CN100509358C - Continuous rolling shaping method of low-temperature thick wall GFRP tube - Google Patents
Continuous rolling shaping method of low-temperature thick wall GFRP tube Download PDFInfo
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- CN100509358C CN100509358C CNB031165990A CN03116599A CN100509358C CN 100509358 C CN100509358 C CN 100509358C CN B031165990 A CNB031165990 A CN B031165990A CN 03116599 A CN03116599 A CN 03116599A CN 100509358 C CN100509358 C CN 100509358C
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Abstract
In the continuous low temperature thick-wall GRP pipe winding process, the materials used include defatted alkali-free glass fiber fabric through coupling treatment and glue compounded with biphenol A type epoxy resin E-51 in 70 % and type 651 II type polyamide resin in 30 %. During the wet normal temperature continuous winding process, glass fabric is formed into GRP pipe in an integral mechanical production line including gluing, glue pressing, glue replenishing, glue scraping and pipe winding. After reaching the outer diameter of GRP pipe, fabric feeding is stopped and the equipment continues curing at normal temperature; and the GRP pipe after being cured is post-cure treated in a stove. The low temperature thick-wall GRP pipe of the present invention has no delamination, and has excellent mechanical property and heat isolating performance.
Description
Technical field
The present invention relates to the continuous roll-forming preparation method of a kind of low temperature thick-wall glass reinforced plastic pipe, particularly a kind of method that adopts the continuous roll-forming of wet method to make the heavy wall glass reinforced plastic pipe is applicable to the heat insulation supporting member of low-temperature storage tank and the heat insulation supporting member of other Cryo Equipments.Belong to cryogenic engineering and cryogenic material manufacture craft technical field.
Background technology
Glass fibre reinforced composion (GFRP) is commonly called as fiberglass, with the glass fibre is reinforcing material, it is a class representative in the fibre reinforced materials, compare with other types of fibers reinforcing material (boron fibre, carbon fiber, alumina fibre, Kevlar fiber etc.), the glass fibre elastic mould value is lower, but that maximum characteristics are the ratio of intensity and thermal conductivity factor is big.Epoxy resin is a class thermosetting resin of extensive use, also is fibre reinforced composites the most a kind of matrix materials of extensive employing in the low temperature field.
Glass fibre reinforced composion has specific strength and specific modulus height, advantage that thermal conductivity factor is low, therefore be widely used in the cryogenic engineering field, the for example container and the cryogenic system of the wind-tunnel under the low temperature, accumulating cryogenic liquid, the especially supporting construction of superconducting magnet part.
According to the molding mode difference, fiberglass has plate, bar and pipe material.
For large-scale low-temperature storage tank, in order to make storage tank can bear big impact, supporting material between its inside and outside jar need be expected fiberglass with pipe, if glass steel disk supporting member with Sheet Metal Processing one-tenth, its poor mechanical property, can not satisfy storage tank and bear the thump performance demands, so must use the fiberglass of tubulose to process the supporting member of storage tank.The low temperature thick-wall glass reinforced plastic pipe has high mechanical performance and excellent heat insulation property.
For large-scale low-temperature storage tank, because its volume is bigger, its used supporting material need be used the heavy wall glass reinforced plastic pipe.Thickness does not have the successfully precedent of making both at home and abroad greater than the glass reinforced plastic pipe of 200mm.In the development process of heavy wall glass reinforced plastic pipe, the interlayer lamination all appears in the glass reinforced plastic pipe that domestic fiberglass manufactory has adopted dry method substep and continuously shaped method to make, and development is not all achieved success in many ways, and main cause is the big interlayer tension of appearance after the moulding.Example adopts the continuously shaped making heavy wall of dry method glass reinforced plastic pipe, and repeatedly making has all produced lamination after cutting; After use dry method multistep molding technology instead and make the heavy wall glass reinforced plastic pipe, after incision, also began to occur serious lamination in several hours.
Summary of the invention
Be deficiency and the defective that overcomes prior art, the present invention proposes with the continuous coiled forming technology of wet method and make the low temperature thick-wall glass reinforced plastic pipe, solve dry-press process technology and make the lamination problem that glass reinforced plastic pipe exists, and make fiberglass have good performance at low temperatures, satisfy the special instructions for use of fiberglass.
