CN102557730B - Surface modification method for silicon carbide ceramic - Google Patents
Surface modification method for silicon carbide ceramic Download PDFInfo
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- CN102557730B CN102557730B CN 201110419263 CN201110419263A CN102557730B CN 102557730 B CN102557730 B CN 102557730B CN 201110419263 CN201110419263 CN 201110419263 CN 201110419263 A CN201110419263 A CN 201110419263A CN 102557730 B CN102557730 B CN 102557730B
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- silicon carbide
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- fusing assistant
- carbon modified
- anhydrous slufuric
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Abstract
The invention discloses a surface modification method for silicon carbide ceramic. According to the method, the ceramic is subjected to surface modification by reaction of compound high-temperature molten sulfate and the silicon carbide ceramic, and mullite fibers are grown on the surface of the silicon carbide ceramic by the chemical reaction of the silicon carbide ceramic and the sulfate. Under the condition that the strength of a silicon carbide body material is not reduced, the feature and the chemical properties of the silicon carbide body material are changed obviously. The silicon carbide/mullite compound material which is prepared by the method has high application value in the fields of ceramic industry, chemical industry, metallurgical industry and the like.
Description
Technical field
The present invention relates to the method for modifying of inorganic materials, be specifically related to a kind of novel method of silicon carbide ceramics surface modification.
Background technology
Silicon carbide ceramics is the compound of the high rigidity that formed by strong Si-C covalent linkage, high strength, high heat conductance, but Si and C all belong to the IV main group element, a little less than attracting electronic capability, are difficult to form ionic linkage.The Si-C bond energy of covalent bond is large, Stability Analysis of Structures, and air atmosphere is heated to 1000 ℃ of long-time uses and also is difficult for oxidized.Due to the stability of chemical structure make its extremely difficulty be modified, its surface can not connect by the method for chemical reaction other chemical group, so can not form stable bonding interface between silicon carbide ceramics and metal, polymer.Therefore in the urgent need to studying the novel method of silicon carbide ceramics surface modification.
Silicon carbide ceramics can be used for the fields such as semi-conductor industry, chemical industry, aerospace, optical precision instrument manufacturing.But the stable Si-C key of silicon carbide makes it be difficult for being modified, thereby causes being connected with element with other material, so, need first the silicon carbide ceramics modifying surface to be processed in many Application Areass.
Surface modification method for silicon carbide ceramic mainly contains: chemical vapour deposition; Physical vapor deposition; The inorganic coating modification; The organo silane coupling agent graft modification; The methods such as ion beam assisted depositing.Wherein chemical vapour deposition need to be used dangerous silane gas, and temperature of reaction need to be more than 1200 ℃; Physical vapor deposition needs complicated valuable plant and instrument, and the first high temperature distillation of the material require that deposits gasification just can be deposited on the surface of base material, thereby energy consumption is very high; The inorganic coating modification is to coat with other inorganic materials simple physics on matrix surface, thereby surface bonding is not tight, and coating material easily comes off; The organo silane coupling agent graft modification is to cause coupling agent and silicon carbide generation chemistry, form chemical bond and organic group is connected to the surface of silicon carbide ceramics matrix, thereby formed surface reforming layer is unimolecular layer, can not be used for the environment such as high temperature, high corrosion; The ion beam assisted depositing method is to utilize plasma body to carry out modification to matrix surface, and the method needs more complicated equipment, and the thickness of modified layer is limited in addition.
Summary of the invention
The object of the present invention is to provide a kind of method of brand-new silicon carbide ceramics surface modification, carry out oxidation to adopt high-temperature fusion salt pair silicon carbide ceramics surface.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of surface modification method for silicon carbide ceramic, detailed process carry out according to the following steps:
Step 1, anhydrous slufuric acid aluminium and fusing assistant are mixed and grinds evenly, obtain Tai-Ace S 150 and fusing assistant mixed powder, wherein, the quality of anhydrous slufuric acid aluminium satisfies with the quality for the treatment of carbon modified SiClx pottery: the aluminium element in anhydrous slufuric acid aluminium with treat that the mol ratio of the element silicon in carbon modified SiClx pottery is 3: (1～2), the quality of fusing assistant are quality and the quality sum for the treatment of carbon modified SiClx pottery 1～2 times of anhydrous slufuric acid aluminium;
Step 2 will treat that carbon modified SiClx pottery is embedded in Tai-Ace S 150 and fusing assistant mixed powder, naturally cooling after being incubated 1～2 hour under 900 ℃～950 ℃;
Step 3 will carbon modified SiClx pottery boils in boiling water bath to the fusing assistant of its remained on surface dissolves fully through treating of processing of step 2, then the silicon carbide ceramics after cooling, washing, drying obtain surface modification.
