CN104130393A - Continuous fiber enhanced thermoplastic composite material prepreg tape preparation method and device for realizing the method - Google Patents
Continuous fiber enhanced thermoplastic composite material prepreg tape preparation method and device for realizing the method Download PDFInfo
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- CN104130393A CN104130393A CN201410317817.1A CN201410317817A CN104130393A CN 104130393 A CN104130393 A CN 104130393A CN 201410317817 A CN201410317817 A CN 201410317817A CN 104130393 A CN104130393 A CN 104130393A
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Abstract
The invention provides a continuous fiber enhanced thermoplastic composite material prepreg tape preparation method and a device for realizing the method. According to the method, molten thermoplastic resin monomer or oligomer is sprayed on the surface of a fiber yarn tape under the existence of a catalyst. Compared with thermosetting resin, heated and molten thermoplastic resin monomer or oligomer has low viscosity, such that the molten resin can easily and fully impregnate the fiber yarn tape. The fiber yarn tape is heated, such that the thermoplastic resin monomer or oligomer is subjected to a polymerization reaction. The temperature is reduced, such that the continuous fiber enhanced thermoplastic composite material prepreg tape is obtained. On the one hand, the prepreg tape has enough toughness and other performances. On the other hand, the porosity between the thermoplastic resin polymer and fiber is greatly reduced, such that prepreg tape interface strength is effectively improved. The device has the advantages of simple structure and low cost. The device is suitable for continuous batch productions of the continuous fiber enhanced thermoplastic composite material prepreg tapes.
Description
Technical field
The present invention relates to technical field of composite materials, relate in particular to a kind of preparation method of continuous fiber reinforced thermoplastic composite material prepreg and realize the equipment of the method.
Background technology
Continuous fiber reinforced thermoplastic composite material has good over-all properties, its prepreg tape can preserve, under high temperature, high humidity, can keep good mechanical property, forming method many for a long time, production efficiency is high, goods can repeat processing, reproducible utilization also, therefore in recent years, demand rapid growth, tempo is than the high several times of same with thermosetting compound material.
At present, the preparation method of the continuous fiber reinforced thermoplastic composite material prepreg of open report mainly comprises solution impregnation, melt impregnation, powder impregnating, although method is a lot, every kind of method all has relative merits separately.
Although solution dipping method simple process, equipment is simple, but will be generally need to be by heating impregnation of fibers to remove the solvent for solution heat plastic resin, and in order to remove this solvent completely, need to desolventize in process in heating, the travelling speed of impregnation of fibers is very slow, even needs to stay for some time; Meanwhile, the volatilization of solvent and recovery need larger investment and energy consumption, are in this way difficult to be applicable in the batch production of serialization.
Melt impregnation method is by impregnation of fibers after thermoplastic resin heating and melting, due to the viscosity high (being generally 500～5000Pas) after resin fusing, and general being difficult to fiber complete wetting, this application to this technological method has brought limitation.
Powder pickling process is mainly by fluidization, electrostatic technique, bundle fiber to be disperseed, and powder is evenly dispersed between fiber, then through baker heat fused.The weak point of this processing method is that the infiltration of fiber only just can complete in molding process, and it is all relevant with size and the distribution situation thereof of diameier to infiltrate required time, temperature, pressure, and the prepreg quality stability of preparation is poor and wayward.
Summary of the invention
For the above-mentioned state of the art, the present invention aims to provide a kind of manufacture method of continuous fiber reinforced thermoplastic composite material prepreg, and the method is simple, and thermoplastic resin easily fully infiltrates fiber, thereby effectively improves the boundary strength of prepreg tape.
In order to realize above-mentioned technical purpose, the technical solution adopted in the present invention is: a kind of preparation method of continuous fiber reinforced thermoplastic composite material prepreg, comprise step: by the monomer of thermoplastic resin or oligopolymer heating and melting, after adding catalyzer to form mixed melt, be sprayed at silvalin belt surface, make its abundant impregnation of fibers cotton yarn tape, then fiber cotton yarn tape is heated up, make monomer or the oligopolymer initiated polymerization of thermoplastic resin.
Described continuous fibre kind is not limit, and comprises continuous glass fibre, continuous carbon fibre etc.
Described resin monomer or oligopolymer are not limit, and comprise hexanolactam, laurolactam, ring-type mutual-phenenyl two acid bromide two alcohol ester (CBT) etc.
