CN107722564A - The preparation method and product of a kind of glass fiber resin compound material - Google Patents
The preparation method and product of a kind of glass fiber resin compound material Download PDFInfo
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- CN107722564A CN107722564A CN201711020582.XA CN201711020582A CN107722564A CN 107722564 A CN107722564 A CN 107722564A CN 201711020582 A CN201711020582 A CN 201711020582A CN 107722564 A CN107722564 A CN 107722564A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The invention belongs to material increasing field, and disclose the preparation method and product of a kind of glass fiber resin compound material.The preparation method includes：Coupling agent modified glass fibre is added in the resin solution for being dissolved completely in organic solvent；Then will be dried after mixed liquor ball milling；By pulverizing and sieving to obtain the composite powder of resin-coating glass fibre；Liquid thermosetting resin is infiltrated again after shaping just base with SLS technologies obtains final drip molding.Present invention also offers the product obtained in the method.By the present invention, drip molding mechanics and excellent electrical properties, the 3D solid shape for any structure that shaping traditional handicraft is difficult to out, short preparation period, solve the problems, such as electrically insulating material due to simple shape and apply limited.
Description
Technical field
The invention belongs to material increasing field, more particularly, to a kind of preparation side of glass fiber resin compound material
Method and product.
Background technology
Selective laser sintering (Selective Laser Sintering, SLS), it is that (also known as 3D is beaten for a kind of increasing material manufacturing
Print) technology.SLS technologies are by the threedimensional model of CAD part, based on successively principle of stacking, in computer control
Powder is selectively sintered according to layering cross section information under system, can obtain the Three-dimensional Entity Components of any labyrinth.
Glass fibre (glass fiber) is a kind of inorganic non-metallic material of excellent performance, and species is various, can be used as in composite
Reinforcing material, electrically insulating material and heat-insulating material, circuit substrate etc. are applied to the every field of national economy.With firm
Property big, good insulating, heat resistance is strong, corrosion resistance is good, the advantages that high mechanical strength.
In recent years, China's power industry develops rapidly, and high voltage, Large Copacity equipment increase severely, and power equipment manufacturer is to multiple
Miscellaneous shape, large-size components product demand rise year by year.At present, the galss fiber reinforced resin composite commonly used both at home and abroad
Manufacturing process has hand lay-up, injection shaping, die forming, molding compound shaping, filament winding moulding, pultrusion etc., but this
A little traditional handicrafts are difficult to parts with complex structures, and have the shortcomings that a lot.The quality of item of hand lay-up is not sufficiently stable, shelves
Secondary not high enough, hardly possible meets the performance requirement of some products.The quality of item of injection shaping depends greatly on operative employee
The production skills of people, pollution are big.Pressure stochastic distribution complex operation, production efficiency are relatively low.Die forming and moulding compound shaping institute
Obtained product is limited by equipment and more protruded, and needs to design mould, and manufacture is complex.The mold design of pultrusion
It is complex, cracking phenomena occurs in forming process, causes product qualification rate to decline to a great extent.
SLS technologies have following advantage compared with traditional forming methods：Without mould, production cost is greatly reduced；Material
Expect that utilization rate is high, production efficiency is high；The labyrinth product that traditional handicraft is difficult to shape can be processed, it is especially especially big or special
Small-sized product, and product is not in cracking phenomena；Whole manufacturing process is all full-automatic process under the control of the computer,
Manual intervention is not needed, it is possible to achieve Unmanned operation and Grid method etc.；The SLS shaping galss fiber reinforced resins of preparation
Based powders, glass fibre are evenly distributed with resin matrix, and the product after shaping is isotropic, are not in larger no fibre
Wei Qu and without resin region, performance is more uniform, and still, current SLS processing methods can not shape parts with complex structures, and material profit
It is low with rate, the cycle length of shaping.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of glass fiber resin compound material
Preparation method and product, being dissolved in alcohol, acetone these organic solvents by using modified glass fibre and resin makes tree
Fat uniformly coats glass fibre, obtains being applied to the dusty material of SLS shapings so that drip molding has excellent mechanical property
And electrical insulation capability, thus solve that shaping parts with complex structures, stock utilization be low and the technical problem of the cycle of shaping length.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of glass fiber resin compound material
Preparation method, it is characterised in that the preparation method comprises the following steps：
(a) it is 4.5~15 by draw ratio：1 glass fibre, which is modified, obtains modified glass fibre so that glass fibre
It can be combined with phenolic resin, weigh phenolic resin and the modified glass fibre, and by the two dissolving in organic solvent
Solution is formed, wherein, the mass ratio of the organic solvent and phenolic resin is 2~6:1；
(b) the modified glass fibre, and ball milling are added again in the solution obtained in step (a), by ball milling
Product drying afterwards, it is derived from the glass fibre powder of dry resin-coating；
(c) by the glass fibre powder grinding and sieving of the resin-coating of the drying, choose wherein particle diameter be 35 μm~
150 μm of powder, the powder is then configured to just base by selective laser sintering, and the first base is carried out at first time solidification
Reason；
(d) the first base after solidification is infiltrated in liquid-state epoxy resin, required glass fibre and resin is obtained after infiltration
Composite.
