CN102530915A - Method for improving phenolic resin carbonized structure - Google Patents
Method for improving phenolic resin carbonized structure Download PDFInfo
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- CN102530915A CN102530915A CN201110437592XA CN201110437592A CN102530915A CN 102530915 A CN102530915 A CN 102530915A CN 201110437592X A CN201110437592X A CN 201110437592XA CN 201110437592 A CN201110437592 A CN 201110437592A CN 102530915 A CN102530915 A CN 102530915A
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Abstract
The invention belongs to the technical field of refractory materials, and mainly relates to a method for improving a phenolic resin carbonized structure. Through adding a catalyst into phenolic resins in advance, phenolic resins are carbonized to generate carbon nanotubes or carbon nanofibers during high temperature application; when phenolic resins prepared by the method of the invention are compared with common phenolic resins, the carbonized structure has greatly improved toughness, and significantly enhanced heat shock resistance.
Description
Technical field
The invention belongs to technical field of refractory materials, relate generally to a kind of method of improving used for refractory material resol carbonization structure.
Background technology
Resol has higher high temperature cohesive strength, and the toxic gas that at high temperature discharges is less, makes wedding agent and be widely used in fire resisting material field.Resol is added in the refractory materials, and carbonization forms the carbon network structure under use temperature, can stand 2000 ℃ high temperature.The carbon structure that forms after the common resol carbonization is a decolorizing carbon, compares with graphite carbon, and decolorizing carbon is prone to oxidation, is fragility, and this becomes a big shortcoming that influences its result of use.
The at present normal shortcoming that adopts following several method to alleviate the amorphous carbonization structure of resol: a kind of is in resol is done the refractory materials of wedding agent, to add graphite; The graphite heat conducting coefficient is high, heat shock resistance; In the refractory materials use, can effectively alleviate the thermal shock stress that huge temperature fluctuation brings, however the adding of graphite; Can increase the carbon content of refractory materials; Along with the development of smelting iron and steel as the Clean Steel direction, carbon content is high in the refractory materials can produce the phenomenon of carburetting in molten steel, influences the molten steel quality; Another kind method is pitch or tar to be mixed with resol to make be used as wedding agent; Can fold staggered or pattern structure by the carbonization form layers in the high temperature use; Can alleviate thermal shock stress preferably; And pitch and tar at high temperature all can discharge a large amount of toxic gases, and severe exacerbation Working environment, many refractory materialss use producer this all to be had restriction.
Summary of the invention
The objective of the invention is to propose a kind of method of improving used for refractory material resol carbonization structure; The method that is proposed can be improved used for refractory material resol high temperature cabonization structure; Make it be difficult for oxidation, improve thermal shock resistance, in the high temperature use, do not produce toxic gas.
Adopt following technical scheme for accomplishing the foregoing invention task:
In recent years, the discovery of carbon nanotube causes huge repercussion in scientific circles, and carbon nanotube is owing to its special nano tubular structure has the performance of a lot of excellences, and in thermomechanical property, the performance of its heat shock resistance very significantly.The present invention is employed in the method that adds catalyzer in the resol, makes resol carbonization in the high temperature use produce carbon nanotube or carbon nanofiber, thereby effectively improves resol high temperature cabonization structure.
The catalyzer that adopts among the present invention is metal nickel powder or nickelous chloride, and described metal nickel powder or nickelous chloride granularity are below 0.5 μ m; Described metal nickel powder or nickelous chloride through with solid phenolic resin or the premixed method of liquid phenolic resin; Join in the refractory materials; In 1000 ℃～1300 ℃ processes of burning till, catalyzer meeting cracking resol vaporization at high temperature gas makes its form with carbon nanotube or carbon nanofiber deposit; Make to form the inner carbon web frame that is dispersed with a large amount of carbon nanotubes or carbon nanofiber under the resol high temperature, improve toughness, the resistance to sudden heating of resol carbonization structure greatly.Adding catalyzer among the present invention is 0.5%～0.75% of resol weight; Because low melting point metal and metal-salt add-on can not be too big in the refractory materials; Adopt catalyzer and resol and method of mixing among the present invention; Can make the catalyzer usage quantity less, good catalytic activity satisfies the refractory materials request for utilization; In the method for improving resol high temperature cabonization structure that the present invention proposes; Add graphite simultaneously; Adopt the inventive method to make refractory materials and compare with the method for original adding graphite, the consumption of graphite can reduce 5%, in the refractory materials of made; Carbon content can reduce 5%, have with background technology in the suitable resistance to sudden heating of method one.
Description of drawings
Fig. 1 is that 0.75% metal nickel powder is made catalyzer, solid phenolic resin high temperature cabonization structure Photomicrograph.
