CN115716748A - Graphite tube modified by resin glassy carbon - Google Patents
Graphite tube modified by resin glassy carbon Download PDFInfo
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- CN115716748A CN115716748A CN202211384660.5A CN202211384660A CN115716748A CN 115716748 A CN115716748 A CN 115716748A CN 202211384660 A CN202211384660 A CN 202211384660A CN 115716748 A CN115716748 A CN 115716748A
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Abstract
The invention discloses a resin glassy carbon modified graphite tube, which is prepared from linear phenolic resin powder, graphite powder and an additive by weight percent of 15 to 25 percent: 65 to 80%:3 to 20 percent by weight and the like as raw materials; the curing agent for the phenolic resin is preferably an epoxy resin, in which a small amount of chopped, dispersed or woven carbon fiber reinforcement is mixed. The invention has the advantages of good anti-permeability of the glassy carbon, better heat transfer performance, higher mechanical strength after the addition of the carbon fiber, no need of high-temperature graphitization, environmental protection, energy conservation and long service life, and can be widely used as a heat exchange pipeline for high-temperature and high-pressure fluid.
Description
Technical Field
The invention relates to a graphite pipe.
Background
Glassy Carbon (GC) is a novel carbon material with high carbon content purity. Known as glassy carbon because of its port morphology and structural features resembling glass, was invented almost simultaneously in 1962 by Davison in the uk and Yamada in japan. Glassy carbon is characterized by high hardness and gas impermeability, and its basic structure is a turbostratic structure with extremely small crystallite size, with the fine structure being non-oriented. Is prepared from phenolic resin, furan resin, cane sugar, cellulose, polyvinylidene chloride, etc through charring.
The glassy carbon has characteristics common to carbon materials, such as high heat resistance, electrical conductivity, corrosion resistance, high thermal conductivity, and the like. But also can be polished in a mirror way, unlike the common carbon material which can be stuck with black carbon powder once contacting. The oxidation resistance of glassy carbon is higher than that of other carbon materials, and for example, the glassy carbon is hardly corroded by concentrated sulfuric acid and concentrated nitric acid, and the oxidation weight loss in air is low.
The influence of the carbonization treatment conditions on the composition and structure of the carbonized phenolic resin product is tested and analyzed in the journal of the university of Beijing technology, beijing, published in 12 months of 2000, wherein the phenol-formaldehyde resin carbonized product is used as a carbon electrode material of a lithium ion battery, and experimental results show that a sample obtained after the carbonization treatment of the phenolic resin at the temperature of 620 ℃ has a weak (100) crystal face diffraction peak, which indicates that some graphite microcrystals are generated, but the graphitization degree of the phenol-formaldehyde resin carbonized product treated at the temperature of 1000 ℃ is lower, and still belongs to the amorphous carbon range. The experimental results show that: the mass fractions of the elements in the resin carbonized product show regular changes along with the increase of the carbonization treatment temperature, wherein the carbon increases along with the increase of the carbonization treatment temperature.
The research on the preparation OF glassy carbon by modified phenolic resin carbonization published in JOURNAL OF SICHHUAN INSTITUTE OF LIGHT INDUSTRY AND CHEMICAL TECHNOLOGY, 3.2004, finds a process for preparing glassy carbon by using a self-made novel modified phenolic resin as a raw material. The relation between the curing and carbonizing process conditions and the product performance is researched. The modified phenolic resin has low viscosity at room temperature, and small molecules are easy to escape during high-temperature curing; the product obtained after rapid temperature rise curing and carbonization has fewer pores and the like.
These documents may give some useful teaching to the present invention.
Disclosure of Invention
The purpose of the invention is as follows:
the invention provides a resin glassy carbon modified graphite tube which has high mechanical strength, does not need high-temperature graphitization treatment and has high permeability resistance.