Described catalyzer is selected according to resin monomer or oligopolymer kind, include but not limited to sodium hydroxide, sodium caprolactam(ate), hexanolactam magnesium bromide, tin class or titanium class, tolylene diisocyanate, isophorone diisocyanate, '-diphenylmethane diisocyanate, dicyclohexyl methane diisocyanate, hexa-methylene-1, the combination of one or more in 6-bis-formyl hexanolactams etc.
The mass ratio of described resin monomer or oligopolymer and catalyzer is 100:0.1～100:20, more preferably 100:0.1～100:10.
For mixed melt is evenly sprayed to silvalin belt surface, as preferably, the spray rate of this mixed melt is that 1～50ml/ second, spray pressure are 0.3～2.0MPa.In order further improving, to spray homogeneity, before spraying, fiber cotton yarn tape to be uniformly dispersed.
In sum, first the present invention is sprayed at silvalin belt surface by the monomer of the thermoplastic resin after melting or oligopolymer under catalyzer existence condition, compare with thermosetting resin, the monomer of the thermoplastic resin of heating and melting or the viscosity of oligopolymer very low (conventionally in 100mpas left and right), therefore be easy to infiltrate fiber cotton yarn tape, and infiltrate fully; Then the fiber cotton yarn tape of the monomer of this thermoplastic resin or oligopolymer infiltration is heated up, make monomer or the oligopolymer initiated polymerization of thermoplastic resin, its molecular chain increases rapidly, molecular weight increases rapidly, obtain continuous fiber reinforced thermoplastic composite material prepreg, this prepreg tape has enough toughness and other performance on the one hand, and the porosity between thermoplastic resin polymer and fiber reduces greatly on the other hand, thereby has effectively improved the boundary strength of prepreg tape.In addition, the processing requirement that the present invention can be prepared according to different thermoplastic resins and prepreg tape is selected different types of catalyzer and catalyst quality ratio, thus Technological adaptability and handiness higher.
The present invention also provides a kind of equipment of realizing above-mentioned continuous fiber reinforced thermoplastic composite material prepreg preparation method, and this equipment comprises yarn divider, primary heater unit, heating immersion system, mixing tank, heated polymerizable device, refrigerating unit and around winding apparatus;
Yarn divider, for continuous fibre is carried out to dividing sinker, smooth, obtains the continuous fibre cotton yarn tape of parallel arrangement;
Primary heater unit is for preheating continuous fibre cotton yarn tape;
Mixing tank, for the resin monomer of melting or oligopolymer are mixed with catalyzer, forms mixed melt;
Heating immersion system at least arranges a nozzle; Mixed melt is the silvalin belt surface after preheating by nozzles spray, makes the monomer of thermoplastic resin or oligopolymer infiltrate fiber cotton yarn tape;
Heated polymerizable device, for making to infiltrate monomer or the oligopolymer polymerization reaction take place at the thermoplastic resin of fiber cotton yarn tape, forms continuous fiber reinforced thermoplastic composite material prepreg;
Refrigerating unit is for cooling by continuous fiber reinforced thermoplastic composite material prepreg;
Around winding apparatus, be used for cooled continuous fiber reinforced thermoplastic composite material prepreg around volume.
Utilize this equipment to prepare the process of continuous fiber reinforced thermoplastic composite material prepreg as follows:
(1) continuous fibre carries out dividing sinker, smooth in yarn divider, obtains the continuous fibre cotton yarn tape of parallel arrangement;
(2) continuous fibre cotton yarn tape enters primary heater unit and carries out preheating;
(3) the continuous fibre cotton yarn tape after preheating enters heating immersion system, the monomer of thermoplastic resin or oligopolymer mix at mixing tank with catalyzer, form mixed melt, then the surface of the continuous fibre cotton yarn tape after preheating by nozzles spray, infiltrates continuous fibre cotton yarn tape;
(4) the continuous fibre cotton yarn tape of infiltration mixed melt enters heated polymerizable device, and the monomer of thermoplastic resin wherein or oligopolymer polymerization reaction take place form continuous fiber reinforced thermoplastic composite material prepreg;
(5) continuous fiber reinforced thermoplastic composite material prepreg enter refrigerating unit with around winding apparatus carry out cooling, around volume.
