CN102290146A - Method for manufacturing reinforced composite cable core - Google Patents
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Abstract
The invention provides a method for manufacturing a reinforced composite cable core, belonging to the field of high performance composites. The reinforced cable cores in the prior art have the following problems: (1) the thickness of the outer insulating layers is not uniform and even carbon fibers are locally exposed; (2) the transverse compressive strength is poor and the cores are easy to crack; and (3) the pultrusion speed is lower and is generally (0.2-0.6)m/min. The method is characterized by selecting epoxy resins (with epoxy value being 0.80-0.95mol/100g) with multi-functional groups, a modified anhydride curing agent, a modified imidazole accelerating agent, an inner release agent and a toughening agent, optimizing the resin mixing proportion, simultaneously introducing the fiber braiding technology and braiding a sleeve layer outside the axially arranged inner core fiber bundles of the reinforced core to prepare the high performance reinforced composite cable core. The cable core has the advantages of uniform insulating layer thickness, high transverse compressive strength, high production speed and high toughness.
Description
Technical field
The present invention relates to the manufacture method that a kind of composite material cable strengthens core.
Background technology
At present, along with the propelling of expanding economy and process of industrialization, the demand of current power is increased day by day.Usually the way that addresses this problem is a new frame transmission line or to the increase-volume of carrying out of original circuit.The former quantities is big, and cost is very huge, and will take valuable land resource, is to solve way first choice of this contradiction by the increase-volume to original circuit therefore.Traditional big capacity steel reinforced aluminium conductor has problems such as weight is big, intensity is low, thermal coefficient of expansion is high, sag is big, heat resistance difference.Units such as many universities and colleges both domestic and external, scientific research institution, company have carried out extensive work to big capacity aerial condutor, adopt fibre-reinforced composite core to replace traditional structure of steel pole.The patent of the patent No. CN 1898085A of the public fabric of U.S. CTC Cable Corp. states that its fiber hybrid composite that adopts strengthens core; usually this plug is at the outer pultrusion layer of glass of carbon fiber core composite material, and skin plays the protection internal layer and prevents the effect of electrochemical corrosion.Shanghai Electrical Cable Research Institute is stated outer increase by one metallic sheath at its composite core rod in its CN 101727998A patent book, the cable of this kind structure does not cause generation space between core and the conductor because the thermal coefficient of expansion between the two matches under the situation of repeatedly expanding with heat and contract with cold.In addition, Daqing oil Shinco Renqing joint anti-corrosion Co., Ltd states that in the utility model patent of its ZL 200820090630.2 its external diameter is hollow greater than the carbon fiber core body of the cable core of 12mm, and fills with filler.These methods have great importance to making the high-performance composite materials electric cable reinforced core, but the product of above-mentioned patent remains in following problem: 1. external insulation layer is in uneven thickness, even the part has carbon fiber exposed; 2. laterally compression strength is poor, vertically easy to crack; 3. pultrusion speed is slower, generally at (0.2～0.6) m/min.
Summary of the invention
The objective of the invention is to introduce the fibrage technology by optimizing the resin embodiment, provide a kind of thickness of insulating layer evenly, laterally compression strength is big, speed of production fast, the high-performance composite materials electric cable reinforced core manufacture method of high tenacity.
