CN103467101A - Rare earth green silicon carbide, application thereof and rare earth green silicon carbide abrasive grinding tool - Google Patents
Rare earth green silicon carbide, application thereof and rare earth green silicon carbide abrasive grinding tool Download PDFInfo
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Abstract
The invention relates to a rare earth green silicon carbide, an application thereof and a rare earth green silicon carbide abrasive grinding tool. Conventional green silicon carbide is low in hardness and toughness, is weak in grinding and cutting performances used as an abrasive, is easy to fragment and low in recovery value. Conventional rare earth cerium silicon carbide is worse in color, is instable in quality and performances as goods, and the quality and the performances are hard to measure. The rare earth green silicon carbide of the invention contains a trace amount of chlorides of rare earth elements. The quality and performances of the rare earth green silicon carbide is easy to measure, the appearance color is close to common green silicon carbide while the performances and usage value are better than those of common green silicon carbide and rare earth cerium silicon carbide. The rare earth green silicon carbide can be used as the abrasive, is substantially improved in microhardness and toughness, and is substantially improved in grinding and cutting performances. The rare earth green silicon carbide of the invention has good mechanical and corrosion resistant performances when used to manufacture a ceramic material. The rare earth green silicon carbide of the invention can be prepared into the rare earth green silicon carbide grinding tool which has better grinding performance.
Description
Technical field
The present invention relates to the solid inorganic material industrial circle, belong to the carbofrax material technology, particularly a kind of high tenacity, high rigidity, wear-resistingly cut, corrosion-resistant, resistant to elevated temperatures rare earth green silicon carbide material technology.
Background technology
Silicon carbide, as a kind of important solid inorganic material, is widely used in the fields such as grinding tool abrasive material, iron and steel and Non-ferrous Metallurgy, ceramic refractory, chemical industry, and Year's consumption is over 1,000,000 tons.Commodity silicon carbide is divided into two kinds of black silicon carbide and green silicon carbides, is all to adopt silica and carbon containing reducer (refinery coke, Graphite Powder 99, hard coal, charcoal etc.) to mix to make raw material at high temperature to smelt generation.Wherein, the smelting of green silicon carbide need to be added appropriate Industrial Salt in raw material, or adopts silica, the carbon containing reducer that purity is very high to smelt and could obtain.
Silicon carbide has high rigidity, from sword, higher physical strength, this makes it become one of most important abrasive material for grinding, cutting.Compare black silicon carbide, green silicon carbide purity is high, quality good, cutting property is superior, and color is pure, is difficult to doping, is widely used in recent years the cutting field of semi-conductor and sun power crystalline silicon, and annual consumption has approached 500,000 tons.Yet it is abnormal that green silicon carbide is applied in the photovoltaic silicon crystal-cut often can to occur the cutting that the hard spot in crystal causes, and cutting cost is also higher, after the silicon carbide after cutting reclaims, the recycling performance is not good.Reason is in silicon crystal, have the silicon carbide hard spot impurity of same hardness can have influence on cutting, and the toughness of green silicon carbide poor, be easy to fragmentation, in cutting, particle becomes rapidly protruding diminishing, cutting force dies down.
1973, Zhengzhou Abrasive Materials, Abrasive Tools, Grinding Inst. (CN) No.1 Huashan R developed a kind of novel silicon carbide, the called after cerium silicon carbide, and it is in salt-free green silicon carbide raw material, adds micro-cerium oxide, through smelting, obtains.Hardness and the toughness of cerium silicon carbide are high than green silicon carbide, as grinding materials and grinding tool raw material ratio green silicon carbide, have better grinding performance, and the highest grinding efficiency that improves is more than one times, and can reduce the damage to the grinding object.1978 and 1985, the national departments concerned popularization cerium silicon carbide of successively holding a meeting twice.Yet, because cerium silicon carbide appearance color and green silicon carbide differ greatly, and approach with black silicon carbide or green silicon carbide inferior, easily be considered to be mixed with black silicon carbide or other impurity, and black silicon carbide purity is low, cost is low, the cerium silicon carbide product of selling on market is difficult to be protected in quality control, graded product after its processing is also because of the narrow application range dull sale, make cerium silicon carbide be difficult to be accepted by market, just eliminated by green silicon carbide and common black silicon carbide gradually after the nineties.