As a kind of implementation, described yarn divider comprises creel, the dividing sinker broach and exhibition yarn roller group with tension controller.The tension control scope of creel is preferably 5N～50N.
As a kind of implementation, described heating immersion system adopts double-cylinder articulated half cap-opening mechanism, to facilitate continuous fibre cotton yarn tape entry or draw; Heat-supplying mode is not limit, and comprises the modes such as resistive heating, Infrared Heating, deep fat heating; The preheating temperature of continuous fibre cotton yarn tape is preferably controlled at 100 ℃～250 ℃.
In order to improve as the monomer of thermoplastic resin or oligopolymer at the wettability of fiber cotton yarn tape, as preferably, dipping stack group is set in described heating immersion system, silvalin belt surface carries out roll-in through dipping stack group after spraying mixed melt.
As preferably, described mixing tank adopts stainless material to make.As preferably, described mixing tank is demountable structure.
Described refrigerating unit adopts the modes such as air cooling or water-cooled to carry out cooling.
As preferably, all pipelines of described mixing tank and nozzle have heating and heat preserving function, and type of heating is not limit, and comprise modes such as adopting oil heating or electrically heated.As further preferred, this temperature adjustable.
Aforesaid device is simple in structure, cost is low, is suitable for continuous batch production continuous fiber reinforced thermoplastic composite material prepreg.
Accompanying drawing explanation
Fig. 1 prepares the structural representation of the equipment of continuous fiber reinforced thermoplastic composite material prepreg in the embodiment of the present invention 1;
Fig. 2 is the enlarged view that heats immersion system in Fig. 1;
Reference numeral in Fig. 1-2 is: 1. creel, 2. yarn group, 3. continuous fibre, 3-1 continuous fibre cotton yarn tape, 4. dividing sinker broach, 5. exhibition yarn roller group, 6. heating container, 7. nozzle, 8. motionless mixer, 9. heating dipping box, 9-1. case lid, 9-2. casing, 10. dipping stack group, 11. heated polymerizable casees, 12. cooling roller groups, 13. traction wind2s.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and it is not played to any restriction effect.
Embodiment 1:
In the present embodiment, for the preparation of the structural representation of the equipment of continuous fiber reinforced thermoplastic composite material prepreg as shown in Figure 1, comprise yarn divider, preheated tank 6, heating dipping box 9, motionless mixer 8, heated polymerizable case 11 and cooling roller group 12 with around winding apparatus 13.
Yarn divider, for continuous fibre is carried out to dividing sinker, smooth, obtains the continuous fibre cotton yarn tape of parallel arrangement, comprises creel 1, yarn group 2, dividing sinker broach 4 and exhibition yarn roller group 5.Yarn group 2 is arranged on the spindle of creel 1, and 20 volumes are installed altogether.Each spindle has cylinder oscillating rod type tension controller structure, tension force precision≤3%, and when every bundle continuous fibre 3 is drawn, tension force equates, and fiber tension force all-the-time stable in operational process is even.Continuous fibre 3 draws successively by dividing sinker broach 4 and exhibition yarn roller group 5.After dividing sinker broach 4, fibrous bundle is arranged parallel even, mutually non-cross, and broach 4 adopts the stainless material of meticulous sanding and polishing to make, ratch diameter 1～3mm, and adjacent teeth spacing is 4～8mm.Exhibition yarn roller group 5 is comprised of two running rollers, and wherein first running roller is adjustable up and down, and to adjust fiber cornerite, roller surface material adopts tetrafluoroethylene.
Preheated tank 6 is for preheating continuous fibre cotton yarn tape;
Motionless mixer 8 arranges the resin monomer of melting or the inlet of oligopolymer and catalyzer inlet, for the resin monomer or the oligopolymer that inject melting are wherein mixed with catalyzer, forms mixed melt.Static mixer 8 adopts stainless steel demountable structure, to facilitate the cleaning after prepared by preimpregnation cotton yarn tape.
Heating dipping box 9 comprises case lid 9-1 and casing 9-2, and case lid 9-1 top arranges three nozzles 7, and mixed melt is sprayed at the silvalin belt surface after preheating by nozzle 7, makes the monomer of thermoplastic resin or oligopolymer infiltrate fiber cotton yarn tape.Dipping stack group 10 is also set in heating dipping box 9, and silvalin belt surface carries out roll-in through dipping stack group after spraying mixed melt, so that the monomer of thermoplastic resin or oligopolymer fully infiltrate fiber cotton yarn tape.Each running roller of dipping stack group 10 all adopts the stainless material of meticulous sanding and polishing to make.