It is further preferred that in step (a), the glass fibre modifying process is carried out according to the following steps, first will
Coupling agent and ethanol water are mixed to form mixed liquor, and glass fibre is calcined, and the glass fibre after calcining are added described mixed
Close and reacted in liquid, thus complete the modification of the glass fibre, wherein the temperature of the calcining is 300 DEG C~450 DEG C, during calcining
Between be 1h~2h, the mass fraction percentage of the coupling agent and the ethanol water is 2%~5%：1.
It is further preferred that in step (d), the infiltration comprises the following steps：
(d1) liquid-state epoxy resin and curing agent needed for infiltration are chosen, and the two is heated respectively, then in the heating
Curing accelerator is added in liquid-state epoxy resin and curing agent afterwards, is mixed and stirred for being formed uniformly infiltration liquid；
(d2) the first base after the solidification is placed in the infiltration liquid, 90 DEG C~110 DEG C is then heated to, in vacuum bar
30min~50min is infiltrated under part so that the liquid-state epoxy resin in the infiltration liquid fills the hole of the first base after the solidification
Gap, thus complete infiltration process；
(d3) the first base after infiltrating will be completed in step (d2) to take out from the infiltration liquid, and carry out secondary solidification, Gu
It is 90 DEG C~200 DEG C to change temperature, and hardening time is 3h~15h.
It is further preferred that the coupling agent is in silane coupler, aluminate coupling agent or titanate coupling agent
It is one or more.
It is further preferred that in step (a), the organic solvent is absolute ethyl alcohol or acetone.
It is further preferred that in step (b), the temperature of the drying is 30 DEG C~55 DEG C.
It is further preferred that in step (c), technological parameter is respectively during the selective laser sintering：Laser work(
Rate is 6W~20W, and sweep speed is 2000mm/s~3500mm/s, and sweep span is 0.2mm~0.4mm, and layering thickness is
0.1mm~0.2mm, preheating temperature are 45 DEG C~70 DEG C.
It is further preferred that in step (c), the temperature of the first time curing process is 160 DEG C~180 DEG C, solidification
Time is 2h~4h.
It is further preferred that the mass ratio of the liquid-state epoxy resin, curing agent and curing accelerator is 100:(60~
90):(0~0.30).
