CN105692589A - Preparation method of glassy carbon material based on modified phenolic resin precursor - Google Patents
Preparation method of glassy carbon material based on modified phenolic resin precursor Download PDFInfo
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- CN105692589A CN105692589A CN201610142651.3A CN201610142651A CN105692589A CN 105692589 A CN105692589 A CN 105692589A CN 201610142651 A CN201610142651 A CN 201610142651A CN 105692589 A CN105692589 A CN 105692589A
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- C01P2006/00—Physical properties of inorganic compounds
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Abstract
The invention discloses a preparation method of a glassy carbon material based on a modified phenolic resin precursor. Anti-oxidation modified phenolic resin is taken as a macromolecule prepolymer precursor for preparing glassy carbon, boron, silicon, titanium and other doping elements which can improve the oxidation resistance are introduced into phenolic resin, the mechanical property, the abrasion performance and the oxidation resistance of the prepared glassy carbon can be remarkably improved on the premise that a conventional preparation process of glassy carbon based on the macromolecule prepolymer precursor is not required to be changed substantially. Through further optimization and improvement of low-temperature curing, carbonization treatment and other process conditions, the preparation cycle is effectively shortened and energy consumption is reduced while the material performance is further improved.
Description
Technical field
The present invention relates to a kind of glass-like carbon material preparation method, particularly relate to a kind of glass-like carbon material preparation method based on phenol-formaldehyde resin modified presoma。
Background technology
Glass-like carbon, as a kind of novel material with carbon element, is referred to as glass-like carbon because of its fracture apperance and the similar glass of architectural feature。Glass-like carbon has needs excellent properties, such as: low-density, high intensity, high rigidity, high connductivity and high-termal conductivity, corrosion-resistant, wear-resistant, ventilative hardly and isotropism etc., it is widely used in electronics industry, semi-conductor industry, metallurgical industry, chemical industry, nuclear industry and medical domain etc.。The macromolecule prepolymer presoma preparing glass-like carbon material at present mainly has phenolic resin, furfuryl alcohol resin, poly furfuryl alcohol, polrvinyl chloride, polyimides etc.。Physical property according to macromolecule prepolymer presoma, by accurately controlling each step process parameter (as solidified heating rate, carbonization heating rate) of production process, can obtain the glass-like carbon goods of clean molding。
Using conventional polymer prepolymer presoma as raw material, the glass-like carbon prepared increasingly cannot meet the industrial circle urgent needs to having complicated shape and high performance material, such as high temp. mechanical sealing, graphite or C/C surface-sealing coating, surface oxidation-resistant painting, coating material etc., glass-like carbon performance requirement is more and more harsher, and its antioxygenic property, anti-wear performance need to improve further。
Chinese patent " CN102618841B; a kind of boron doped-glass Carbon Materials and preparation method thereof " adopts chemical gaseous phase depositing process, with graphite for depositing base, using Hydrocarbon as carbon source, using halogenation boron or borine as boron source, at 1100-1400 DEG C, prepare the glass-like carbon that boron doping amount is 2-15at%。The material structure even compact prepared and there is good antioxygenic property。But the method adopting chemical vapour deposition (CVD) can only prepare coating sample at substrate material surface, and the thickness of glass-like carbon is restricted。It addition, adopt the chemical vapour deposition technique cannot the block materials of one-shot forming various shape and specification。
Summary of the invention
The technical problem to be solved is in that to overcome prior art not enough, a kind of glass-like carbon material preparation method based on phenol-formaldehyde resin modified presoma is provided, can quickly prepare the both bulk glasses Carbon Materials of the excellent performances such as density, bending strength, oxidation resistance。
The present invention specifically solves above-mentioned technical problem by the following technical solutions:
A kind of glass-like carbon material preparation method based on phenol-formaldehyde resin modified presoma, is sequentially carried out low-temperature setting to the mixed solution of macromolecule prepolymer presoma Yu organic solvent and carbonization processes, obtain glass-like carbon material；Described macromolecule prepolymer presoma is the phenol-formaldehyde resin modified that antioxidation is modified。
Preferably, the phenol-formaldehyde resin modified that described antioxidation is modified is a kind of or two kinds and the two or more mixture in following phenol-formaldehyde resin modified: Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium Si modification phenolic resin。