Main points of the present invention are selection, the proportioning of glue and the determining of moulding process of fiberglass with the degreasing glass cloth: by continuously shaped on the mechanization streamline of gluing on the degreasing alkali-free glass cloth, moulding, benefit glue, frictioning, pipe crimping one, after the normal temperature cooling, carry out the back again and solidify the heavy wall glass reinforced plastic pipe material that processing obtains not having lamination.Whole technical process rolls on the equipment at the special glass steel pipe and finishes, and this equipment mainly comprises cloth beam, 4 rolls, pressure roller, loose tool and motor etc.
Specific embodiment is as follows:
1. the selection of glass fabric.Glass fibre is the reinforcing material of fiberglass.The glass fabric of using among the present invention is that model is VN-EW100B-100Y through the degreasing alkali-free glass fiber cloth of fertile blue coupling processing.Fertile blue oil content≤1.5%.Glass fabric before rolling through 80 ℃, baking goes tide to handle more than 8 hours; When rolling, every bundle glass cloth preceding two-layer and last two-layer all cut need not, stop dust and pollution.
2. the selection of glue and preparation.Used glue is the mixture of epoxy resin and curing agent among the present invention.Epoxy resin is the matrix material of fiberglass, adopts bisphenol A type epoxy resin E-51 as matrix material among the present invention.The curing agent of using among the present invention is 651 II type polyamides.The glue amount of each modulation is no more than 2kg, the allotment ratio: epoxy resin 70%, and curing agent 30%, by stirring to keep even, used vessel use by turns in the use.
3. cleaning production equipment.Loose tool, roll and 1～2 layer of mylar of pressure roller bag that will clean through acetone, outer surface is used the acetone scrub again, and two ends jointing adhesive band cements, and the mylar on roll and the pressure roller was changed once in 8 hours.Every meter length topping roll and pressure roller quality are 290 ± 20kg.
4. before beginning to roll, loose tool, following two rolls (the 3rd roll and the 4th roll) are placed on the production line; Above two rolls (first roll and second roll) and pressure roller be not placed on the production line.A bolt is set on the cloth beam, when beginning to roll, the Bradley time-out is just carried out gluing to fiber cloth, draw toward the loose tool place on gluing limit, limit, when fiber cloth is pulled to the loose tool place, and the hand rotation loose tool, fiber cloth is put first roll, second roll and pressure roller after volume on the loose tool is to 3～4 layers.
5. start and drive the motor that loose tool rotates.Rotating speed of motor is adjustable, guarantees that the linear velocity that in whole glass reinforced plastic pipe roll-forming process gluing glass cloth advances loose tool is 1.5～2.0m/min.
6. in the process of rolling, fiber cloth is carried out gluing, fiber cloth is mended glue, before pressure roller, carry out frictioning at the second roll place at the first roll place.
7. when in the process of rolling, needing to change glass fabric, repeating step 4.In step 4 implementation process, the gluing glass cloth will be cut in the joint neatly, newly laying below and the overlapping 150～200mm of former cloth of gluing, and carry out the mark of joint, guarantee that all joints are uniform on 360 °.When changing cloth, adopt the glue of new preparation without exception, forbid with having used the glue a period of time of after.
8. after the glass reinforced plastic pipe external diameter reaches given size, wrap up 1 ~ 2 layer of mylar on the glass reinforced plastic pipe outer surface, change the mylar on the pressure roller, and pressure roller is placed on the production line, motor remains in operation and carries out normal temperature cure, and the normal temperature cure time is not less than 8 hours.
9. after normal temperature cure finished, disable motor took off rolled glass reinforced plastic pipe and advances baking oven, rolled glass reinforced plastic pipe is carried out the back solidify processing.The baking oven of using among the present invention is super-huge air dry oven, the temperature inside the box fluctuation degree≤± 1 ℃, the unevenness of the temperature inside the box≤± 2.5%.Solidify in the processing procedure in whole back, guarantee that glass reinforced plastic pipe temperature lowest part need reach 100 ℃ and maintain and be no less than 2 hours under this temperature.
Among the present invention, also should carry out following operating condition:
Among the present invention when making glass reinforced plastic pipe, should guarantee the few dust of glass reinforced plastic pipe moulding make-up room, temperature is controlled at 15 ℃～25 ℃, relative humidity should be not more than 75%.