Above-mentioned fusing assistant is vitriolate of tartar or sodium sulfate.
The method that the present invention relates to does not belong to any method of existing modification, and the principle that adopts is also a kind of brand-new modification theory.Utilize high-temperature sulfuric acid salt to decompose the sulphur trioxide of generation the silicon carbide oxidation, the silicon oxide that generates is dissolved in the sulfate composite salt-melting, then react the surface that generates the mullite nano fiber and be attached to silicon carbide ceramics, the final composite structure that forms mullite fiber coating silicon carbide forms coarse mullite upper layer.Gained is material modified to be with a wide range of applications in fields such as ceramic industry, chemical industry, metallurgical industry.
At present, still do not utilize composite molten vitriol to the research report of silicon carbide ceramics modifying surface both at home and abroad.The applicant is carrying out finding the SO that the vitriol pyrolytic decomposition produces during molten-salt growth method prepares the nano material process
3Has extremely strong oxidisability, the Si-C covalent linkage in can the Zirconia/silicon carbide pottery and form mullite crystal whisker on its surface.This discovery belongs to first in the world, upward there is no relevant report both at home and abroad, has great using value.
The advantage of present method: change has occured in the silicon carbide ceramics surface property, and the surface has become Al-O key and Si-O key by the Si-C key; Technological process is simple, and is with low cost, is easy to industrialization promotion.Mainly contain following variation by the silicon carbide ceramics after present method modification: (a) variation has occured, mullite (3Al in the physical pattern on surface
2O
32SiO
2) whisker growth obviously increased specific surface area on the silicon carbide ceramics surface.(b) variation has occured in surface chemical property, has been become Al-O, the Si-O key of mullite by the Si-C covalent linkage of silicon carbide, and the formation of mullite crystal whisker makes the high-temperature oxidation resistance of silicon carbide ceramics matrix significantly improve.
Description of drawings
Fig. 1 is the stereoscan photograph for the treatment of carbon modified SiClx fracture in embodiment 1;
Fig. 2 is the stereoscan photograph of the silicon carbide fracture after modification in embodiment 1.
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment
Method of modifying of the present invention is to adopt the fused salt of Tai-Ace S 150-sodium sulfate or the fused salt of Tai-Ace S 150-vitriolate of tartar at high temperature to react with silicon carbide, and its reaction equation is as follows:
Al
2(SO
4)
3→γ-Al
2O
3+3SO
3 (1)
SiC+4SO
3→SiO
2+CO
2+4SO
2 (2)
3γ-Al
2O
3+2SiO
2→3Al
2O
3·2SiO
2 (3)
Decompose under Tai-Ace S 150 high temperature and generate γ-Al
2O
3And SO
3, SO
3Have extremely strong oxidisability in high-temperature molten salt, generate SiO with the silicon carbide ceramics reaction
2, CO
2And SO
2, γ-Al
2O
3And SiO
2Reaction generation mullite crystal whisker is coated on the surface of silicon carbide ceramics in fused salt, thereby realizes the modification to silicon carbide ceramics.Utilize the reaction of high temperature composite molten vitriol and silicon carbide ceramics to generate the mullite fiber bundle and silicon carbide ceramics is carried out surface modification, can make the silicon carbide ceramics surface topography occur obviously to change.This method of modifying is with a wide range of applications in fields such as ceramic industry, chemical industry, metallurgical industry.Specifically can be undertaken by following step:
Step 1, anhydrous slufuric acid aluminium and mixed being incorporated in ceramic mortar of fusing assistant are fully ground evenly, obtain Tai-Ace S 150 and fusing assistant mixed powder, wherein, the quality of anhydrous slufuric acid aluminium and treat that the quality of carbon modified SiClx pottery satisfies: the aluminium element in anhydrous slufuric acid aluminium is 3 with mol ratio between the element silicon for the treatment of in carbon modified SiClx pottery: (1～2), the quality of fusing assistant are the quality of anhydrous slufuric acid aluminium and the quality sum for the treatment of carbon modified SiClx pottery 1～2 times;
Step 2 will treat that carbon modified SiClx pottery is embedded in Tai-Ace S 150 and fusing assistant mixed powder, be placed in corundum crucible naturally cooling after the resistance furnace under 900 ℃～950 ℃ conditions is incubated 1～2 hour;
Step 3 will carbon modified SiClx pottery boils in boiling water bath to the fusing assistant of its remained on surface dissolves fully through treating of processing of step 2, then the silicon carbide ceramics after cooling, washing, drying obtain surface modification.