Fig. 2 is that 0.5% nickelous chloride is made catalyzer, solid phenolic resin high temperature cabonization structure Photomicrograph.
Fig. 3 is that 0.6% metal nickel powder is made catalyzer, solid phenolic resin high temperature cabonization structure Photomicrograph.
Fig. 4 is that 0.7% nickelous chloride is made catalyzer, liquid phenolic resin high temperature cabonization structure Photomicrograph.
Embodiment
In conjunction with accompanying drawing the present invention is specified:
Embodiment 1
This instance adds resin quality percentage ratio in solid phenolic resin be 0.75% metal nickel powder; The nickel powder granularity is 0.1 μ m, and solid phenolic resin and metallic nickel dried bean noodles are mixed the 15min mixing, has the resol of catalyzer to make wedding agent with this uniform mixing and makes refractory materials; Fired 3 hours at 1100 ℃; The carbon nanotube that intersects that in resol carbonization structure, forms as shown in Figure 1, diameter is about 100nm, and length is about 3 μ m.
Embodiment 2
This instance adds resin quality percentage ratio in solid phenolic resin be 0.5% nickelous chloride; Solid phenolic resin and metallic nickel dried bean noodles are mixed the 15min mixing; There is the resol of catalyzer to make wedding agent with this uniform mixing and makes refractory materials, fired 3 hours, the carbon nanofiber that in resol carbonization structure, forms a large amount of groups bunch shape as shown in Figure 2 at 1000 ℃; Diameter is about 20nm, and length is about 1 μ m.
Embodiment 3
This instance adds resin quality percentage ratio in solid phenolic resin be 0.6% metal nickel powder; The nickel powder granularity is 0.5 μ m, and solid phenolic resin and metallic nickel dried bean noodles are mixed the 15min mixing, has the resol of catalyzer to make wedding agent with this uniform mixing and makes refractory materials; Fired 3 hours at 1300 ℃; As shown in Figure 3ly in resol carbonization structure, form a large amount of carbon nanotubes, diameter is about 100nm, and length is about 3 μ m.
Embodiment 4
This instance adds resin quality percentage ratio in liquid phenolic resin be 0.7% nickelous chloride; Add an amount of alcohol again, stirring is dissolved in the resol liquid nickelous chloride, makees wedding agent with this resol that is mixed with catalyzer and makes refractory materials; Fired 3 hours at 1150 ℃; The carbon managed network decussate texture that in resol carbonization structure, forms as shown in Figure 4, carbon pipe diameter is about 80nm, and length is about 5 μ m.
Claims (4)
1. method of improving resol carbonization structure; It is characterized in that: it is even in resol, to add catalyst mix in advance; Make resol carbonization in the high temperature use produce carbon nanotube or carbon nanofiber, thereby improve the toughness of resol carbonization structure; The said catalyzer that in resol, adds is metal nickel powder or nickelous chloride.
2. a kind of method of improving resol carbonization structure according to claim 1 is characterized in that: the add-on of described catalyzer is 0.5%～0.75% of a resol weight.
3. a kind of method of improving resol carbonization structure according to claim 1 is characterized in that: the metal nickel powder of said adding, nickelous chloride granularity are below 0.5 μ m.
4. a kind of method of improving resol carbonization structure according to claim 1 is characterized in that: described resol carbonization temperature scope is 1000 ℃～1300 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201110437592XA CN102530915A (en) | 2011-12-23 | 2011-12-23 | Method for improving phenolic resin carbonized structure |
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| CN201110437592XA CN102530915A (en) | 2011-12-23 | 2011-12-23 | Method for improving phenolic resin carbonized structure |
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| CN102530915A true CN102530915A (en) | 2012-07-04 |
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| CN201110437592XA Pending CN102530915A (en) | 2011-12-23 | 2011-12-23 | Method for improving phenolic resin carbonized structure |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103318880A (en) * | 2013-07-09 | 2013-09-25 | 中钢集团洛阳耐火材料研究院有限公司 | Method for low-temperature graphitization of phenolic resin |
| CN107140993A (en) * | 2017-07-13 | 2017-09-08 | 华北理工大学 | A kind of modified bonding agent |