According to another aspect of the present invention, there is provided a kind of glass fibre tree according to obtained by above-mentioned preparation method
Resin composite material product.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect：
1st, the present invention is by using by the glass fibre dissolving of resin and modification, in organic solvent, organic solvent dissolving is set
Fat coats glass fibre, make resin and fiber be sufficiently mixed uniformly, reduce in test specimen and occur without pars fibrosa and without resin region phenomenon,
Isotropic product is obtained after SLS shapes；
2nd, the mode of the invention by using ball milling so that glass fibre can be mixed uniformly with phenolic resin, and heating makes
Fiberglass surfacing coats one layer of phenolic resin for making binding agent after solvent evaporation；
3rd, the present invention by sieve screening particle diameter be 35 μm~150 μm powder, good powdering effect can be obtained, avoid because
Particle diameter is excessive and product caused by causing powdering process shifts；
4th, the present invention can increase the densification of product by the way that infiltration is handled in the infiltration liquid of configuration by the first base after solidification
Degree, improves the intensity of product, meets requirement；
5th, the present invention improves the mechanical property of product by using solidification twice, merely through the epoxy resin of first time
Curing process, phenolic resin and the ammonia and hydrone of hexamethylenetetramine reaction release are difficult to be excluded from the sample of solidification,
Cause to occur space in network structure and hinder reaction to continue, not sufficiently reactive part is there is a possibility that system generation lacks
Fall into, stress concentration is also easy to produce around it, reduces the mechanics and electric property of final product；
6th, the present invention changes the surface free energy of glass fibre, increases glass fibers by using modified glass fibre
Tie up the bonding strength between resin, improve the mechanics and electric property of product, in modifying process, can go out in fiberglass surfacing
The film of existing tens hundreds of molecular thickness, one end of these membrane moleculars can react with resin, inorganic as connecting
" bridge " between glass and organic resin, improve the interfacial adhesion of glass fibre and phenolic resin, improve the mechanics of product
Performance；
7th, the present invention can quickly obtain product with complex shape by using the mode of selective laser sintering, reduce
In actual applications because of shape, the production efficiency the problems such as and caused by limitation.
Brief description of the drawings
Fig. 1 is the flow according to the glass fiber resin compound material preparation method constructed by the preferred embodiments of the present invention
Figure.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Conflict can is not formed each other to be mutually combined.
Fig. 1 is the flow according to the glass fiber resin compound material preparation method constructed by the preferred embodiments of the present invention
Figure, as shown in figure 1, the preparation method comprises the following steps
(1) glass fibre is placed in Muffle furnace under the conditions of 300 DEG C~450 DEG C and calcined 1~2 hour；Cool down standby, glass
The draw ratio of fiber is 4.5~15：1；
(2) glass fibre is placed in coupling agent with completing modifying process in the mixed liquor of deionized water and absolute ethyl alcohol, changed
It is dried for standby after property at 80 DEG C~110 DEG C, wherein, the ratio of absolute ethyl alcohol and deionized water is：90wt%~95wt%:5wt%
~10wt%, coupling agent quality shared in ethanol water are 2wt%~5wt%, and coupling agent is silane coupler, aluminic acid
One or more in esters coupling agent, titante coupling agent；
(3) glass fibre and resin of surface modification are weighed by volume, are dissolved completely in toner by stirring
In organic solvent, add surface modification glass fibre in ball mill with 300r/min~400r/min rotating speed ball milling 1
It is placed in after~2 hours in baking oven and is dried at 30~55 DEG C, organic reagent is any one in absolute ethyl alcohol, acetone, organic
The mass ratio 2 of reagent and resin:1~6:1；
(4) mixture of glass fibers of resin-coating after drying is crushed and sieved with pulverizer, obtain average grain diameter point
Cladding powder of the cloth at 150 μm~35 μm；
(5) the first base of hole is obtained with SLS equipment machining composite materials；Heating makes glass/phenolic resin just base first
Secondary solidification；Technological parameter is that laser power is 6W~20W during selective laser sintering, sweep speed be 2000mm/s~
3500mm/s, sweep span are 0.2mm~0.4mm, and layering thickness is 0.1mm~0.2mm.Preheating temperature is 45 DEG C~70 DEG C,
First time curing process temperature is 160 DEG C~180 DEG C, and soaking time is 2 hours~5 hours.
(6) the first base that curing process is crossed carries out the infiltration processing of liquid thermosetting resin again, and the process of post processing is as follows：
6.1) liquid resin and curing agent are heated to 90 DEG C~110 DEG C respectively, after then both are well mixed, added
After a certain amount of curing accelerator stirs, quickly the homogeneous mixture of three is poured into the container equipped with first base sample to liquid
Face there was not sample, resin just：Curing agent：Curing accelerator=100:(60~90):(0~0.30), wherein, liquid resin and
It is in order to avoid liquid-state epoxy resin is sent out in heating process when being reheated after the two mixing that curing agent remixes after separately heating
Raw solidification；
6.2) vacuumize process 30min~50min at a temperature of 90 DEG C~110 DEG C, the first base of liquid resin filling is made
Hole；Sample is taken out to be placed in baking oven from liquid resin and solidified, the temperature of processing is 90 DEG C~200 DEG C, is incubated 3h
~15h.Product after grinding process infiltration, makes its any surface finish.