Summary of the invention
One of purpose of the present invention is to overcome existing green silicon carbide lower hardness, defect that toughness is low, provides grinding and cutting property novel rare-earth green silicon carbide better, that simultaneously have strict outward appearance to distinguish with black silicon carbide again.A further object of the present invention is to provide the manufacture method of this novel rare-earth green silicon carbide, and the purposes of the abrasive material for grinding and cutting of this novel rare-earth green silicon carbide, and the purposes of making thyrite, silicon nitride combined silicon carbide material.Another object of the present invention is to provide a kind of rare earth green SiC abrasives, has better grinding performance.The objective of the invention is to realize by following scheme.
The invention provides a kind of rare earth green silicon carbide, contain 0.01～3% with silication rare earth and carbonization rare earth form, exist with at least one element in next group rare-earth element: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, it is characterized in that, also contain the muriate of this rare earth element of trace.Wherein, the muriatic cl content of the rare earth element of described trace is lower than 0.2%, and is preferably 0.01～999ppm, and 0.01～500ppm more preferably.Wherein, the rare earth element muriate of trace of the present invention closely is combined on the crystal grain of rare earth green silicon carbide or in the crystalline phase of crystal grain and on macroscopic view and distributes relatively equably, thereby makes after surface cleaning that the rare earth element muriate of described trace can not be by the crystal grain to described rare earth green silicon carbide or multi-stage crushing and clean institute and remove fully.
According to the present invention, the rare earth element contained in described rare earth silicon carbide is except the trace rare-earth chloride form with above-mentioned exists, and mainly form or the phase with silication rare earth or carbonization rare earth exists and be combined in carborundum grain.With molar content, weigh, the amount of rare earth element, exceed more than 5 times of chlorine amount of element, generally can exceed 10 times to 1000 times, even 100,000 times.For example, for the lanthanum cerium green silicon carbide that contains Rare Earth Lanthanum, cerium of the present invention, its lanthanum contained, cerium mainly exist with silication lanthanum, lanthanum carbide and silication cerium, cerium carbide form.
The present invention finds, contain the muriatic rare earth green silicon carbide of trace rare-earth, the more common rare earth green silicon carbide of chloride element not fully, there is better green appearance, make its color class be same as common green silicon carbide, and/or there is higher grain density, crystal grain has crystal boundary and defect concentration still less, and higher hardness, stronger toughness, higher resistance to compression and physical strength, and better high temperature resistant, corrosion resistance nature, better high temperature sintering performance.
The present invention finds, contain the muriatic rare earth green silicon carbide of trace rare-earth, the height of its rare earth chloride content, can indicate the relative superior or inferior of quality and the performance of described rare earth green silicon carbide: the content of rare earth chloride is lower, quality and the performance of described rare earth green silicon carbide are better, and the content of rare earth chloride is higher, quality and the performance of described rare earth green silicon carbide are poorer.Therefore, the rare earth green silicon carbide that contains micro-rare earth chloride, can, by measuring the content of its muriate or chlorine, monitor and control its quality, thereby greatly improve the value of its industrial application.
The present invention also provides the manufacture method that contains the muriatic rare earth green silicon carbide of trace rare-earth, comprise: according to following chemical equation: SiO2+3C--->SiC+2CO, to meet the silica containing raw material of quality proportioning of this chemical equation and the raw material of carbon containing, with the appropriate raw material containing rare earth, and appropriate chloride salt is mixed into mix, this mix is placed in to the resistance-type sic smelting furnace and carries out pyrotic smelting, take off resistance heater green silicon carbide on every side after cooling, through or without fragmentation, clean, dry, obtain the muriatic rare earth green silicon carbide of trace rare-earth that contains of the present invention.
The present invention finds, adopts higher smelting temperature, or leaves the nearer position of resistance heater, and what obtain contains the muriatic rare earth green silicon carbide of trace rare-earth, and its chlorinity is lower, even below 1ppm.
According to the manufacture method of rare earth green silicon carbide of the present invention, wherein, the described raw material containing rare earth can be rare earth or its compound arbitrarily, for example, and rare earth metal, rare earth oxide, rare earth carbonate, rare earth chloride, etc.