| CN107309396A (en) * | 2017-07-14 | 2017-11-03 | 保定宁信新型材料有限公司 | A kind of preparation method of the low gas forming amount screen pack of used in aluminium alloy casting |
| CN110240466A (en) * | 2019-07-13 | 2019-09-17 | 南昌航空大学 | A kind of low-carbon Ultra-low carbon carbon containing refractory and preparation method thereof combined containing the micro-nano graphite flake phenolic resin of two dimension removed in situ |
| CN110282971A (en) * | 2019-07-13 | 2019-09-27 | 南昌航空大学 | A kind of zirconium carbon refractory and preparation method thereof of continuous casting immersion outlet low-carbon Ultra-low carbon |
| CN110330319A (en) * | 2019-07-13 | 2019-10-15 | 南昌航空大学 | A kind of aluminium carbon firing refractory material of low-carbon Ultra-low carbon and preparation method thereof |
| CN110330314A (en) * | 2019-07-13 | 2019-10-15 | 南昌航空大学 | A kind of steel-making refining inner lining of furnace low-carbon Ultra-low carbon mg-ca-carbon refractory and preparation method thereof |
| CN110330320A (en) * | 2019-07-13 | 2019-10-15 | 南昌航空大学 | A kind of aluminium silicon carbide carbon refractory of low-carbon Ultra-low carbon and preparation method thereof |
| CN111628181A (en) * | 2020-05-25 | 2020-09-04 | 常熟氢能源研究院有限公司 | Process for preparing gas diffusion layer for fuel cell by using wood as raw material |
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| CN1247212A (en) * | 1998-09-05 | 2000-03-15 | 中国科学院山西煤炭化学研究所 | Process for preparing mesoporous phenolic resin based spherical activated carbon |
| CN101254911A (en) * | 2007-12-14 | 2008-09-03 | 内蒙古科技大学 | Method for preparing carbon nano-tube and carbon nano-fibre by using phenol resin as carbon source |
| CN101553428A (en) * | 2006-10-31 | 2009-10-07 | 艾尔坎技术及管理有限公司 | Materials containing carbon nanotubes, process for producing them and use of the materials |
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Patent Citations (3)
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| CN1247212A (en) * | 1998-09-05 | 2000-03-15 | 中国科学院山西煤炭化学研究所 | Process for preparing mesoporous phenolic resin based spherical activated carbon |
| CN101553428A (en) * | 2006-10-31 | 2009-10-07 | 艾尔坎技术及管理有限公司 | Materials containing carbon nanotubes, process for producing them and use of the materials |
| CN101254911A (en) * | 2007-12-14 | 2008-09-03 | 内蒙古科技大学 | Method for preparing carbon nano-tube and carbon nano-fibre by using phenol resin as carbon source |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103318880A (en) * | 2013-07-09 | 2013-09-25 | 中钢集团洛阳耐火材料研究院有限公司 | Method for low-temperature graphitization of phenolic resin |
| CN103318880B (en) * | 2013-07-09 | 2015-07-22 | 中钢集团洛阳耐火材料研究院有限公司 | Method for low-temperature graphitization of phenolic resin |
| CN107140993A (en) * | 2017-07-13 | 2017-09-08 | 华北理工大学 | A kind of modified bonding agent |
| CN107309396A (en) * | 2017-07-14 | 2017-11-03 | 保定宁信新型材料有限公司 | A kind of preparation method of the low gas forming amount screen pack of used in aluminium alloy casting |
| CN107309396B (en) * | 2017-07-14 | 2019-04-02 | 保定宁信新型材料有限公司 | A kind of preparation method of the low gas forming amount filter screen of used in aluminium alloy casting |
| CN110240466A (en) * | 2019-07-13 | 2019-09-17 | 南昌航空大学 | A kind of low-carbon Ultra-low carbon carbon containing refractory and preparation method thereof combined containing the micro-nano graphite flake phenolic resin of two dimension removed in situ |
| CN110282971A (en) * | 2019-07-13 | 2019-09-27 | 南昌航空大学 | A kind of zirconium carbon refractory and preparation method thereof of continuous casting immersion outlet low-carbon Ultra-low carbon |
| CN110330319A (en) * | 2019-07-13 | 2019-10-15 | 南昌航空大学 | A kind of aluminium carbon firing refractory material of low-carbon Ultra-low carbon and preparation method thereof |
| CN110330314A (en) * | 2019-07-13 | 2019-10-15 | 南昌航空大学 | A kind of steel-making refining inner lining of furnace low-carbon Ultra-low carbon mg-ca-carbon refractory and preparation method thereof |
| CN110330320A (en) * | 2019-07-13 | 2019-10-15 | 南昌航空大学 | A kind of aluminium silicon carbide carbon refractory of low-carbon Ultra-low carbon and preparation method thereof |
| CN111628181A (en) * | 2020-05-25 | 2020-09-04 | 常熟氢能源研究院有限公司 | Process for preparing gas diffusion layer for fuel cell by using wood as raw material |
| CN111628181B (en) * | 2020-05-25 | 2021-07-23 | 常熟氢能源研究院有限公司 | Process for preparing gas diffusion layer for fuel cell by using wood as raw material |
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Application publication date: 20120704 |