2. in the overall process of product, forbid oil and fat in the glass reinforced plastic pipe.
3. operating room should be equipped with fire-fighting equipment and ventilation equipment, and livewire work should have full-time special messenger to be responsible for, and can not there be naked light at the scene, permits no smoking welding.
Low temperature thick-wall glass reinforced plastic pipe with method of the present invention is made lamination can not occur, and has good mechanical character and heat-proof quality.
Description of drawings
Fig. 1 is that glass reinforced plastic pipe of the present invention rolls the device structure schematic diagram.
The specific embodiment
Low temperature glass steel pipe manufacturing technology below in conjunction with accompanying drawing and three kinds of different wall is further described technical scheme of the present invention.
Whole technical process of the present invention rolls on the equipment at the special glass steel pipe and finishes, and this equipment mainly comprises cloth beam, 4 rolls (first roll～the 4th roll), pressure roller, loose tool and motor etc.
Example one
The making wall thickness is that the technology of 145 ± 2mm glass reinforced plastic pipe is as follows:
Scene temperature is 20 ℃, and humidity is 65%.
1. select the degreasing alkali-free glass fiber cloth through fertile blue coupling processing for use, model is VN-EW100B-100Y.Before rolling, fiber cloth goes tide to handle through baking in 10 hours under 80 ℃ of environment in baking oven.
2. glue is that 651II type polyamide is formulated by bisphenol A type epoxy resin E-51 and curing agent.The allotment ratio: epoxy resin 70%, curing agent 30% is modulated glue 1.5kg at every turn.
3. loose tool, roll and 2 layers of mylar of pressure roller bag that will clean through acetone, outer surface is used the acetone scrub again, and two ends jointing adhesive band cements, and the mylar on roll and the pressure roller was changed once in 8 hours.Roll quality is 270kg/m.The pressure roller quality is 280kg/m.The loose tool diameter is 290mm.
4. before beginning to roll, loose tool, the 3rd roll and the 4th roll are placed on the production line; First roll, second roll and pressure roller are not placed on the production line.A bolt is set on the cloth beam, when beginning to roll, the Bradley time-out is just carried out gluing to fiber cloth, draw toward the loose tool place on gluing limit, limit, when fiber cloth is pulled to the loose tool place, and the hand rotation loose tool, fiber cloth is put first roll, second roll and pressure roller after volume on the loose tool is to 3 layers.
5. start and drive the motor that loose tool rotates.Roll in the process at glass reinforced plastic pipe that to regulate the linear velocity that motor speed guarantees that glass cloth advances loose tool be 1.5m/min.
6. in the process of rolling, fiber cloth is carried out gluing, fiber cloth is mended glue, before pressure roller, carry out frictioning at the second roll place at the first roll place.
7. when in the process of rolling, needing to change glass fabric, repeating step 4.In step 4 implementation process, the gluing glass cloth will be cut in the joint neatly, newly laying below and the overlapping 150mm of former cloth of gluing, and carry out the mark of joint, guarantee that all joints are uniform on 360 °.When changing cloth, adopt the glue of new preparation without exception, forbid with having used the glue a period of time of after.
8. reach 146mm through measuring glass reinforced plastic pipe thickness, stop work feed.2 layers of mylar of wrapping are changed the mylar on the pressure roller on the glass reinforced plastic pipe outer surface, and pressure roller is placed on the production line, and motor remains in operation and carries out normal temperature cure, stops after 8 hours, finishes normal temperature cure.
9. after normal temperature cure finished, disable motor took off rolled glass reinforced plastic pipe and sends baking oven to, rolled glass reinforced plastic pipe is carried out the back solidify processing.Solidify in the processing procedure in whole back, guarantee that glass reinforced plastic pipe temperature lowest part need reach 100 ℃ and maintain and be no less than 2 hours under this temperature.Finally obtaining thickness is the heavy wall glass reinforced plastic pipe of 145 ± 2mm (ф 290～ф 580mm, 290mm are the loose tool diameter, and 580mm is the glass reinforced plastic pipe overall diameter).
Example two
The making wall thickness is that the technology of 205 ± 2mm glass reinforced plastic pipe is as follows:
Scene temperature is 15 ℃, and humidity is 60%.