Preferably, described organic solvent is methanol, ethanol or acetone。
Preferably, in described mixed solution, the content of macromolecule prepolymer presoma is 10～60wt%。
Preferably, the process conditions of described low-temperature setting are specific as follows: be warming up to 60～80 DEG C with the heating rate of 0.5～2 DEG C/h, are incubated 10～20h；It is continuously heating to 100 DEG C with the heating rate of 0.5～2 DEG C/h, is incubated 10～20h；It is continuously heating to 120 DEG C with the heating rate of 0.5～2 DEG C/h, is incubated 10～20h；It is continuously heating to 150 DEG C with the heating rate of 0.5～2 DEG C/h, is incubated 10～20h；Cooling。
Preferably, the process conditions that described carbonization processes are specific as follows: be warming up to 250～300 DEG C with the heating rate of 10～30 DEG C/h, are incubated 2h；It is continuously heating to 550～700 DEG C with the heating rate of 10～20 DEG C/h, is incubated 2h；It is warming up to 1000～1100 DEG C with the heating rate of 10～20 DEG C/h again, is incubated 2h；Cooling。
Further, described glass-like carbon material preparation method is additionally included in the graphitization processing step carried out after carbonization processes, and the treatment temperature of described graphitization processing is 2500 DEG C, and the process time is 2h。
A kind of glass-like carbon material, is prepared by preparation method described in as above any technology scheme。
Compared to existing technology, technical solution of the present invention has the advantages that
The performances such as the density of glass-like carbon material prepared by the inventive method, bending strength, oxidation resistance are utilized all to have very big raising compared to existing technology, it is applicable to high temp. mechanical sealing, graphite or C/C surface-sealing coating, surface oxidation-resistant painting, coating material etc., to the more stringent field of glass-like carbon performance requirement；
The inventive method can prepare the both bulk glasses Carbon Materials of any thickness, shape；
The process conditions that low-temperature setting and carbonization are processed by the present invention have carried out further optimization, and preparation time is shorter, consume the energy less, significant for improving production efficiency and energy-saving and emission-reduction。
Detailed description of the invention
In order to quickly prepare the both bulk glasses Carbon Materials of the excellent performances such as density, bending strength, oxidation resistance, the invention thinking of the present invention is to improve in the preparation method that conventional polymer prepolymer presoma is raw material, using the modified phenol-formaldehyde resin modified of the antioxidation such as Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium Si modification phenolic resin as macromolecule prepolymer precursor power glass-like carbon material。
Phenol-formaldehyde resin modified is as the derivant of phenolic resin, and the characteristic such as its impact flexibility modified, caking property, mechanical strength, thermostability, dimensional stability, curing rate, moulded manufacturability can respectively obtain raising。Difference according to performance improvement direction, the kind of current phenol-formaldehyde resin modified mainly has: Pioloform, polyvinyl acetal phenol-formaldehyde resin modified, polyimide modified phenolic resin, epoxy modified phenolic resin, Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium-modified phenolic resin, titanium Si modification phenolic resin etc.。
Discovery is studied through inventor, in many different types of phenol-formaldehyde resin modifieds, adopt the phenol-formaldehyde resin modified that the antioxidation such as Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium Si modification phenolic resin modifiy as macromolecule prepolymer presoma, can obtain the glass-like carbon material that relatively traditional method performance is substantially improved, overcome again many restrictions of the aspects such as material thickness existing when adopting chemical vapour deposition technique, shape, specification simultaneously。On this basis, other process conditions are optimized improvement by the present invention further, while promoting material property further, effectively reduce manufacturing cycle, decrease energy resource consumption。
For the ease of public understanding, with several specific embodiments, technical solution of the present invention is further elaborated below。
Embodiment 1
The phenol-formaldehyde resin modified that antioxidation is modified is dissolved in ethanol by the mass ratio of 40wt%。
Then solution prepared by above-mentioned steps is poured in mould and put into and baking oven carries out low-temperature setting。During solidification, it is warming up to 60-80 DEG C with the heating rate of 2 DEG C/h, is incubated 10h；It is warming up to 100 DEG C with the heating rate of 2 DEG C/h from 80 DEG C, is incubated 10h；It is warming up to 120 DEG C with the heating rate of 2 DEG C/h, is incubated 10h；It is warming up to 150 DEG C with the heating rate of 2 DEG C/h again, is incubated 20h；Glass-like carbon green compact are prepared after cooling。
