and temperature, crystallization appears in fiber may make filament contraction and destruction.
Glass for crystallization phases, is in the steady state that is situated between below its balance liquidus temperature, maximum system energy is higher, therefore the trend of oriented crystal transition.When glass generation crystallization changed, the variation of system total energy was by the difference Δ G of glassy phase and crystalline phase two-phase free energy of chemistry, the interfacial energy U of the crystalline phase of separating out and glassy phase formation
fWith strain energy U
sThree parts form.In the crystallization transition process of glass, U
f+ U
s=Δ G, the variation of therefore main consideration system free energy of chemistry.The nucleus that forms in the glass, its growth depend on the transition process of glassy phase and crystalline phase near interface atom.The vibrational frequency of atom be v its cross the interface from glassy phase and change crystalline phase over to and need activation energy.
It is v that atom is crossed the frequency that the interface changes crystalline phase over to from glassy phase
1=v exp[-E/ (RT)] in the formula, R is gas law constant, and T is thermodynamic temperature, and v is the atomic vibration frequency.Owing to the migration of atom causes system free energy decline Δ G.For reverse procedure, namely atom changes glassy phase over to from crystalline phase and need to cross potential barrier (E+ Δ G), and jump frequency is v
2=v exp[(E+ Δ G)/(RT)] so the clean jump frequency of atom from the glassy phase to the crystalline phase is v
1-v
2If nucleating surface growth one deck atom, phase interface migration distance be all then nucleus along one-dimensional square to growth velocity:
U＝λ(v?
1-v?
2)＝λv?exp(-E/(RT){1-exp[-ΔG/(RT)]} (1)
Make k
0=v{1-exp[-Δ G/ (RT)] } (2)
Then formula (1) can be write as U=λ k
0[exp (E/ (RT)], E is devitrification of glass activation energy.k
0Be commonly referred to as frequency factor, and be considered to irrelevant with temperature T, and in fact this only just strictly sets up under isothermal condition.For non-isothermal process, by formula (2) as can be known, k
0Relevant with T, as to try to achieve with diverse ways k
0Value differ sometimes an order of magnitude.Only in certain temperature range, the rising of temperature cause v increase and glassy phase and crystalline phase free energy difference Δ G reduce to cancel out each other a part time just can be similar to and regard constant as.
The present invention no longer includes crystallization and occurs through after Overheating Treatment.Can be found out by 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 of having improved to a certain extent fiber, reduced the tendency towards devitrification of system.The content of phosphorus unicorn of the present invention can further improve the flowing property after the 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 alternative pottery of the present invention is refractory fibre, and, both can be dissolved in human body fluid, 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 1050 degrees centigrade.
Claims (5)
1. the ecological solubility environmental protection of a degree Calucium Silicate powder refractory fibre is characterized in that, mass percent is as follows: SiO
250-70%, CaO 20-40%, ZrO
20.5-1.0%, P
2O
50.1-0.5%, other foreign matter contents are not higher than 5%.
2. according to the ecological solubility environmental protection of the 1050 described Calucium Silicate powder of degree claim 1 refractory fibre, it is characterized in that, mass percent is as follows: SiO
250-60%, CaO 20-30%, ZrO
20.5-0.8%, P
2O
50.1-0.3%, other foreign matter contents are not higher than 5%.
3. according to the ecological solubility environmental protection of the 1050 described Calucium Silicate powder of degree claim 1 refractory fibre, it is characterized in that the following SiO of mass percent
260-70%, CaO 30-40%, ZrO
20.8-1.0%, P
2O
50.3-0.5%, other foreign matter contents are not higher than 5%.
4. according to the ecological solubility environmental protection of the 1050 described Calucium Silicate powder of degree claim 1 refractory fibre, it is characterized in that, mass percent is as follows: SiO
255-65%, CaO25-35%, ZrO
20.6-0.9%, P
2O
50.2-0.4%, other foreign matter contents are not higher than 5%.
5. according to the ecological solubility environmental protection of the 1050 described Calucium Silicate powder of degree claim 1 refractory fibre, it is characterized in that, mass percent is as follows: SiO
258-62%, CaO32-36%, ZrO
20.7-0.8%, P
2O
50.3-0.4%, other foreign matter contents are not higher than 5%.
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|---|---|---|---|
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|---|---|---|---|
| CN2012105683689A CN103073307A (en) | 2012-12-12 | 2012-12-12 | 1,050-DEG C calcium silicate ecological soluble environment-friendly refractory fibre |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662077A (en) * | 2020-07-07 | 2020-09-15 | 湖北烁砺新材料科技有限公司 | 1260 ℃ biosoluble environment-friendly refractory fiber and preparation process thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1612845A (en) * | 2002-01-04 | 2005-05-04 | 摩根坩埚有限公司 | Saline soluble inorganic fibres |
-
2012
- 2012-12-12 CN CN2012105683689A patent/CN103073307A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1612845A (en) * | 2002-01-04 | 2005-05-04 | 摩根坩埚有限公司 | Saline soluble inorganic fibres |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662077A (en) * | 2020-07-07 | 2020-09-15 | 湖北烁砺新材料科技有限公司 | 1260 ℃ biosoluble environment-friendly refractory fiber and preparation process thereof |
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Application publication date: 20130501 |