Be below the embodiment that the contriver provides, need to prove, following embodiment further explains to of the present invention, and the present invention is not limited to these embodiment.
The Tai-Ace S 150 of experiment use is placed under the condition of 300 ℃, oven dry can get anhydrous slufuric acid aluminium.
Embodiment 1:
Step 1, anhydrous slufuric acid aluminium and mixed being incorporated in ceramic mortar of fusing assistant sodium sulfate are fully ground evenly, obtain Tai-Ace S 150 and sodium sulfate mixed powder, wherein, the quality of anhydrous slufuric acid aluminium and treat that the quality of carbon modified SiClx satisfies: the aluminium element in anhydrous slufuric acid aluminium and treat that the mol ratio between element silicon in carbon modified SiClx pottery is 3: 2, be Al: the mol ratio of Si is 3: 2, and the quality of sodium sulfate is the quality and the quality sum for the treatment of carbon modified SiClx pottery of anhydrous slufuric acid aluminium;
Step 2 will treat that carbon modified SiClx pottery is embedded in Tai-Ace S 150 and fusing assistant mixed powder, naturally cooling after being incubated 1 hour under 900 ℃;
Step 3 will boil in boiling water bath that residual sodium sulfate dissolves fully to the silicon carbide ceramics surface through the carbon modified SiClx pottery for the treatment of that step 2 was processed, then the silicon carbide ceramics after cooling, washing, drying obtain surface modification.
Compare with original sample through the silicon carbide ceramics flexural strength of above process modification and there is no noticeable change.But change has occured in its surface topography, observes the variation of its microscopic appearance by stereoscan photograph.Fig. 1 is the fracture apperance of the original silicon carbide of the present embodiment, as can be seen from the figure, silicon carbide ceramics is fine and close sintered compact, and is tightly packed between the silicon carbide ceramics particle, the particle profile is clear but there is no obvious fibrous morphology, forms sharp-featured fracture apperance after brittle rupture; Fig. 2 is the pattern after the modification of the present embodiment process composite molten vitriol, can see that therefrom the surface is replaced by the fibre bundle of mullite, mullite fiber is from the Surface Vertical growth of silicon carbide ceramics, close-packed arrays forms mullite fiber bundle similar " hedgehog ", each fiber is the monocrystalline of a mullite, is formed by silicon-oxy tetrahedron and aluminum-oxygen tetrahedron alternative arrangement.As shown in table 1,2, the EDS power spectrum shows that considerable change has occured modification front and rear surfaces element.Unmodified silicon carbide energy spectrum analysis demonstration only has two kinds of elements of C and Si on fracture, weight percent is C 25.34%, and Si 74.66%, and atomic percent is C 44.24%, and Si 55.76%.After modification, the energy spectrum analysis of silicon carbide ceramics fracture shows, C, O, Al and four kinds of elements of Si are arranged, its weight percent is respectively: C16.49%, and O 31.12%, and Al 43.49%, Si 8.9%, four kinds of atomic percents corresponding to element are respectively: C 26.16%, O37.07%, and Al 30.72%, Si 6.4%, illustrates after modification to have generated mullite crystal whisker on the silicon carbide ceramics surface.Simultaneously by nitrogen adsorption desorption curve determination the variation of specific surface area before and after the silicon carbide ceramics modification, before modification, the specific surface area of silicon carbide ceramics is 5.5487m
2/ g, after modification, specific surface area is 14.1414m
2/ g illustrates that the specific surface area of modification silicon carbide ceramics obviously increases.