Prepared glass-like carbon green compact are placed in retort and carry out carbonization process。During carbonization, it is warming up to 250 DEG C with the heating rate of 30 DEG C/h, is incubated 2h；It is warming up to 550 DEG C with the heating rate of 20 DEG C/h from 250 DEG C, is incubated 2h；It is warming up to 1000 DEG C with the heating rate of 20 DEG C/h again, is incubated 2h；It is cooled to room temperature and obtains glass-like carbon。
In order to improve material property further, the glass-like carbon that above-mentioned steps is prepared is put into by the present embodiment in high temperature graphitization process stove and carry out graphitization processing。Treatment temperature is 2500 DEG C, and the process time is 2h, namely obtains final glass-like carbon material。
In the present embodiment, the density of glass-like carbon, the porosity, bending strength and the 600 DEG C of oxidations weight-loss ratios of 24 hours that prepare for macromolecule prepolymer presoma with Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium Si modification phenolic resin are in Table 1。
The performance of the glass-like carbon of preparation in table 1 embodiment 1
Embodiment 2:
The phenol-formaldehyde resin modified that antioxidation is modified is dissolved in ethanol by the mass ratio of 50wt%。
Then solution prepared by above-mentioned steps is poured in mould and put into and baking oven carries out low-temperature setting。During solidification, it is warming up to 60-80 DEG C with the heating rate of 1 DEG C/h, is incubated 10h；It is warming up to 100 DEG C with the heating rate of 1 DEG C/h from 80 DEG C, is incubated 10h；It is warming up to 120 DEG C with the heating rate of 1 DEG C/h, is incubated 10h；It is warming up to 150 DEG C with the heating rate of 1 DEG C/h again, is incubated 20h；Cooling, prepares glass-like carbon green compact。
Prepared glass-like carbon green compact are placed in retort and carry out carbonization process。During carbonization, it is warming up to 270 DEG C with the heating rate of 20 DEG C/h, is incubated 2h；It is warming up to 650 DEG C with the heating rate of 15 DEG C/h from 270 DEG C, is incubated 2h；It is warming up to 1050 DEG C with the heating rate of 15 DEG C/h again, is incubated 2h；It is cooled to room temperature and obtains glass-like carbon。
Glass-like carbon above-mentioned steps prepared is put in high temperature graphitization process stove and is carried out graphitization processing。Treatment temperature is 2500 DEG C, and the process time is 2h, namely obtains final glass-like carbon material。
In the present embodiment, refer to table 2 with the density of glass-like carbon, the porosity, bending strength and the 600 DEG C of oxidations weight-loss ratio of 24 hours that Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium Si modification phenolic resin prepare for macromolecule prepolymer presoma。
The performance of the glass-like carbon of preparation in table 2 embodiment 2
Embodiment 3:
The phenol-formaldehyde resin modified that antioxidation is modified is dissolved in ethanol by the mass ratio of 60wt%。
Then solution prepared by above-mentioned steps is poured in mould and put into and baking oven carries out low-temperature setting。During solidification, it is warming up to 60-80 DEG C with the heating rate of 0.5 DEG C/h, is incubated 10h；It is warming up to 100 DEG C with the heating rate of 0.5 DEG C/h from 80 DEG C, is incubated 10h；It is warming up to 120 DEG C with the heating rate of 0.5 DEG C/h, is incubated 10h；It is warming up to 150 DEG C with the heating rate of 0.5 DEG C/h again, is incubated 20h；Cooling prepares glass-like carbon green compact。
Prepared glass-like carbon green compact are placed in retort and carry out carbonization process。During carbonization, it is warming up to 300 DEG C with the heating rate of 10 DEG C/h, is incubated 2h；It is warming up to 700 DEG C with the heating rate of 10 DEG C/h from 300 DEG C, is incubated 2h；It is warming up to 1100 DEG C with the heating rate of 10 DEG C/h again, is incubated 2h；It is cooled to room temperature and obtains glass-like carbon。
Glass-like carbon above-mentioned steps prepared is put in high temperature graphitization process stove and is carried out graphitization processing。Treatment temperature is 2500 DEG C, and the process time is 2h, namely obtains final glass-like carbon material。
In the present embodiment, refer to table 3 with the density of glass-like carbon, the porosity, bending strength and the 600 DEG C of oxidations weight-loss ratio of 24 hours that Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium Si modification phenolic resin prepare for macromolecule prepolymer presoma。
The performance of the glass-like carbon of preparation in table 3 embodiment 3
Can be seen that according to three above embodiment, comparing the tradition glass-like carbon with phenolic resin for macromolecule prepolymer presoma, the phenol-formaldehyde resin modified adopting antioxidation modified is that the glass-like carbon that macromolecule prepolymer presoma prepares all significantly exceeds in many characteristics such as density of material, the porosity, intensity, antioxidation。