According to the manufacture method of rare earth green silicon carbide of the present invention, wherein, described chloride salt can be villaumite, for example sodium-chlor, calcium chloride, or Chlorates, for example sodium perchlorate, potassium perchlorate.For example, rare earth metal, rare earth oxide, rare earth carbonate, rare earth chloride, etc.
Particularly, according to a kind of manufacture method of rare earth green silicon carbide of the present invention, be, by carbonaceous materials such as the silica of suitable proportion, refinery cokes, and appropriate Industrial Salt, together with appropriate rare earth oxide, the common mixing, be placed in silicon carbide resistance smelting furnace, the energising heating, continue to smelt appropriate time, then the green silicon carbide that cooling, taking-up obtains, be rare earth green silicon carbide of the present invention.The time of smelting according to furnace binding, power and charge amount and difference needs 6～160 hours usually, makes mixing raw material be heated to 1600～2000 ℃ or higher, and maintains for some time.
The present invention finds, the rare earth green silicon carbide containing Micro Amounts of Chlorine of the present invention, and owing to having with respect to common black silicon carbide, green silicon carbide, hardness, toughness and sword that even common rare earth green silicon carbide is higher, and high-temperature stability, be suitable as abrasive material.For example, rare earth green silicon carbide of the present invention is used as to the abrasive material of manufacturing set on emery wheel, grinding tool, grinding knife tool, or, the coated abrasives on emery cloth, or the free abrasive as using in grinding or cutting, comprise dry grind material or dispersion liquid abrasive suspension.The latter's a concrete purposes is, by rare earth green silicon carbide of the present invention be mixed with line cutting suspension mortar, for the sliced crystal silicon chip.The hardness that it has higher than common silicon carbide, while making its cutting silicon, can avoid the detrimentally affect of silicon carbide hard spot to cutting in silicon crystal, and cutting efficiency is higher.
The present invention's discovery, owing to having physical strength and high temperature sintering performance preferably, rare earth green silicon carbide of the present invention also is applicable to manufacture stupalith.For example, rare earth green silicon carbide of the present invention, for the manufacture of thyrite, is made to micro mist aftershaping, the normal pressure-sintered rare earth green silicon carbide pottery of making of process by the rare earth green silicon carbide; Or make refractory ceramic material, as silicon carbide refractory brick, silicon carbide deck, silicon carbide kiln furniture, silicon carbide nozzle (comprising abrasive jets, high temperature slurry nozzle); Or make the high temperature corrosion-resisting stupalith, the anti-corrosion brick of silicon carbide of using as aluminum electrolytic tank, etc.Again for example, adopt rare earth green silicon carbide of the present invention to manufacture the silicon nitride combined silicon carbide pottery.The stupalith that adopts rare earth green silicon carbide of the present invention to make, have high breaking tenacity and good sintering character.
The present invention also provides a kind of rare earth green SiC abrasives, by base material, with the abrasive material anchored on base material, form, wherein, abrasive package contains of the present invention containing the muriatic rare earth green silicon carbide of trace rare-earth, wherein, described rare earth green silicon carbide contain total amount be 0.01～3% with silicide and carbide form, exist with at least one in next group rare-earth element: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium; Wherein, rare earth green silicon carbide abrasive material can adopt the methods such as sintering, bonding, plating, embedding, coating to anchor on base material.According to the difference of the aspects such as base material shape and material, this rare earth green SiC abrasives can be divided into the different grinding tools such as grinding abrasive disk, sand paper, grinding knife tool.Described " set ", comprise fixed set and coated set.
Further illustrate the present invention below in conjunction with embodiment.
Embodiment
Embodiment 1, a kind of rare earth green silicon carbide containing Micro Amounts of Chlorine, the weight percent of the present embodiment rare earth elements is 0.5%, rare earth element is taken from at least one in next group element for appointing: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 1～100ppm.
Embodiment 2, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is 0.01%, rare earth element is taken from at least one in next group element for appointing: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.01～1ppm.
Embodiment 3, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is 0.02%, rare earth element is taken from at least one in next group element for appointing: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.01～20ppm.