1. select the degreasing alkali-free glass fiber cloth through fertile blue coupling processing for use, model is VN-EW100B-100Y.Before rolling, fiber cloth goes tide to handle through baking in 9 hours under 80 ℃ of environment in baking oven.
2. glue is that 651 II type polyamides are formulated by bisphenol A type epoxy resin E-51 and curing agent.The allotment ratio: epoxy resin 70%, curing agent 30% is modulated glue 2kg at every turn.
3. loose tool, roll and 2 layers of mylar of pressure roller bag that will clean through acetone, outer surface is used the acetone scrub again, and two ends jointing adhesive band cements, and the mylar on roll and the pressure roller was changed once in 8 hours.Roll quality is 280kg/m.The pressure roller quality is 290kg/m.The loose tool diameter is 340mm.
4. before beginning to roll, loose tool, the 3rd roll and the 4th roll are placed on the production line; First roll, second roll and pressure roller are not placed on the production line.A bolt is set on the cloth beam, when beginning to roll, the Bradley time-out is just carried out gluing to fiber cloth, draw toward the loose tool place on gluing limit, limit, when fiber cloth is pulled to the loose tool place, and the hand rotation loose tool, fiber cloth is put first roll, second roll and pressure roller after volume on the loose tool is to 3.5 layers.
5. start and drive the motor that loose tool rotates.Roll in the process at glass reinforced plastic pipe that to regulate the linear velocity that motor speed guarantees that glass cloth advances loose tool be 1.6m/min.
6. in the process of rolling, fiber cloth is carried out gluing, fiber cloth is mended glue, before pressure roller, carry out frictioning at the second roll place at the first roll place.
7. when in the process of rolling, needing to change glass fabric, repeating step 4.In step 4 implementation process, the gluing glass cloth will be cut in the joint neatly, newly laying below and the overlapping 175mm of former cloth of gluing, and carry out the mark of joint, guarantee that all joints are uniform on 360 °.When changing cloth, adopt the glue of new preparation without exception, forbid with having used the glue a period of time of after.
8. reach 207mm through measuring glass reinforced plastic pipe thickness, stop work feed.2 layers of mylar of wrapping are changed the mylar on the pressure roller on the glass reinforced plastic pipe outer surface, and pressure roller is placed on the production line, and motor remains in operation and carries out normal temperature cure, stops after 10 hours, finishes normal temperature cure.
9. after normal temperature cure finished, disable motor took off rolled glass reinforced plastic pipe and sends baking oven to, rolled glass reinforced plastic pipe is carried out the back solidify processing.Solidify in the processing procedure in whole back, guarantee that glass reinforced plastic pipe temperature lowest part need reach 100 ℃ and maintain and be no less than 2 hours under this temperature.Finally obtaining thickness is the heavy wall glass reinforced plastic pipe of 205 ± 2mm (ф 340～ф 750mm, 340mm are the loose tool diameter, and 750mm is the fiberglass overall diameter).
Example three
The making wall thickness is that the technology of 262.5 ± 2mm glass reinforced plastic pipe is as follows:
Scene temperature is 25 ℃, and humidity is 55%.
1. select the degreasing alkali-free glass fiber cloth through fertile blue coupling processing for use, model is VN-EW100B-100Y.Before rolling, fiber cloth goes tide to handle through baking in 8.5 hours under 80 ℃ of environment in baking oven.
2. glue is that 651II type polyamide is formulated by bisphenol A type epoxy resin E-51 and curing agent.The allotment ratio: epoxy resin 70%, curing agent 30% is modulated glue 2kg at every turn.
3. loose tool, roll and 2 layers of mylar of pressure roller bag that will clean through acetone, outer surface is used the acetone scrub again, and two ends jointing adhesive band cements, and the mylar on roll and the pressure roller was changed once in 8 hours.Roll quality is 290kg/m.The pressure roller quality is 300kg/m.The loose tool diameter is 395mm.
4. before beginning to roll, loose tool, the 3rd roll and the 4th roll are placed on the production line; First roll, second roll and pressure roller are not placed on the production line.A bolt is set on the cloth beam, when beginning to roll, the Bradley time-out is just carried out gluing to fiber cloth, draw toward the loose tool place on gluing limit, limit, when fiber cloth is pulled to the loose tool place, and the hand rotation loose tool, fiber cloth is put first roll, second roll and pressure roller after volume on the loose tool is to 4 layers.