Additionally, the research according to inventor, when the content of described phenol-formaldehyde resin modified is more than 30wt%, when carbonization processes, the porosity of glass-like carbon goods is low, bending strength is higher, and oxidation resistance strengthens。In above three embodiment, particularly when the content of phenol-formaldehyde resin modified is 60wt%, the density of glass-like carbon goods, bending strength, oxidation resistance are best。
Above-described, it is only presently preferred embodiments of the present invention, is not limited to the scope of the present invention, the above embodiment of the present invention can also make a variety of changes。Namely every claims according to the present patent application and description are made change simple, equivalent and modification, fall within the claims of patent of the present invention。The not detailed description of the present invention be routine techniques content。
Claims (10)
1., based on a glass-like carbon material preparation method for phenol-formaldehyde resin modified presoma, the mixed solution of macromolecule prepolymer presoma Yu organic solvent is sequentially carried out low-temperature setting and carbonization processes, obtain glass-like carbon material；It is characterized in that, described macromolecule prepolymer presoma is the phenol-formaldehyde resin modified that antioxidation is modified。
2. glass-like carbon material preparation method as claimed in claim 1, it is characterized in that, the phenol-formaldehyde resin modified that described antioxidation modifiies is a kind of or two kinds and the two or more mixture in following phenol-formaldehyde resin modified: Effect of Organosilicon-modified Phenol-formaldehyde Resin, boron modified phenolic resin, molybdenum phenol-formaldehyde resin modified, titanium Si modification phenolic resin。
3. glass-like carbon material preparation method as claimed in claim 1, it is characterised in that described organic solvent is methanol, ethanol or acetone。
4. glass-like carbon material preparation method as claimed in claim 1, it is characterised in that in described mixed solution, the content of macromolecule prepolymer presoma is 10 ~ 60wt%。
5. glass-like carbon material preparation method as claimed in claim 4, it is characterised in that in described mixed solution, the content of macromolecule prepolymer presoma is 30 ~ 60wt%。
6. glass-like carbon material preparation method as claimed in claim 5, it is characterised in that in described mixed solution, the content of macromolecule prepolymer presoma is 60wt%。
7. glass-like carbon material preparation method as claimed in claim 1, it is characterised in that the process conditions of described low-temperature setting are specific as follows: be warming up to 60～80 with the heating rate of 0.5～2 DEG C/hoC, is incubated 10～20h；With 0.5～2oThe heating rate of C/h is continuously heating to 100oC, is incubated 10～20h；With 0.5～2oThe heating rate of C/h is continuously heating to 120oC, is incubated 10～20h；With 0.5～2oThe heating rate of C/h is continuously heating to 150oC, is incubated 10～20h；Cooling。
8. glass-like carbon material preparation method as claimed in claim 1, it is characterised in that the process conditions that described carbonization processes are specific as follows: with 10～30oThe heating rate of C/h is warming up to 250～300oC, is incubated 2h；With 10～20oThe heating rate of C/h is continuously heating to 550～700oC, is incubated 2h；Again with 10～20oThe heating rate of C/h is warming up to 1000～1100oC, is incubated 2h；Cooling。
9. glass-like carbon material preparation method as claimed in claim 1, it is characterised in that being additionally included in the graphitization processing step carried out after carbonization processes, the treatment temperature of described graphitization processing is 2500oC, the process time is 2h。
10. a glass-like carbon material, it is characterised in that prepared by preparation method as described in any one of claim 1～8。
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Cited By (4)
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| CN106187192A (en) * | 2016-07-18 | 2016-12-07 | 中国科学院上海应用物理研究所 | The preparation method of a kind of glass-like carbon goods and glass-like carbon goods |
| CN106496851A (en) * | 2016-10-26 | 2017-03-15 | 安徽飞达电气科技有限公司 | A kind of metallized film of anti-surge capacity device and preparation method thereof |
| CN106747668A (en) * | 2017-02-17 | 2017-05-31 | 南通市苏中纺织有限公司 | The modifies high heat conduction C/C composites of ZrC organosilane precursors |
| TWI744970B (en) * | 2019-07-01 | 2021-11-01 | 日商揖斐電股份有限公司 | Graphite material and its manufacturing method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187192A (en) * | 2016-07-18 | 2016-12-07 | 中国科学院上海应用物理研究所 | The preparation method of a kind of glass-like carbon goods and glass-like carbon goods |
| CN106187192B (en) * | 2016-07-18 | 2019-01-29 | 中国科学院上海应用物理研究所 | A kind of preparation method and glass carbon product of glass carbon product |
| CN106496851A (en) * | 2016-10-26 | 2017-03-15 | 安徽飞达电气科技有限公司 | A kind of metallized film of anti-surge capacity device and preparation method thereof |
| CN106747668A (en) * | 2017-02-17 | 2017-05-31 | 南通市苏中纺织有限公司 | The modifies high heat conduction C/C composites of ZrC organosilane precursors |
| TWI744970B (en) * | 2019-07-01 | 2021-11-01 | 日商揖斐電股份有限公司 | Graphite material and its manufacturing method |
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