Heated polymerizable case 11 makes to infiltrate monomer or the oligopolymer polymerization reaction take place at the thermoplastic resin of fiber cotton yarn tape, forms continuous fiber reinforced thermoplastic composite material prepreg.
Utilize this device that continuous fibre 3 is prepared as to continuous fiber reinforced thermoplastic composite material prepreg, continuous fibre 3 is continuous high-strength glass fibre SC8-960, and thermoplastic resin material is nylon 6, is specially anionic polymerization nylon 6, is called for short APA6.Selecting thermoplastic resin alicyclic monomer is hexanolactam resin monomer, catalyzer is by Primary Catalysts and help Primary Catalysts to form, Primary Catalysts is sodium hydroxide, sodium caprolactam(ate) or hexanolactam magnesium bromide, promotor is tolylene diisocyanate, isophorone diisocyanate, '-diphenylmethane diisocyanate, dicyclohexyl methane diisocyanate or hexa-methylene-1,6-bis-formyl hexanolactams etc.Concrete preparation process is as follows:
(1) initial tension of each spindle is set as to 5N, continuous fibre 3 is drawn from creel 1, by dividing sinker broach 4 dividing sinkers, by exhibition yarn roller group 5, flatten again, obtain smooth, obtain fibrous bundle parallel arrangement, mutually non-cross, and smooth continuous fibre cotton yarn tape, for example continuous fibre cotton yarn tape 3-1;
(2) the continuous fibre cotton yarn tape flattening enters preheated tank 6 and dries and preheating, and preheating temperature is set as 120 ℃～150 ℃;
(3) the continuous fibre cotton yarn tape after preheating enters heating dipping box 9, and the Temperature Setting of heating dipping box 9 is 100 ℃～120 ℃; Now, the hexanolactam resin monomer of high-temperature fusion and catalyzer and promotor are squeezed into static mixer 8 under glue-injection machine effect, the mass ratio of hexanolactam resin monomer and tin class or titanium class catalyst A is set as 100:0.1～100:3, injecting glue rate setting is 30ml/ second, pressure setting is 0.5MPa, by three nozzles 7, mixed with resin melt is evenly sprayed to glass continuous filament yarn belt surface respectively after sufficiently mixing, impregnation of fibers cotton yarn tape, then by dipping stack group 10 further abundant impregnation of fibers cotton yarn tapes; Glue-injection machine adopts silicon rubber heat tape be coated and heat to all metal tubes outside surfaces of nozzle 7, and the Heating temperature of silicon rubber heat tape is set as 120 ℃;
(4) the continuous fibre cotton yarn tape after fully flooding enters heated polymerizable case 11, hexanolactam resin monomer wherein completes polymerization at 150 ℃～220 ℃ of temperature, then be pulled by cooling roller group 12, cooling roller group 12 adopts circulating water, finally by 13 rollings of traction wind2, stock, the pulling speed of wind2 is set as 10～30m/min.
Embodiment 2:
In the present embodiment, identical with the equipment in embodiment 1 for the preparation of the equipment of continuous fiber reinforced thermoplastic composite material prepreg.
Utilize this device that continuous fibre 3 is prepared as to continuous fiber reinforced thermoplastic composite material prepreg, continuous fibre 3 is continuous carbon fibre T700-12K, and thermoplastic resin material is CBT.Selecting thermoplastic resin alicyclic monomer is ring-type mutual-phenenyl two acid bromide two alcohol ester monomer, and catalyzer is tin class or titanium class catalyst B.
Preparation process in concrete preparation process and embodiment 1 is basic identical, and difference is: the drying and forewarm Temperature Setting of heating container 6 is 200 ℃～250 ℃; The Temperature Setting of heating dipping box 9 is 190 ℃; The Heating temperature of silicon rubber heat tape is set as 190 ℃～220 ℃.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any modifications of making within the scope of principle of the present invention, supplement or similar fashion substitutes etc., within all should being included in protection scope of the present invention.