5. start and drive the motor that loose tool rotates.Roll in the process at glass reinforced plastic pipe that to regulate the linear velocity that motor speed guarantees that glass cloth advances loose tool be 1.7m/min.
6. in the process of rolling, fiber cloth is carried out gluing, fiber cloth is mended glue, before pressure roller, carry out frictioning at the second roll place at the first roll place.
7. when in the process of rolling, needing to change glass fabric, repeating step 4.In step 4 implementation process, the gluing glass cloth will be cut in the joint neatly, newly laying below and the overlapping 200mm of former cloth of gluing, and carry out the mark of joint, guarantee that all joints are uniform on 360 °.When changing cloth, adopt the glue of new preparation without exception, forbid with having used the glue a period of time of after.
8. reach 265mm through measuring glass reinforced plastic pipe thickness, stop work feed.2 layers of mylar of wrapping are changed the mylar on the pressure roller on the glass reinforced plastic pipe outer surface, and pressure roller is placed on the production line, and motor remains in operation and carries out normal temperature cure, stops after 10 hours, finishes normal temperature cure.
9. after normal temperature cure finished, disable motor took off rolled glass reinforced plastic pipe and sends baking oven to, rolled glass reinforced plastic pipe is carried out the back solidify processing.Solidify in the processing procedure in whole back, guarantee that glass reinforced plastic pipe temperature lowest part need reach 100 ℃ and maintain and be no less than 2 hours under this temperature.Finally obtaining thickness is the heavy wall glass reinforced plastic pipe of 262.5 ± 2mm (ф 395～ф 920mm, 395mm are the loose tool diameter, and 920mm is the fiberglass overall diameter).
Claims (8)
1, the continuous roll-forming preparation method of a kind of low temperature thick-wall glass reinforced plastic pipe, it is characterized in that adopting the continuous coiled forming technology of wet method, be to take off the continuous roll-forming of ester alkali-free glass fiber cloth on the mechanization streamline of one at gluing, moulding, benefit glue, frictioning, pipe crimping, after the normal temperature cure, carry out the back again and solidify the heavy wall glass reinforced plastic pipe material that processing obtains not having lamination; The used glue of the present invention is that 70% bisphenol A type epoxy resin E-51 and the allotment of 30%651II type polyamide form, and the glue amount of each modulation is no more than 2kg; Normal temperature cure is after the glass reinforced plastic pipe external diameter reaches given size, on the glass reinforced plastic pipe outer surface, wrap up 1～2 layer of mylar, change the mylar on the pressure roller, and pressure roller is placed on the production line, motor remains in operation and carries out normal temperature cure, and the normal temperature cure time is not less than 8 hours.
2, the continuous roll-forming preparation method of low temperature thick-wall glass reinforced plastic pipe according to claim 1, its feature also is, glass fabric is the degreasing alkali-free glass fiber cloth through fertile blue coupling processing among the present invention, model is VN-EW100B-100Y, fertile blue oil content≤1.5%, glass fabric rolling before through 80 ℃, the tide processing is gone in baking more than 8 hours; When rolling, preceding two-layer and last two-layer all the cutting of every bundle glass fabric do not used, and stops dust and pollution.
3, the continuous roll-forming preparation method of low temperature thick-wall glass reinforced plastic pipe according to claim 1, its feature also is, before rolling, loose tool, roll and 1～2 layer of mylar of pressure roller bag that will clean through acetone, outer surface is used the acetone scrub again, two ends jointing adhesive band cements, and the mylar on roll and the pressure roller was changed once in 8 hours; Every meter length topping roll and pressure roller quality are 290 ± 20kg.
4, the continuous roll-forming preparation method of low temperature thick-wall glass reinforced plastic pipe according to claim 1, its feature also are, before beginning to roll, loose tool, the 3rd roll and the 4th roll are placed on the production line; First roll, second roll and pressure roller are not placed on the production line; A bolt is set on the cloth beam, when beginning to roll, the Bradley time-out is just carried out gluing to fiber cloth, draw toward the loose tool place on gluing limit, limit, when fiber cloth is pulled to the loose tool place, and the hand rotation loose tool, fiber cloth is put first roll, second roll and pressure roller after volume on the loose tool is to 3～4 layers.