The technical scheme is as follows:
the invention provides a resin glassy carbon modified graphite tube, which is prepared from linear phenolic resin powder, graphite powder and a small amount of additives (including phenolic resin curing agent, reinforcing material or plasticizer and other additives) as raw materials, wherein the linear phenolic resin: graphite: additive =15 to 25%: 70-80%: 3 to 20 percent (weight ratio).
The curing agent of the phenolic resin can be common formaldehyde, urotropin, (urotropin, hexamethylenetetramine, and the like which are commonly used as curing agents of resin and plastics, vulcanization accelerators of rubber, and the like), or other acidic curing agents and crosslinking curing agents.
The method comprises the following molding processes:
(1) Mixing linear phenolic resin powder, graphite powder and a small amount of additive, and pressing the mixture in a pipe blank mold to form a pipe blank or extruding the pipe blank into a pipe in a pipe extruding machine; preferably, 80 to 300 meshes of graphite powder and 80 to 180 meshes of linear phenolic resin powder are easy to mix in the convergence of particle sizes, the particle size of the graphite powder covers the linear phenolic resin powder, and a basically uniform homogeneous composite material with the linear phenolic resin powder surrounded by the graphite powder is formed after molding.
(2) And heating the pipe parison by adopting 130 to 240 ℃ (higher than the melting point of the phenolic resin and lower than the decomposition temperature of the phenolic resin and the curing agent), wherein the powder forms a plastic deformation state with the molten phenolic resin and the solid graphite powder until thermal forming and curing.
(3) Roasting the cured pipe at 380-620-1100 deg.c for 24-48 hr to release small molecules of decomposed phenolic resin, carbonizing the phenolic resin and sintering with graphite powder to form hard impervious graphite pipe containing glassy carbon.
The traditional graphite pipe has good heat conduction performance, high strength and good corrosion resistance; however, in the traditional kneading system of asphalt and coke, because the asphalt expands at the curing temperature, pores are blocked, small molecules accumulated in the asphalt are not easy to release smoothly, and the purity of the small molecule impurities in carbon which cannot be discharged in time is not high enough. It is necessary to perform graphitization treatment using a high graphitization temperature. The later graphite product has more pores on the surface and more carbon dust.
The graphite powder is directly used as one of the raw materials instead of coke, so that the high-temperature graphitization treatment process can be reduced, and the graphite material has the traditional good heat transfer conductivity. The invention adopts the phenolic resin doped with the formula to perform thermocuring and roasting, does not need a higher-temperature graphitization treatment process, and can prepare the graphite tube with higher strength, the same electric and heat conductivity, better acid and alkali resistance and impermeability and high content of glassy carbon.
Preferably, a carbon fiber reinforcement material (or graphite fiber) of a chopped dispersion, felt-like, or net-like fabric (material is carbonaceous, and heat conductivity is superior to that of glass fiber or polymer fiber) is mixed in the graphite powder or the phenol-formaldehyde novolac resin powder to enhance the tensile and bending mechanical strength of the graphite tube.