Embodiment 4, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is 2%, rare earth element is taken from at least 2 kinds in next group element for appointing: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 1～999ppm.
Embodiment 5, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is 0.05%, rare earth element is taken from at least one in next group element for appointing: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.01～100ppm.
Embodiment 6, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is 0.1%, rare earth element is taken from at least one in next group element for appointing: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.02～200ppm.
Embodiment 7, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is 0.2%, rare earth element is taken from at least one in next group element for appointing: yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.02～200ppm.
Embodiment 8, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is 0.3%, rare earth element is taken from at least one in next group element for appointing: yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.05～300ppm.
Embodiment 9, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is 0.4%, rare earth element is taken from at least one in next group element for appointing: yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.01～400ppm.
Embodiment 10, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is 0.6%, rare earth element is taken from at least one in next group element for appointing: yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.05～200ppm.
Embodiment 11, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is 0.7%, and rare earth element is taken from at least one in next group element for appointing: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
Embodiment 12, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is: 0.8%, rare earth element is taken from at least 3 kinds in next group element for appointing: yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.05～200ppm.
Embodiment 13, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is: 0.9%, rare earth element is taken from at least one in next group element for appointing: yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.2～200ppm.
Embodiment 14, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is: 1.0%, rare earth element is taken from at least one in next group element for appointing: yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 1～500ppm.
Embodiment 15, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is: 1.5%, rare earth element is taken from at least one in next group element for appointing: yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.3～1000ppm.
Embodiment 16, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is: 2.0%, rare earth element is taken from at least one in next group element for appointing: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.1～1000ppm.
Embodiment 17, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is: 3.0%, rare earth element is taken from at least one in next group element for appointing: yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.1～1100ppm.
Embodiment 18, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is: 4.0%, rare earth element is taken from at least one in next group element for appointing: yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.2～1200ppm.
Embodiment 19, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is: 5.0%, rare earth element is taken from at least one in next group element for appointing: yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the muriatic cl content of its trace rare-earth contained is 0.2～1000ppm.
Embodiment 20, a kind of rare earth green silicon carbide, the weight percent of the present embodiment rare earth elements is: 0.6%, rare earth element includes the mishmetal of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, wherein, and lanthanum 0.1%, cerium 0.3%, neodymium 0.15%, other rare earth elements add up to 0.05%, and the muriatic cl content of its trace rare-earth contained is 0.02～200ppm.
Embodiment 21, a kind of rare earth green silicon carbide, and the weight percent of the present embodiment rare earth elements is: 0.7%, include yttrium, lanthanum, cerium mischmetal element, wherein, yttrium 0.15%, cerium 0.35%, lanthanum 0.2%, the muriatic cl content of its trace rare-earth contained is 0.02～300ppm.
Embodiment 22, and a kind of cerium green silicon carbide contains cerium 0.4% in green silicon carbide in the present embodiment.Wherein, cerium mainly exists with silication cerium, cerium carbide phase, and the muriatic cl content of its trace rare-earth contained is 0.01～100ppm.
Embodiment 23, and a kind of cerium green silicon carbide contains cerium 0.5% in green silicon carbide in the present embodiment.Wherein, cerium mainly exists with silication cerium, cerium carbide phase, and the muriatic cl content of its trace rare-earth contained is 0.01～999ppm.
Embodiment 24, and a kind of cerium green silicon carbide contains cerium 0.6% in green silicon carbide in the present embodiment, and the muriatic cl content of its trace rare-earth contained is 10ppm.
Embodiment 25, and a kind of cerium green silicon carbide contains cerium 0.3% in green silicon carbide in the present embodiment, and the muriatic cl content of its trace rare-earth contained is 1～10ppm.
Embodiment 26, and a kind of cerium green silicon carbide contains cerium 0.2% in green silicon carbide in the present embodiment, and the muriatic cl content of its trace rare-earth contained is 0.01～1ppm.
Embodiment 27, and a kind of cerium green silicon carbide contains cerium 0.1% in green silicon carbide in the present embodiment, and the muriatic cl content of its trace rare-earth contained is 0.01～0.1ppm.
Embodiment 28, and a kind of cerium green silicon carbide contains cerium 1.6% in green silicon carbide in the present embodiment, and the muriatic cl content of its trace rare-earth contained is 0.1～30ppm.