The unmodified silicon carbide of table 1
Silicon carbide after table 2 modification
| Element | Weight percent | Atomic percent |
| CK | 16.49 | 26.16 |
| OK | 31.12 | 37.07 |
| AlK | 43.49 | 30.72 |
| SiK | 8.90 | 6.04 |
| Total amount | 100.00 |
Embodiment 2:
This embodiment difference from Example 1 is: in this embodiment, the quality of sodium sulfate is the quality and 1.5 times of quality sum for the treatment of carbon modified SiClx pottery of anhydrous slufuric acid aluminium; Under 900 ℃, insulation is 2 hours.
Embodiment 3:
This embodiment difference from Example 1 is: the mol ratio of Al in this embodiment: Si is 3: 1, and the quality of sodium sulfate is the quality of anhydrous slufuric acid aluminium and the quality sum for the treatment of carbon modified SiClx pottery 2 times; Under 850 ℃, insulation is 1 hour.
Embodiment 4:
This embodiment difference from Example 1 is: the mol ratio of Al in this embodiment: Si is 3: 1, and the quality of sodium sulfate is the quality and the quality sum for the treatment of carbon modified SiClx pottery of anhydrous slufuric acid aluminium; Under 950 ℃, insulation is 1 hour.
Embodiment 5:
This embodiment difference from Example 1 is: the fusing assistant in this embodiment is vitriolate of tartar, and the quality of vitriolate of tartar is the quality and the quality sum for the treatment of carbon modified SiClx pottery of anhydrous slufuric acid aluminium; Under 900 ℃, insulation is 1 hour.
Embodiment 6:
This embodiment difference from Example 5 is: the quality of the vitriolate of tartar in this embodiment is the quality of anhydrous slufuric acid aluminium and the quality sum for the treatment of carbon modified SiClx pottery 1.5 times; Under 900 ℃, insulation is 2 hours.
Embodiment 7:
This embodiment difference from Example 5 is: the mol ratio of the Al in this embodiment: Si is 3: 1.5, and the quality of vitriolate of tartar is the quality of anhydrous slufuric acid aluminium and the quality sum for the treatment of carbon modified SiClx pottery 2 times; Under 930 ℃, insulation is 1 hour.
Embodiment 8:
This embodiment difference from Example 7 is: the quality of the vitriolate of tartar in this embodiment is the quality and the quality sum for the treatment of carbon modified SiClx pottery of anhydrous slufuric acid aluminium; Under 950 ℃, insulation is 1 hour.
Claims (1)
1. a surface modification method for silicon carbide ceramic, is characterized in that, detailed process is carried out according to the following steps:
Step 1, anhydrous slufuric acid aluminium and fusing assistant are mixed and grinds evenly, obtain Tai-Ace S 150 and fusing assistant mixed powder, wherein, the quality of anhydrous slufuric acid aluminium satisfies with the quality for the treatment of carbon modified SiClx pottery: the aluminium element in anhydrous slufuric acid aluminium with treat that the mol ratio of the element silicon in carbon modified SiClx pottery is 3:(1～2), the quality of fusing assistant is quality and the quality sum for the treatment of carbon modified SiClx pottery 1～2 times of anhydrous slufuric acid aluminium;
Step 2 will treat that carbon modified SiClx pottery is embedded in Tai-Ace S 150 and fusing assistant mixed powder, naturally cooling after being incubated 1～2 hour under 900 ℃～950 ℃;
Step 3 will carbon modified SiClx pottery boils in boiling water bath to the fusing assistant of its remained on surface dissolves fully through treating of processing of step 2, then the silicon carbide ceramics after cooling, washing, drying obtain surface modification;
Described fusing assistant is vitriolate of tartar or sodium sulfate.
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| CN113651633B (en) * | 2021-07-27 | 2022-10-21 | 武汉工程大学 | Mullite fiber reinforced silicon carbide ceramic filter tube and preparation method thereof |
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