5, the continuous roll-forming preparation method of low temperature thick-wall glass reinforced plastic pipe according to claim 1, its feature also are, start the motor that drives the loose tool rotation; Rotating speed of motor is adjustable, guarantee that the linear velocity that in whole glass reinforced plastic pipe roll-forming process gluing glass cloth advances loose tool is 1.5～2.0m/min, in the process of rolling, fiber cloth is carried out gluing at the first roll place, at the second roll place fiber cloth is mended glue, before pressure roller, carry out frictioning.
6, the continuous roll-forming preparation method of low temperature thick-wall glass reinforced plastic pipe according to claim 1, its feature also is, when in the process of rolling, needing to change glass fabric, the gluing glass cloth will be cut in the joint neatly, newly laying below and the overlapping 150～200mm of former cloth of gluing, and carry out the mark of joint, guarantee that all joints are uniform on 360 °; When changing cloth, adopt the glue of new preparation without exception, forbid with having used the glue a period of time of after.
7, the continuous roll-forming preparation method of low temperature thick-wall glass reinforced plastic pipe according to claim 1, its feature are that also after normal temperature cure finished, disable motor took off rolled glass reinforced plastic pipe and sends baking oven to, rolled glass reinforced plastic pipe is carried out the back solidify processing; The baking oven of using among the present invention is an air dry oven, the temperature inside the box fluctuation degree≤± 1 ℃, the unevenness of the temperature inside the box≤± 2.5%; Solidify in the processing procedure in whole back, guarantee that glass reinforced plastic pipe temperature lowest part need reach 100 ℃ and maintain and be no less than 2 hours under this temperature.
8, the continuous roll-forming preparation method of low temperature thick-wall glass reinforced plastic pipe according to claim 1, its feature also is, among the present invention when making glass reinforced plastic pipe, should guarantee the few dust of glass reinforced plastic pipe moulding make-up room, temperature is controlled at 15 ℃～25 ℃, relative humidity should be not more than 75%, forbids oil and fat.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031165990A CN100509358C (en) | 2003-04-24 | 2003-04-24 | Continuous rolling shaping method of low-temperature thick wall GFRP tube |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031165990A CN100509358C (en) | 2003-04-24 | 2003-04-24 | Continuous rolling shaping method of low-temperature thick wall GFRP tube |
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| Publication Number | Publication Date |
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| CN1448261A CN1448261A (en) | 2003-10-15 |
| CN100509358C true CN100509358C (en) | 2009-07-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB031165990A Expired - Fee Related CN100509358C (en) | 2003-04-24 | 2003-04-24 | Continuous rolling shaping method of low-temperature thick wall GFRP tube |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1318790C (en) * | 2005-02-04 | 2007-05-30 | 连云港中复连众复合材料集团有限公司 | High-pressure glass fibre reinforced plastic pipe and producing technology thereof |
| CN104559816A (en) * | 2015-02-05 | 2015-04-29 | 曾昭峰 | Splicing method of glass felts |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111736A (en) * | 1994-12-03 | 1995-11-15 | 兰亚军 | Pipe material made from plastic alloy double-composite modified reinforced fibre glass and manufacturing method thereof |
| US5629062A (en) * | 1993-09-13 | 1997-05-13 | Petoca, Ltd. | Fiber reinforced plastic pipe and process for producing the same |
| CN2440649Y (en) * | 2000-08-21 | 2001-08-01 | 陈美兰 | Glass fiber reinforced plastic winding machine |
-
2003
- 2003-04-24 CN CNB031165990A patent/CN100509358C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5629062A (en) * | 1993-09-13 | 1997-05-13 | Petoca, Ltd. | Fiber reinforced plastic pipe and process for producing the same |
| CN1111736A (en) * | 1994-12-03 | 1995-11-15 | 兰亚军 | Pipe material made from plastic alloy double-composite modified reinforced fibre glass and manufacturing method thereof |
| CN2440649Y (en) * | 2000-08-21 | 2001-08-01 | 陈美兰 | Glass fiber reinforced plastic winding machine |
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Granted publication date: 20090708 Termination date: 20120424 |