Embodiment 29, and a kind of cerium green silicon carbide abrasive material, contain cerium 0.6% in the present embodiment medium green silicon carbide abrasive, and wherein cerium mainly exists with silication cerium, cerium carbide form, and the muriatic cl content of its trace rare-earth contained is 0.01～1ppm.
Embodiment 30, and a kind of yttrium green silicon carbide contains yttrium 0.2% in green silicon carbide in the present embodiment, and the muriatic cl content of its trace rare-earth contained is 0.01～1ppm.
Embodiment 31, and a kind of lanthanum green silicon carbide contains lanthanum 0.3% in green silicon carbide in the present embodiment, and the muriatic cl content of its trace rare-earth contained is 0.01～1ppm.
Embodiment 32, and a kind of lanthanum cerium green silicon carbide, contain lanthanum 0.2%, cerium 0.3% in green silicon carbide in the present embodiment.Wherein, cerium mainly exists with silication cerium phase, and lanthanum mainly exists with silication lanthanum phase, and the muriatic cl content of its trace rare-earth contained is 0.01～1ppm.
Embodiment 33, and a kind of cerium yttrium green silicon carbide, contain yttrium 0.1%, cerium 0.4% in green silicon carbide in the present embodiment, and the muriatic cl content of its trace rare-earth contained is 0.01～1ppm.
Embodiment 34, and a kind of scandium cerium green silicon carbide, contain scandium 0.01% in green silicon carbide in the present embodiment, cerium 0.4%, and the muriatic cl content of its trace rare-earth contained is 0.01～1ppm.
Embodiment 35, a kind of manufacture method of rare earth green silicon carbide of the present invention: get the silica granule of purity 98%, the petroleum coke particles of carbon containing 90%, with appropriate granular Industrial Salt, powder-mixed rare earth oxide, be mixed together evenly, pack in sic smelting furnace, the energising heating is smelted 48 hours, cooling, take out electrode green silicon carbide on every side, obtain rare earth green silicon carbide of the present invention.It on average contains rare earth 0.5%, chloride 0.5ppm.
Embodiment 36, a kind of manufacture method of rare earth green silicon carbide of the present invention: get the silica granule of purity 97.5%, the petroleum coke particles of carbon containing 85%, with the granular Industrial Salt that accounts for raw material total amount 8%, account for the Powdered cerium oxide of raw material total amount 0.1%, be uniformly mixed together, in the sic smelting furnace of packing into, the energising heating is smelted 160 hours, cooling, take out green silicon carbide, obtain cerium green silicon carbide of the present invention, it is containing rare earth 0.25%, chloride average 1ppm.Through careful detection, can find, from progressively outwards can find the rare earth green silicon carbide of six positions near electrode, its cl content is respectively 0.01ppm, 0.1ppm, 1ppm, 10ppm, 100ppm, 999ppm.
Embodiment 37, a kind of manufacture method of rare earth green silicon carbide of the present invention: get appropriate amount of quartz sand, refinery coke, salt, weary material, silica powder, Graphite Powder 99, green secondary, yellow bulk, add appropriate content 90% mishmetal, after mixing, pack in sic smelting furnace, the energising heating is smelted 48 hours, cooling, takes out electrode green silicon carbide on every side, cleaning-drying, obtain of the present invention containing the muriatic rare earth green silicon carbide of trace rare-earth.Wherein, weary material, green secondary, yellow bulk, be the foundry returns during silicon carbide is produced.
The inventor finds, containing the muriatic rare earth green silicon carbide of trace rare-earth, can indicate this rare earth green silicon carbide whether to use chloride salt in manufacturing processed.The rare earth green silicon carbide that uses chloride salt to manufacture, although its production process is strong to equipment corrosion, raw material availability descends, its outward appearance of product, the quality and performance that obtain are better.Utilization detects in the rare earth green silicon carbide whether contain chlorine, and the content size of chlorine, can judge quality and the performance of this rare earth chlorine silicon carbide.And the detection by quantitative of Micro Amounts of Chlorine is relatively convenient.Like this, just make the evaluation of originally more complicated silicon carbide products quality and performance become simple, low-cost, thus, improved the commercial value of rare earth green silicon carbide.