Composite material cable involved in the present invention strengthens core and comprises inner core and external coating.Inner core is composited by fiber and thermosetting resin, and external coating is composited by fibrage sleeve pipe and thermosetting resin.For achieving the above object, the present invention selects polyfunctional epoxy resin (epoxide number 0.80～0.95mol/100g), modified anhydride curing agent, modified imidazole promoter, inner pattern releasing agent applicable and flexibilizer for use, by optimizing the resin mixed ratio, introduce the fibrage technology simultaneously, outside the inner core fibre bundle of arranging, work out one deck fiber sleeve at the enhancing mandrel, make the high-performance composite materials electric cable reinforced core.The concrete operations scheme is as follows:
A. glue preparation: with epoxide number is that polyfunctional epoxy resin, modified anhydride curing agent, modified imidazole promoter, inner pattern releasing agent applicable, the nano core-shell rubber toughening agent of 0.80～0.95mol/100g is 100 with mass ratio: (100～150): (0.1～10): (0.1～2): mix (5～25), fully stirs to leave standstill after 30～60 minutes that to obtain glue in 2～3 hours stand-by;
B. interior core preforming: with carbon, Kev draw, one or more fibers in basalt, glass, aromatic polyamides, boron, liquid crystal and the carbon nano-fiber 60～100 ℃ down oven dry be installed on the creel after 1～2 hour and draw, the glue groove I that is placed with the glue for preparing in the steps A by inside carries out the impregnation first time, and forming the cross section by preforming tool afterwards is circular inner core; Glue groove I temperature is 30～50 ℃;
C. external coating preforming: with carbon, Kev draw, one or more fibers in basalt, glass, aromatic polyamides, boron, liquid crystal and the carbon nano-fiber 60～100 ℃ of oven dry 1～2 hour down, remove the moisture in the fiber before use; Then fiber is installed on the braiding machine, and behind the thick fiber sleeve of inner core outside braiding one deck 0.5～1.5mm, carries out the impregnation second time, the glue that prepare among the A in steps glue groove II inside, 40～70 ℃ of glue groove II temperature by glue groove II;
D. pultrusion is solidified: the intermediate products after the external coating preforming enter mold cured and are shaped under the effect of tractive effort, hauling speed is 1.0～1.3m/min, long 0.6～the 1.5m of mould, temperature is divided into three sections from the outlet that enters the mouth, implement sectional temperature-controlled, first section temperature is 150～180 ℃, and second section temperature is 180～230 ℃, and the 3rd section temperature is generally than second section low 10～20 ℃; Through the cured after heat-treatment furnace carries out of the product after the mold cured, heat-treatment furnace is divided into two sections, and every segment length is 2～3 meters, and first section temperature is 180～230 ℃, and second section temperature is than first section high 5～20 ℃; Make composite material cable and strengthen core.
The method that the present invention relates to is compared with additive method, has following advantage; 1. the imidazoles promoter of modification, (25 ℃) are in a liquid state under the normal temperature, and viscosity only is (300～700) mPa.s, is convenient to the even mixing with resin system.This system is under 50 ℃, and be applicable to pultrusion technology greater than 10 hours pot life.2. as shown in table 1, the adding of the imidazoles promoter of modification can be shortened the gel time of system greatly, and speed of production (being hauling speed) can be increased to (0.8～1.5) m/s, increases substantially pultrusion production efficiency.3. in the imidazoles promoter molecular structure of modification tertiary amine is arranged, when acid anhydrides/epoxy systems solidifies, help to improve the degree of cross linking, and then improve the thermal endurance of solidfied material; In addition, long molecule chain link is arranged in this promoter molecular structure, thereby help to improve the toughness of solidfied material; 4. as shown in table 2, the adding of nano core-shell rubber toughening agent does not only reduce the glass transition temperature (Tg) of solidfied material, has improved its toughness on the contrary greatly.5. owing to introduce the fibrage technology at external coating, can guarantee that carbon-free fibre is exposed, and the product thickness of insulating layer is even, does not vertically have cracking, when wrap angle was 45 °, laterally compression strength had improved 70%.
Gel time under table 1. modified imidazole promoter LMY2404 and the promoter commonly used
* test condition: adopt the gel time analyzer, instrument is warming up to test temperature, put into the resin for preparing, timing begins, and constantly stirs, and till resin produces gel, stops timing.The time of measuring is the gel time of resin system under this temperature.
Resin cured matter performance under the different flexibilizer of table 2
* the condition of cure of system: 50 ℃ of beginning vacuum defoamation 1h, the speed with (3～5) ℃/min is warming up to 180 ℃ then, cools to naturally below 60 ℃ behind the insulation 1h.Breakdown strength is to measure under the distortion condition of plane.
Description of drawings
Fig. 1: material schematic diagram of the present invention.1 is inner core among the figure, and 2 is external coating.