Claims (11)
1. a preparation method for continuous fiber reinforced thermoplastic composite material prepreg, is characterized in that: comprise the steps:
By the monomer of thermoplastic resin or oligopolymer heating and melting, be sprayed at silvalin belt surface after adding catalyzer to form mixed melt, make its abundant impregnation of fibers cotton yarn tape, then fiber cotton yarn tape is heated up, make monomer or the oligopolymer initiated polymerization of thermoplastic resin.
2. the preparation method of continuous fiber reinforced thermoplastic composite material prepreg as claimed in claim 1, is characterized in that: described continuous fibre is continuous glass fibre or continuous carbon fibre.
3. the preparation method of continuous fiber reinforced thermoplastic composite material prepreg as claimed in claim 1, is characterized in that: described resin monomer or oligopolymer are hexanolactam, laurolactam, or ring-type mutual-phenenyl two acid bromide two alcohol ester.
4. the preparation method of continuous fiber reinforced thermoplastic composite material prepreg as claimed in claim 1, it is characterized in that: described catalyzer is sodium hydroxide, sodium caprolactam(ate), hexanolactam magnesium bromide, tin class or titanium class, tolylene diisocyanate, isophorone diisocyanate, '-diphenylmethane diisocyanate, dicyclohexyl methane diisocyanate, hexa-methylene-1 combination of one or more in 6-bis-formyl hexanolactams.
5. the preparation method of continuous fiber reinforced thermoplastic composite material prepreg as claimed in claim 1, is characterized in that: the mass ratio of described resin monomer or oligopolymer and catalyzer is 100:0.1～100:20.
6. the preparation method of continuous fiber reinforced thermoplastic composite material prepreg as claimed in claim 1, is characterized in that: the spray rate of described mixed melt is that 1～50ml/ second, spray pressure are 0.3～2.0MPa.
7. the equipment of realizing continuous fiber reinforced thermoplastic composite material prepreg preparation method claimed in claim 1, is characterized in that: comprise yarn divider, primary heater unit, heating immersion system, mixing tank, heated polymerizable device, refrigerating unit and around winding apparatus;
Yarn divider, for continuous fibre is carried out to dividing sinker, smooth, obtains the continuous fibre cotton yarn tape of parallel arrangement;
Primary heater unit is for preheating continuous fibre cotton yarn tape;
Mixing tank, for the resin monomer of melting or oligopolymer are mixed with catalyzer, forms mixed melt;
Heating immersion system at least arranges a nozzle; Mixed melt is the silvalin belt surface after preheating by nozzles spray, makes the monomer of thermoplastic resin or oligopolymer infiltrate fiber cotton yarn tape;
Heated polymerizable device, for making to infiltrate monomer or the oligopolymer polymerization reaction take place at the thermoplastic resin of fiber cotton yarn tape, forms continuous fiber reinforced thermoplastic composite material prepreg;
Refrigerating unit is for cooling by continuous fiber reinforced thermoplastic composite material prepreg;
Around winding apparatus, be used for cooled continuous fiber reinforced thermoplastic composite material prepreg around volume.
8. the equipment of preparing continuous fiber reinforced thermoplastic composite material prepreg as claimed in claim 7, is characterized in that: preparation process is as follows:
(1) continuous fibre carries out dividing sinker, smooth in yarn divider, obtains the continuous fibre cotton yarn tape of parallel arrangement;
(2) continuous fibre cotton yarn tape enters primary heater unit and carries out preheating;
(3) the continuous fibre cotton yarn tape after preheating enters heating immersion system, the monomer of thermoplastic resin or oligopolymer mix at mixing tank with catalyzer, form mixed melt, then the surface of the continuous fibre cotton yarn tape after preheating by nozzles spray, infiltrates continuous fibre cotton yarn tape;
(4) the continuous fibre cotton yarn tape of infiltration mixed melt enters heated polymerizable device, and the monomer of thermoplastic resin wherein or oligopolymer polymerization reaction take place form continuous fiber reinforced thermoplastic composite material prepreg;
(5) continuous fiber reinforced thermoplastic composite material prepreg enter refrigerating unit with around winding apparatus carry out cooling, around volume.
9. the equipment of preparing continuous fiber reinforced thermoplastic composite material prepreg as claimed in claim 7, is characterized in that:
Described yarn divider comprises creel, the dividing sinker broach and exhibition yarn roller group with tension controller.