Embodiment 38, a kind of purposes as abrasive material of rare earth green silicon carbide of the present invention: get cerium green silicon carbide of the present invention, fragmentation, cleaning, classification, the cerium green silicon carbide particle obtained is used as to the abrasive particle of emery wheel, through bonding, plating or sintering on the emery wheel substrate, make rare earth green silicon carbide emery wheel, can be used for the grinding of various Wimet.
Test shows, the emery wheel that uses cerium green silicon carbide of the present invention to make, for the grinding titanium alloy sample, than the emery wheel made from green silicon carbide, same substandard once finishing, but the sample quantities of the former grinding is the latter 2～3 times, show that cerium green silicon carbide emery wheel increases substantially than green silicon carbide emery wheel wearing quality.Find simultaneously, compare the green silicon carbide emery wheel, while using the multiple Wimet sample of cerium green silicon carbide wheel grinding, the tiny crack of specimen surface significantly reduces even disappearance, and grinding speed also increases significantly.
Embodiment 39, a kind of cerium green SiC abrasives containing micro-Cerium II Chloride: get metal or pottery, paper, cloth, binding agent etc. as base material, rare earth green silicon carbide abrasive grain is bonded on base material, obtain rare earth green SiC abrasives of the present invention.According to the present invention, described bonding can be the bonding of any kind, for example, paint or resin as the bonding of binding agent.
Embodiment 40, a kind of cerium green SiC abrasives containing micro-Cerium II Chloride: get metal as base material, will electroplate on base material containing the cerium green silicon carbide abrasive grain of micro-Cerium II Chloride, obtain rare earth green SiC abrasives of the present invention.
Embodiment 41, a kind of rare earth green SiC abrasives: get pottery as base material, rare earth green silicon carbide abrasive grain high temperature sintering of the present invention, on base material, is obtained to rare earth green SiC abrasives of the present invention.
Embodiment 42, a kind of rare earth green silicon carbide emery wheel: get resin as base material, rare earth green silicon carbide abrasive grain of the present invention is disperseed to be bonded in base material, make emery wheel, obtain rare earth green silicon carbide emery wheel grinding tool of the present invention.
Embodiment 43, a kind of purposes as abrasive material of rare earth green silicon carbide of the present invention: get rare earth green silicon carbide of the present invention, fragmentation, cleaning, classification, obtain the rare earth green silicon carbide molecule of D50=9 micron, multi-wire saw abrasive sand by this particle as crystalline silicon, be mixed into the suspension mortar with dispersion liquid, for the silicon chip cutting of silicon single crystal or polysilicon.
Embodiment 44, a kind of purposes as abrasive material of cerium green silicon carbide of the present invention: get 45～55 parts of the cerium green silicon carbide powders that D50 value of the present invention is 8～9 microns, be mixed into the suspension mortar with 55～45 parts of polyoxyethylene glycol dispersion liquids, for the silicon chip cutting of silicon single crystal or polysilicon.
Test shows, the silicon chip line cutting suspension mortar that uses cerium green silicon carbide of the present invention to make, for cutting solar energy polycrystalline silicon sheet, than the suspension mortar made from common green silicon carbide powder, silicon chip surface roughness, total thickness deviation TTV obviously descend, simultaneously, silicon chip collapse that limit, silicon fall, little unfilled corner fraction defective descends, the hard spot outage also significantly descends, and comprehensive qualified rate can improve 0.5～3% left and right.Simultaneously, cerium green silicon carbide size distribution after use is more concentrated, broken obviously minimizing, under microscope, the sword degree of particle also is significantly improved than green silicon carbide recovery sand, and the cutting power that the mortar cutting power of preparing again after recovery also reclaims green silicon carbide powder is significantly improved.This shows, uses the cerium green silicon carbide containing micro-Cerium II Chloride of the present invention as silicon chip cutting abrasive material, and than using green silicon carbide, cutting property and cost all have significant advantage.
Embodiment 45, a kind of purposes as abrasive material of cerium green silicon carbide of the present invention: get 25～30 parts of the cerium green silicon carbide powders that D50 value of the present invention is 8～9 microns, get 20～25 parts of the common green silicon carbide powders of identical D50 value, be mixed into the suspension mortar with 55～45 parts of polyoxyethylene glycol dispersion liquids, for the silicon chip cutting of silicon single crystal or polysilicon.