Embodiment
The present invention relates to a kind of high-performance composite materials electric cable reinforced core, now will describe exemplary arrangement of the present invention more fully with reference to accompanying drawing hereinafter.It is to be noted that 1. the present invention can be presented as many different forms, is not limited in the embodiment that this paper proposes; 2. the fiber of using among the present invention comprises that carbon, glass, Kev draw one or more in (kevlar), basalt, aromatic polyamides, boron, liquid crystal and the carbon nano-fiber; 3. the glass transition temperature of mentioning among the present invention (Tg) is the T that adopts differential scanning calorimetry (DSC) to record
Midpoint
Example 1
As shown in Figure 1, electric cable reinforced core of the present invention comprises inner core C and external coating S.Inner core C and external coating S are formed by plurality of fibers or its fabric and resin compounded.Inner core C adopts TORAY T700S (12K) carbon fiber, external coating S adopts the non-twist fibre glass roving of Nanjing Glass Fibre Research and Design Institute HS2 (SC-1200), used resin is the JEh-012 modified multicomponent glycidyl amine high-temperature-resistant epoxy resin that Changhu Jiafa chemistry Co., Ltd. produces, its epoxide number is (0.80～0.85) mol/100g, used curing agent is the modification tetrahydrophthalic anhydride that Changhu Jiafa chemistry Co., Ltd. produces, promoter is that the liquid imidazoles promoter of LMY-2404 modification that hundred million development in science and technology Co., Ltds produce is managed in Shanghai, release agent is the INT-1890M that U.S. AXEL company produces, and flexibilizer is the ICAM-8610 nano core-shell rubber toughening agent that Shenzhen establishment Applied Materials Inc produces.Its manufacturing process is as follows:
1. preparation:
● is 100: 130: 8 with epoxy resin, curing agent, promoter, release agent and flexibilizer with mass ratio: mix and stir at 1: 25 leave standstill after 30 minutes 2 hours stand-by;
● 78 bundle carbon fibers and 24 bundle glass fibres were dried 1 hour in 80 ℃ of baking ovens, and it is contained in respectively on the spindle of creel and braiding machine.
● parameter setting: the temperature of glue groove I and II is respectively 40 ℃ and 50 ℃, and three sections temperature of mould are set to 175 ℃ respectively, and 205 ℃, 195 ℃.The temperature of heat-treatment furnace is set at 205 ℃ respectively, 215 ℃;
2. interior core preforming
Carbon fiber is drawn by creel, and the glue groove I that is placed with aforementioned stand-by glue by inside carries out the impregnation first time, and forming the cross section by preforming tool afterwards is circular inner core C.
3. external coating preforming
Inner core C is by the centre bore of braiding machine, according to 35 ° of braiding angles behind the thick glass fibre coating layer S of inner core outside braiding one deck 1.0mm, carry out the impregnation second time by glue groove II.
4. pultrusion
Above-mentioned preform under the effect of pulling equipment tractive effort, is entered the mold cured moulding.Hauling speed 1.0m/min;
The glue of being prepared in this example is behind vacuum defoamation 1h, and the glass transition temperature (Tg) that solidifies the resin-cast body of gained under the condition of 90 ℃/2h+120/2h+150 ℃/4h is 212 ℃.The diameter of preparation is that the composite material of 9.50mm strengthens core, and hot strength reaches 2.41Gpa.Laterally resistance to compression load can reach 75kN, and compressive strength is 78.9MPa, does not adopt the composite material of braided sleeving to strengthen core than external coating and has improved nearly 50%.
Example 2
As shown in Figure 1, the used Araldite MY 721 multifunctional bundle high-temperature-resistant epoxy resins that step the production of (Huntsman) company for U.S.'s Hensel in this example, its epoxide number is (0.90～0.95) mol/100g, used curing agent is the liquid modified tetrahydrophthalic anhydride that Tianjin synthetic material industry research institute produces, promoter is the liquid imidazoles of modification that Tianjin chemistry chemical reagents corporation produces, and other components and execution mode are with example 1.The glue of this example is 100: 145: 1 with mass ratio: mix at 0.7: 15.External coating S is the thick glass fibre external coating S of one deck 1mm of braiding, is cured respectively and back curing through the laggard mould of the impregnation second time and heat-treatment furnace.The temperature of glue groove I and II is respectively 45 ℃, 54 ℃, and three sections temperature of mould are set to 175 ℃, and 210 ℃, 188 ℃, hauling speed 1.1m/min.This system is through 210 ℃, solidifies the hot strength that the composite material that makes strengthens core after 225 ℃ two sections and reaches 2.23Gpa, and laterally compression strength has improved 54%.The glue of being prepared in this example is behind vacuum defoamation 1h, and the glass transition temperature (Tg) that solidifies the resin-cast body of gained under the condition of 90 ℃/2h+120/2h+150 ℃/4h is 223 ℃.