10. the equipment of preparing continuous fiber reinforced thermoplastic composite material prepreg as claimed in claim 7, it is characterized in that: described primary heater unit, heating immersion system, heated polymerizable device all adopt double-cylinder articulated half cover-opening structure, described heat-supplying mode is that thermopair is controlled, resistive heating or Infrared Heating.
11. equipment of preparing continuous fiber reinforced thermoplastic composite material prepreg as claimed in claim 7, it is characterized in that: dipping stack group is set in described heating immersion system, and silvalin belt surface carries out roll-in through dipping stack group after spraying mixed melt.
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| CN105504269A (en) * | 2016-01-06 | 2016-04-20 | 东华大学 | Thermoplastic-resin-based carbon fiber composite and preparing method thereof |
| CN106239937A (en) * | 2016-09-07 | 2016-12-21 | 东华大学 | A kind of device preparing continuous fiber reinforced thermoplastic prepreg tape |
| CN106478942A (en) * | 2016-09-30 | 2017-03-08 | 湖南工业大学 | A kind of high obstructing performance rotational moulding nylon products and preparation method thereof |
| CN107298813A (en) * | 2017-06-25 | 2017-10-27 | 长沙善道新材料科技有限公司 | A kind of prepreg tape based on high-temperature-resistant thermoplastic composite resin and preparation method thereof |
| CN108858883A (en) * | 2018-05-30 | 2018-11-23 | 江苏兆鋆新材料股份有限公司 | A kind of method that phenoxy resin prepreg and hot melt prepare the phenoxy resin prepreg |
| CN109177219A (en) * | 2018-09-25 | 2019-01-11 | 北航（四川）西部国际创新港科技有限公司 | It is driven production method of shaft and transmission shaft |
| CN110587854A (en) * | 2019-08-07 | 2019-12-20 | 深圳大学 | Fiber resin compound and preparation method thereof |
| CN111098527A (en) * | 2018-10-26 | 2020-05-05 | 约翰斯曼维尔公司 | System for producing fully impregnated thermoplastic prepregs |
| CN111761844A (en) * | 2020-06-30 | 2020-10-13 | 诺思贝瑞新材料科技（苏州）有限公司 | Continuous fiber composite material for 3D printing and preparation method and device thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504269A (en) * | 2016-01-06 | 2016-04-20 | 东华大学 | Thermoplastic-resin-based carbon fiber composite and preparing method thereof |
| CN105504269B (en) * | 2016-01-06 | 2018-02-23 | 东华大学 | A kind of thermoplastic resin-based carbon fiber composite and preparation method thereof |
| CN106239937A (en) * | 2016-09-07 | 2016-12-21 | 东华大学 | A kind of device preparing continuous fiber reinforced thermoplastic prepreg tape |
| CN106239937B (en) * | 2016-09-07 | 2018-07-17 | 东华大学 | A kind of device preparing continuous fiber reinforced thermoplastic prepreg tape |
| CN106478942A (en) * | 2016-09-30 | 2017-03-08 | 湖南工业大学 | A kind of high obstructing performance rotational moulding nylon products and preparation method thereof |
| CN107298813A (en) * | 2017-06-25 | 2017-10-27 | 长沙善道新材料科技有限公司 | A kind of prepreg tape based on high-temperature-resistant thermoplastic composite resin and preparation method thereof |
| CN108858883A (en) * | 2018-05-30 | 2018-11-23 | 江苏兆鋆新材料股份有限公司 | A kind of method that phenoxy resin prepreg and hot melt prepare the phenoxy resin prepreg |
| CN109177219A (en) * | 2018-09-25 | 2019-01-11 | 北航（四川）西部国际创新港科技有限公司 | It is driven production method of shaft and transmission shaft |
| CN111098527A (en) * | 2018-10-26 | 2020-05-05 | 约翰斯曼维尔公司 | System for producing fully impregnated thermoplastic prepregs |
| CN110587854A (en) * | 2019-08-07 | 2019-12-20 | 深圳大学 | Fiber resin compound and preparation method thereof |
| CN111761844A (en) * | 2020-06-30 | 2020-10-13 | 诺思贝瑞新材料科技（苏州）有限公司 | Continuous fiber composite material for 3D printing and preparation method and device thereof |
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Application publication date: 20141105 |