Embodiment 46, a kind of purposes as abrasive material of cerium green silicon carbide of the present invention: get 40～52 parts of the cerium green silicon carbide powders that D50 value of the present invention is 8～9 microns, get 3～5 parts of the boron carbide micro powders of identical or approaching D50 value, be mixed into the suspension mortar with 55～45 parts of polyoxyethylene glycol dispersion liquids, for the silicon chip cutting of silicon single crystal or polysilicon.
Embodiment 47, a kind of purposes as abrasive material of lanthanum cerium green silicon carbide of the present invention: get 45～55 parts of the lanthanum cerium green silicon carbide powders that D50 value of the present invention is 12～18 microns, be mixed into the suspension mortar with 55～45 parts of polyoxyethylene glycol dispersion liquids, can be used for the silicon ingot evolution cutting of silicon single crystal or polysilicon.
Embodiment 48, a kind of purposes as abrasive material of cerium green silicon carbide of the present invention: get 25～30 parts of the cerium green silicon carbide powders that D50 value of the present invention is 8～9 microns, with 20～25 parts of the common microcrystalline alumina micro mists of identical D50 value, be mixed into the suspension mortar with 55～45 parts of polyoxyethylene glycol dispersion liquids, for the multi-thread silicon chip cutting of silicon single crystal or polysilicon.
Get the cerium green silicon carbide containing cerium 0.5% of the present invention, measuring its microhardness is 36GPa, than green silicon carbide, exceeds 10～15%; The toughness values of measuring by static pressure method is 95～99%, and the raising of highly significant is arranged than the toughness values of green silicon carbide 80% left and right.Toughness values shows that under static pressure, abrasive grain keeps not broken ratio, cerium green silicon carbide toughness values data of the present invention show, under continuously compressive pressure when the cracked ratio of green silicon carbide abrasive grain reaches 20%, cerium green silicon carbide particle only has less than 5% generation fragmentation, and percentage of damage has reduced by 75%.According to the above-mentioned data of cerium green silicon carbide of the present invention, can expect, cerium green silicon carbide of the present invention is as abrasive material, and its grinding performance has the raising of highly significant than green silicon carbide.It, can be cut or the grinding hard spot because cerium silicon carbide has than the higher microhardness of silicon carbide hard spot in silicon smoothly for cutting silicon wafer, thereby will make the crystal silicon cutting can not be subject to the detrimentally affect of hard spot again.
Embodiment 49, cerium green silicon carbide of the present invention for the manufacture of stupalith: get cerium green silicon carbide powder of the present invention, through silicon carbide ceramics art breading such as batching, slurrying, moulding, sintering, make cerium green silicon carbide pottery.
Embodiment 50, cerium yttrium green silicon carbide of the present invention for the manufacture of the silicon nitride combined silicon carbide stupalith: get of the present invention containing the muriatic cerium yttrium of Trace Cerium yttrium green silicon carbide powder, with metallic silicon power, mix, process through silicon nitride combined silicon carbide ceramic processes such as batching slurrying, moulding, oven dry, nitrogen atmosphere sintering, make silicon nitride bonded silicon cerium yttrium green silicon carbide pottery of the present invention.
Embodiment 51, cerium yttrium lanthanum green silicon carbide of the present invention for the manufacture of the carborundum porous ceramics material: get of the present invention containing the muriatic cerium yttrium of Trace Cerium yttrium lanthanum lanthanum green silicon carbide powder, mix, moulding, the art breading such as burn till through ball milling with pore-forming material, additive, make cerium yttrium lanthanum green silicon carbide porous ceramics of the present invention.
Embodiment 52, cerium yttrium lanthanum green silicon carbide of the present invention for the manufacture of silicon carbide ceramics refractory brick: get of the present invention containing the muriatic cerium yttrium of Trace Cerium yttrium lanthanum lanthanum green silicon carbide powder, mix, slurrying, casting, drying, the art breading such as burn till through ball milling with binding agent, additive, make cerium yttrium lanthanum green silicon carbide ceramic fire resistant brick of the present invention.