Example 3
The execution mode of example 3 is with example 1, adopt 38 bundle TORAY T700S (12K) carbon fibers and 24 bundle Nanjing Glass Fibre Research and Design Institute HS2 (SC-1200) glass fibres, can make external diameter is the composite material enhancing core of 7.11mm, and hot strength reaches 2.28Gpa, and laterally compression strength improves 60%.As a same reason, can strengthen core according to the carbon fibre composite of diameter that how much make of fiber number from 5mm to the 15mm different size.General fiber volume fraction is at (60～80) %.
Example 4
Inner core C in this example adopts 38 bundle TORAY T700S (12K) carbon fibers, the 24 bundle 1200tex basalt fibres that external coating S adopts Jiangsu Tianlong Xuanwu CBF High-Technology Co., Ltd. to produce, and glue and execution mode are with example 1.Hauling speed 1.3m/min.The glass transition temperature that makes composite material reaches 184 ℃, and the hot strength that composite material strengthens core reaches 2.30Gpa, and laterally compression strength improves 50%.
Example 5
In this example, inner core C adopts 44 bundle TORAY T700S (12K) carbon fibers, Nanjing glass fibre 24 bundle HS2 (SC8-960) rovings that external coating S adopts, and glue and execution mode are with example 1.Hauling speed 1.2m/min, the glass transition temperature that makes composite material reaches 182 ℃, and the hot strength that composite material strengthens core reaches 2.62Gpa, and laterally compression strength also improves 45%.
Claims (1)
1. a composite material cable strengthens the manufacture method of core, it is characterized in that step is as follows:
A. glue preparation: with epoxide number is that polyfunctional epoxy resin, modified anhydride curing agent, modified imidazole promoter, inner pattern releasing agent applicable, the nano core-shell rubber toughening agent of 0.80～0.95mol/100g is 100 with mass ratio: (100～150): (0.1～10): (0.1～2): mix (5～25), fully stirs to leave standstill after 30～60 minutes that to obtain glue in 2～3 hours stand-by;
B. interior core preforming: with carbon, Kev draw, one or more fibers in basalt, glass, aromatic polyamides, boron, liquid crystal and the carbon nano-fiber 60～100 ℃ down oven dry be installed on the creel after 1～2 hour and draw, the glue groove I that is placed with the glue for preparing in the steps A by inside carries out the impregnation first time, and forming the cross section by preforming tool afterwards is circular inner core; Glue groove I temperature is 30～50 ℃;
C. external coating preforming: with carbon, Kev draw, one or more fibers in basalt, glass, aromatic polyamides, boron, liquid crystal and the carbon nano-fiber 60～100 ℃ of oven dry 1～2 hour down, remove the moisture in the fiber before use; Then fiber is installed on the braiding machine, and behind the thick fiber sleeve of inner core outside braiding one deck 0.5～1.5mm, carries out the impregnation second time, the glue that prepare among the A in steps glue groove II inside, 40～70 ℃ of glue groove II temperature by glue groove II;
D. pultrusion is solidified: the intermediate products after the external coating preforming enter mold cured and are shaped under the effect of tractive effort, hauling speed is 1.0～1.3m/min, long 0.6～the 1.5m of mould, temperature is divided into three sections from the outlet that enters the mouth, implement sectional temperature-controlled, first section temperature is 150～180 ℃, and second section temperature is 180～230 ℃, and the 3rd section temperature is generally than second section low 10～20 ℃; Through the cured after heat-treatment furnace carries out of the product after the mold cured, heat-treatment furnace is divided into two sections, and every segment length is 2～3 meters, and first section temperature is 180～230 ℃, and second section temperature is than first section high 5～20 ℃; Make composite material cable and strengthen core.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102604328A (en) * | 2012-02-28 | 2012-07-25 | 常熟佳发化学有限责任公司 | Matrix resin composition of resin-based fabric reinforced composite mandrel for overhead wire and application method of the resin composition |