Preferably, a small-diameter cylindrical bar is taken as a core mold, two or more layers of cylindrical shell-shaped carbon fiber cloth cages (the unfolded shape is similar to a large-size carbon nano tube, a three-dimensional integral woven net and the weaving method can adopt the weaving method of a fishing net cage) with different coaxial diameters are taken as reinforcing materials, so that a mixture of graphite powder, linear phenolic resin powder and a curing agent can be conveniently wrapped and clamped and placed in a large-cylindrical outer mold shell; filling the gap with the mixed powder, pressing into a pipe parison, heating to cure phenolic resin, impregnating the cured carbon fiber into the phenolic resin to form a fibrous reinforcing material of a phenolic resin matrix, and forming a particle reinforcing material of the matrix by using graphite powder to form a composite material with higher mechanical property of a single-phase matrix material of the dual-phase reinforcing material; then the graphite tube is baked into glass carbon reinforced by a carbon fiber cloth cage. But also can obtain the pipe with much higher radial and axial mechanical strength, which is not easy to break and fracture. More preferably, the curing agent of the linear phenolic resin is epoxy resin, or the linear phenolic resin is epoxy resin modified linear phenolic resin (the name of linear phenolic epoxy resin is linear phenolic polyglycidyl ether, which is poly (2 or 3) glycidyl ether containing a linear phenolic resin structure, and the linear phenolic resin can be prepared by performing polycondensation reaction on phenol and formaldehyde in an acid medium to obtain linear phenolic resin, and then performing polycondensation reaction on the linear phenolic resin and excessive propylene oxide in the presence of sodium hydroxide. Hydroxyl in the phenolic resin molecules can perform ring-opening polymerization reaction with epoxy groups in the epoxy resin molecules, and the bonding strength between the epoxy resin and the carbon fiber is higher than that between the epoxy resin and the phenolic resin, so that the mechanical strength of the graphite pipe against collision damage is further improved. This is because the specific strength and specific modulus of the carbon fiber reinforced epoxy resin composite material are the highest among the existing engineering materials. And oxygen atoms released during epoxy roasting are combined with carbon atoms into CO2 which can be directly discharged into the atmosphere without special environment-friendly process treatment.
Has the advantages that:
the invention has the main advantages that the glass carbon has good anti-permeability, and carbon powder is not easy to scrape in later processing or use; moreover, the mechanical strength is higher after the carbon fiber, especially the carbon fiber cloth cage is added; can be used for conveying higher pressure fluids and for heat exchange. When the epoxy resin modified linear phenolic resin is used as a raw material, the carbon fiber, graphite and phenolic resin common matrix has higher bonding strength and higher toughness, and the pipe is not easy to crack, and resists high temperature, high pressure and corrosive fluid. The invention has excellent heat-conducting property, is mainly used for heat exchange pipelines, is not used as a graphite electrode for steelmaking, and normally has the temperature lower than hundreds of degrees, so high-temperature graphitization treatment process treatment is not needed; the manufacturing method saves energy and reduces consumption, has no basic dust pollution in use, is not easy to damage and has long service life.
Drawings
Fig. 1 is a partial three-dimensional shape of a carbon fiber cloth cage in the present invention.
Detailed Description
The first embodiment is as follows:
the invention adopts NOVOLAC oxalic acid catalyzed thermoplastic phenolic resin with the purity: 99.5 percent of powder with 100 to 110 meshes; thermosetting temperature: 160 to 200 ℃.
Graphite powder: purity: 99.5 percent and 100 to 200 meshes of powder.
Curing agent: urotropine powder.
Phenolic resin: graphite: urotropin =18 to 22%:72 to 75%:5-10 wt%, or plasticizer and anti-aging agent.
The production process comprises the following steps:
1) Mixing the three powders or the auxiliary agent according to the formula, and fully and uniformly mixing the powders in a dry powder swing type mixing bed.
2) Extruding the pipe by a spiral pipe extruder; forming a tube blank;
3) Heating the tube blank at 150-230 ℃ to enable the phenolic resin to carry out curing reaction;
4) The tube blank is roasted by stages (380-580 ℃); the time period is as follows: releasing small molecules in the decomposed phenolic resin after 24-30 hours; and then roasting (580-980 ℃) for 10-18 hours to completely carbonize the phenolic resin, so as to obtain the phenolic resin glassy carbon modified graphite pipe, wherein the specific gravity is as follows: 1.78 to 1.80.
Example two:
the invention relates to a resin glassy carbon modified graphite tube, which is prepared from raw materials of phenolic novolac resin powder, graphite powder and a small amount of additives, wherein the phenolic novolac resin: graphite: curing agent weight ratio =15 to 18%:70 to 75%:7 to 9 percent.
The additive contains a curing agent of phenolic resin, namely epoxy resin (2 glycidyl ether), and the phenolic resin and the epoxy resin are basically equivalent. And 8-10% of carbon fiber reinforced material.