The stupalith that adopts rare earth green silicon carbide of the present invention to manufacture, have good sintering character, and good mechanical property, corrosion resistance nature.
Embodiment 53, of the present invention containing the muriatic cerium yttrium of Trace Cerium yttrium lanthanum lanthanum green silicon carbide for the manufacture of carborundum coating: get of the present invention containing the muriatic cerium yttrium of Trace Cerium yttrium lanthanum lanthanum green silicon carbide powder, with binding agent, additive through ball milling mix, slurrying, make cerium yttrium lanthanum green silicon carbide coating of the present invention, this coating can be applied to material surface, form heatproof, anti-corrosion, wear-resisting, shock-resistant, there is good infrared radiation property, and the cerium yttrium lanthanum green silicon carbide coating of conduction.For example, it can be used for forming engine inner wall coating, coat of silicon carbide heating element, Industrial Stoves inside coating, etc.
Embodiment 54, useless lanthanum cerium green silicon carbide powder in the useless slurry formed after the suspension mortar that in embodiments of the invention 47, lanthanum cerium green silicon carbide abrasive material is made is used separates, reclaims, through cleaning, drying, obtain the useless lanthanum cerium green silicon carbide powder reclaimed, mix, slurrying, casting, drying, the art breading such as burn till through ball milling with binding agent, additive, make cerium yttrium lanthanum green silicon carbide ceramic fire resistant brick of the present invention.
Specification sheets of the present invention and embodiment are exemplary, consider the invention spirit that specification sheets and practice disclose herein, those skilled in the art is apparent, in the situation that do not depart from scope of the present invention or design, can make various modifications and variations to disclosed scheme and method.
Claims (10)
1. a rare earth green silicon carbide, contain 0.01～3% with silication rare earth and carbonization rare earth form, exist with at least one element in next group rare-earth element: scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, it is characterized in that, also contain the muriate of this rare earth element of trace.
2. rare earth green silicon carbide according to claim 1, is characterized in that, the muriatic cl content of described rare earth element is at 0.01～999ppm.
3. according to the described rare earth green silicon carbide of any one in claim 1～2, it is characterized in that, described rare earth element is cerium.
4. according to the described rare earth green silicon carbide of any one in claim 1～2, it is characterized in that, described rare earth element is yttrium.
5. according to the described rare earth green silicon carbide of any one in claim 1～2, it is characterized in that, described rare earth element is lanthanum.
According to the described rare earth green silicon carbide of any one in claim 1～5 for the manufacture of silicon nitride combined silicon carbide material.
According to the described rare earth green silicon carbide of any one in claim 1～5 for the manufacture of thyrite.
8. be used as abrasive material according to the described rare earth green silicon carbide of any one in claim 1～5.
9. the purposes of rare earth green silicon carbide according to claim 8, is characterized in that, by the rare earth green silicon carbide be mixed with line cutting suspension mortar, for the sliced crystal silicon chip.
10. a rare earth green SiC abrasives, consist of base material and the abrasive material anchored on base material, it is characterized in that, described abrasive material contains just like the described rare earth green silicon carbide of any one in claim 1～5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923570A (en) * | 2014-05-06 | 2014-07-16 | 济南大学 | Preparation method of rare earth-doped silicon carbide composite polishing powder |
| WO2022000997A1 (en) * | 2020-06-30 | 2022-01-06 | 山东天岳先进科技股份有限公司 | Rare earth element-doped silicon carbide powder |
| CN115608589A (en) * | 2022-11-03 | 2023-01-17 | 包头市安德窑炉科技有限公司 | Energy-saving method for spraying black body material on inner wall of steel rolling heating furnace |
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2012
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923570A (en) * | 2014-05-06 | 2014-07-16 | 济南大学 | Preparation method of rare earth-doped silicon carbide composite polishing powder |
| WO2022000997A1 (en) * | 2020-06-30 | 2022-01-06 | 山东天岳先进科技股份有限公司 | Rare earth element-doped silicon carbide powder |
| CN115608589A (en) * | 2022-11-03 | 2023-01-17 | 包头市安德窑炉科技有限公司 | Energy-saving method for spraying black body material on inner wall of steel rolling heating furnace |
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