| CN102708941A (en) * | 2012-06-27 | 2012-10-03 | 嘉兴宝盈通复合材料有限公司 | Cable core and cable comprising same |
| CN103529526A (en) * | 2013-09-27 | 2014-01-22 | 江苏亨通光电股份有限公司 | Method for manufacturing basalt fiber rod |
| CN104952565A (en) * | 2015-06-18 | 2015-09-30 | 西安高强绝缘电气有限责任公司 | Manufacturing method of large-diameter multi-core combined core rod |
| CN104974471A (en) * | 2015-07-14 | 2015-10-14 | 江苏兆鋆新材料股份有限公司 | Preparation method of high-heat-resistance high-toughness epoxy resin carbon-fiber composite material |
| CN106638067A (en) * | 2016-12-06 | 2017-05-10 | 太仓大唐化纤厂 | Durable fiber composite reinforced rope and manufacturing method thereof |
| CN108202486A (en) * | 2018-03-13 | 2018-06-26 | 远东电缆有限公司 | A kind of composite core production line and its production technology |
| CN109637722A (en) * | 2018-11-06 | 2019-04-16 | 深圳烯湾科技有限公司 | Carbon nano-tube fibre conducting wire |
| CN111029057A (en) * | 2019-12-13 | 2020-04-17 | 广东粤通实业有限公司 | Manufacturing method of cable protection sleeve |
| CN111081411A (en) * | 2019-12-09 | 2020-04-28 | 河北碳垣纳米科技有限公司 | Carbon nanotube fiber flexible cable |
| JP2021170432A (en) * | 2020-04-14 | 2021-10-28 | 日本特殊陶業株式会社 | Wire, assembled wire and element including the same |
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| CN102604328A (en) * | 2012-02-28 | 2012-07-25 | 常熟佳发化学有限责任公司 | Matrix resin composition of resin-based fabric reinforced composite mandrel for overhead wire and application method of the resin composition |
| CN102708941A (en) * | 2012-06-27 | 2012-10-03 | 嘉兴宝盈通复合材料有限公司 | Cable core and cable comprising same |
| CN102708941B (en) * | 2012-06-27 | 2014-11-19 | 嘉兴宝盈通复合材料有限公司 | Cable core and cable comprising same |
| CN103529526A (en) * | 2013-09-27 | 2014-01-22 | 江苏亨通光电股份有限公司 | Method for manufacturing basalt fiber rod |
| CN104952565A (en) * | 2015-06-18 | 2015-09-30 | 西安高强绝缘电气有限责任公司 | Manufacturing method of large-diameter multi-core combined core rod |
| CN104974471A (en) * | 2015-07-14 | 2015-10-14 | 江苏兆鋆新材料股份有限公司 | Preparation method of high-heat-resistance high-toughness epoxy resin carbon-fiber composite material |
| CN104974471B (en) * | 2015-07-14 | 2017-12-05 | 江苏兆鋆新材料股份有限公司 | A kind of high heat-resisting, high-toughness epoxy resin carbon fibre composite preparation method |
| CN106638067B (en) * | 2016-12-06 | 2019-05-21 | 江苏丝丝缘纤维有限公司 | A kind of durable fiber composite strengthen rope and preparation method thereof |
| CN106638067A (en) * | 2016-12-06 | 2017-05-10 | 太仓大唐化纤厂 | Durable fiber composite reinforced rope and manufacturing method thereof |
| CN108202486A (en) * | 2018-03-13 | 2018-06-26 | 远东电缆有限公司 | A kind of composite core production line and its production technology |
| CN108202486B (en) * | 2018-03-13 | 2023-05-16 | 远东电缆有限公司 | Composite core production line and production process thereof |
| CN109637722A (en) * | 2018-11-06 | 2019-04-16 | 深圳烯湾科技有限公司 | Carbon nano-tube fibre conducting wire |
| CN111081411A (en) * | 2019-12-09 | 2020-04-28 | 河北碳垣纳米科技有限公司 | Carbon nanotube fiber flexible cable |
| CN111029057A (en) * | 2019-12-13 | 2020-04-17 | 广东粤通实业有限公司 | Manufacturing method of cable protection sleeve |
| JP2021170432A (en) * | 2020-04-14 | 2021-10-28 | 日本特殊陶業株式会社 | Wire, assembled wire and element including the same |
| JP7453046B2 (en) | 2020-04-14 | 2024-03-19 | 日本特殊陶業株式会社 | Electric wires, collective wires, and elements equipped with them |
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