The preparation method comprises the following steps:
(1) Mixing linear phenolic resin powder, graphite powder, epoxy resin and short carbon fiber, and pressing the mixture in a pipe blank mold to form a pipe blank;
(2) Heating the pipe blank at 170-210 ℃ until the phenolic resin is cured and shaped;
(3) The cured tube is roasted for 30 hours at the early stage at 400-600 ℃, and then roasted for 6 hours at the later stage at 620-1050 ℃ to form the graphite tube containing glassy carbon.
Example three:
the resin glassy carbon modified graphite tube provided by the invention comprises raw materials of phenolic novolac resin powder, graphite powder and a small amount of additives, wherein the phenolic novolac resin: graphite: curing agent weight ratio =15 to 18%:70 to 75%:7 to 9 percent.
The additive contains a curing agent of phenolic resin, namely epoxy resin (2 glycidyl ether), and the phenolic resin and the epoxy resin are basically equivalent. And two layers of carbon fiber cloth cage reinforcing materials with different diameters as shown in figure 1 account for 8-10% of the weight.
A cylindrical bar with a small diameter is taken as a core mold, two layers of cylindrical shell-shaped carbon fiber cloth cages with coaxial and different diameters are taken as reinforcing materials, so that a mixture of graphite powder, linear phenolic resin powder and a curing agent can be conveniently wrapped and clamped, and the mixture is placed in a large cylindrical outer mold shell; filling the gap with the mixed powder, pressing into a pipe blank (at the moment, the cloth cage is compressed to shrink), heating to cure the phenolic resin, impregnating the cured carbon fiber into the phenolic resin to form a fibrous reinforcing material of a phenolic resin matrix, and forming a granular reinforcing material of the matrix by using graphite powder to form a composite material with higher mechanical property of a single-phase matrix material of the two-phase reinforcing material; then the graphite tube is baked into the glass carbon reinforced by the carbon fiber cloth cage. The obtained tube has radial and axial mechanical strength far higher than that of the traditional graphite tube, and is not easy to break.
Claims (7)
1. A resin glassy carbon modified graphite tube is prepared from phenolic novolac resin powder, graphite powder and a small amount of additives, wherein the phenolic novolac resin: graphite: the additive weight ratio =15 to 25%: 70-80%: 3 to 20 percent; the additive comprises a phenolic resin curing agent or other additives.
2. A plexiglas carbon-modified graphite tube as claimed in claim 1, wherein: the additive contains a curing agent of phenolic resin and a carbon fiber reinforcing material.
3. A plexiglas carbon-modified graphite tube according to claim 2 wherein: the curing agent is epoxy resin.
4. A plexiglas carbon-modified graphite tube according to claim 2 wherein: the carbon fiber reinforced material is one layer, two layers or multiple layers of carbon fiber cloth cages which are coaxial with the central axis of the ink tube.
5. A molding process of a resin glassy carbon modified graphite tube is characterized in that: the following sequence of process steps is adopted:
(1) Mixing linear phenolic resin powder, graphite powder and a small amount of additive, and pressing the mixture in a pipe blank mold to form a pipe blank or extruding the pipe blank into a pipe in a pipe extruding machine;
(2) Heating the pipe parison at 130 to 240 ℃ until the phenolic resin is cured and shaped;
(3) The cured tube is roasted for 24-48 hours in stages at 380-1100 ℃ to form the hard impervious graphite tube containing phenolic resin glassy carbon.
6. The process of forming a plexiglas carbon-modified graphite tube as claimed in claim 5, wherein: in the process step (3), the cured pipe is roasted for 24 hours at 380-620 ℃, and then the pipe is roasted for 24-48 hours at 620-1100 ℃.
7. The process of forming a plexiglas carbon-modified graphite tube as claimed in claim 5, wherein: in the process step (1), a cylindrical bar with a small diameter is taken as a core mold, two or more layers of cylindrical shell-shaped carbon fiber cloth cages with different diameters and coaxial diameters are taken as reinforcing materials, and a mixture of graphite powder, linear phenolic resin powder and a curing agent is wrapped and clamped and placed in an outer mold shell with a large cylinder shape; then the mixed powder is used for filling the gap and is pressed into a pipe blank.
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| CN202211270260 | 2022-10-18 | ||
| CN2022112702601 | 2022-10-18 |
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| CN115716748A true CN115716748A (en) | 2023-02-28 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116813365A (en) * | 2023-06-30 | 2023-09-29 | 浙江星辉新材料科技有限公司 | High-temperature-resistant large-size carbon-carbon bearing plate and preparation method thereof |
| CN118548745A (en) * | 2024-07-29 | 2024-08-27 | 南通山剑防腐科技有限公司 | Carbon fiber reinforced resin heat exchange tube |
Citations (7)
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| JPH0532457A (en) * | 1991-07-26 | 1993-02-09 | Kanebo Ltd | Carbon fiber-reinforced carbon composite material and its production |
| CN1431417A (en) * | 2003-01-09 | 2003-07-23 | 冯圣君 | Carbon fiber graphite tube with high strength, high transmit heat and its production method |
| CN102807355A (en) * | 2011-05-30 | 2012-12-05 | 南通三鑫碳素石墨设备有限公司 | Carbon fiber-reinforced compressed graphite tube |
| CN105968706A (en) * | 2016-07-11 | 2016-09-28 | 南通星球石墨设备有限公司 | Graphite pipe |
| CN108036123A (en) * | 2018-01-03 | 2018-05-15 | 江苏澳盛复合材料科技有限公司 | A kind of carbon fiber glass fiber hybrid multiple tube and preparation method thereof |
| CN110628169A (en) * | 2019-07-04 | 2019-12-31 | 南通星球石墨设备有限公司 | Furan resin graphite tube and preparation method thereof |
| CN113044378A (en) * | 2021-03-17 | 2021-06-29 | 中国科学院上海应用物理研究所 | Preparation method of molten salt storage container and molten salt storage container |
-
2022
- 2022-11-07 CN CN202211384660.5A patent/CN115716748A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0532457A (en) * | 1991-07-26 | 1993-02-09 | Kanebo Ltd | Carbon fiber-reinforced carbon composite material and its production |
| CN1431417A (en) * | 2003-01-09 | 2003-07-23 | 冯圣君 | Carbon fiber graphite tube with high strength, high transmit heat and its production method |
| CN102807355A (en) * | 2011-05-30 | 2012-12-05 | 南通三鑫碳素石墨设备有限公司 | Carbon fiber-reinforced compressed graphite tube |
| CN105968706A (en) * | 2016-07-11 | 2016-09-28 | 南通星球石墨设备有限公司 | Graphite pipe |
| CN108036123A (en) * | 2018-01-03 | 2018-05-15 | 江苏澳盛复合材料科技有限公司 | A kind of carbon fiber glass fiber hybrid multiple tube and preparation method thereof |
| CN110628169A (en) * | 2019-07-04 | 2019-12-31 | 南通星球石墨设备有限公司 | Furan resin graphite tube and preparation method thereof |
| CN113044378A (en) * | 2021-03-17 | 2021-06-29 | 中国科学院上海应用物理研究所 | Preparation method of molten salt storage container and molten salt storage container |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116813365A (en) * | 2023-06-30 | 2023-09-29 | 浙江星辉新材料科技有限公司 | High-temperature-resistant large-size carbon-carbon bearing plate and preparation method thereof |
| CN116813365B (en) * | 2023-06-30 | 2024-03-01 | 浙江星辉新材料科技有限公司 | High-temperature-resistant large-size carbon-carbon bearing plate and preparation method thereof |
| CN118548745A (en) * | 2024-07-29 | 2024-08-27 | 南通山剑防腐科技有限公司 | Carbon fiber reinforced resin heat exchange tube |
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