It is an advantage of the current invention that coating glass fibre by using organic solvent dissolving resin, resin and fibre can be made
Dimension, which is sufficiently mixed in uniform, reduction test specimen, to be occurred without pars fibrosa and without resin region phenomenon, is obtained after SLS shapes isotropic
Product.Because material used all has excellent mechanical property and electrical insulation properties, therefore drip molding has superior mechanics
And electric property.SLS technologies can shape the 3D solid shape for any structure that traditional handicraft is difficult to out, manufacturing cycle
It is short, can solve the problems, such as electrically insulating material due to simple shape and apply limited.
The present invention is further illustrated below in conjunction with specific embodiments.
Embodiment 1
(1) glass fibre is placed in Muffle furnace under the conditions of 300 DEG C and calcined 2 hours；Cool down standby；The draw ratio of fiber is
4.5:1；
(2) glass fibre is placed in silane coupler with completing to be modified in the mixed liquor of deionized water and absolute ethyl alcohol
Journey, it is modified to be dried for standby at 110 DEG C.Absolute ethyl alcohol and the ratio of deionized water are：90wt%:10wt%, silane coupler exist
Shared quality is 2wt% in ethanol water；
(3) the glass fibre 50vol% and phenolic resin 50vol% of surface modification are weighed by volume, will by stirring
Toner is dissolved completely in organic solvent, and the glass fibre for adding surface modification is turned in ball mill with 300r/min
Dried in the baking oven for the atmosphere that fast ball milling is placed in 55 DEG C after 2 hours；Wherein, the mass ratio 6 of organic reagent and resin:1；
(4) mixture of glass fibers of resin-coating after drying is crushed and sieved with pulverizer, obtaining average grain diameter is
35 μm of cladding powder；
(5) processed to obtain the first base with hole, porosity 50% with SLS equipment；Forming parameter is：Laser power is
6W, sweep speed 2000mm/s, sweep span 0.2mm, layering thickness are 0.1mm.Preheating temperature is 70 DEG C.Heating makes glass
The just base solidification of fibre/phenolic resin：Sample is placed in 160 DEG C of atmosphere and is incubated 5 hours；
(6) the first base after solidifying carries out the infiltration processing of liquid thermosetting resin again, and the process of processing is as follows：
6.1) epoxy resin E51 and curing agent methyl tetrahydro phthalic anhydride (M-THPA) are heated to 110 DEG C respectively；Then by two
After person is mixed evenly, add after a certain amount of curing accelerator DMP-30 after stirring, quickly by the uniformly mixed of three
Compound is poured into the container equipped with first base sample did not had sample just to liquid level；Ratio is 100:60:0.30
6.2) the vacuumize process 30min at a temperature of 110 DEG C, the hole of the first base of liquid resin filling is made；By sample from
Take out to be placed in baking oven in liquid resin and solidified, curing process is 90 DEG C of 1h+150 DEG C of 2h.System after grinding process infiltration
Part, make its any surface finish.
Embodiment 2
(1) glass fibre is placed in Muffle furnace under the conditions of 450 DEG C and calcined 1 hour；Cool down standby；The draw ratio of fiber is
4.5:1；
(2) glass fibre is placed in silane coupler with completing to be modified in the mixed liquor of deionized water and absolute ethyl alcohol
Journey, it is modified to be dried for standby at 110 DEG C.Absolute ethyl alcohol and the ratio of deionized water are：95wt%:5wt%, silane coupler is in second
Shared quality is 3wt% in alcohol solution；
(3) the glass fibre 60vol% and phenolic resin 40vol% of surface modification are weighed by volume, will by stirring
Toner is dissolved completely in organic solvent, and the glass fibre for adding surface modification is turned in ball mill with 300r/min
Fast ball milling is placed in the baking oven of 50 DEG C of atmosphere after 2 hours and dried；Wherein, the mass ratio 3 of organic reagent and resin:1；
(4) mixture of glass fibers of resin-coating after drying is crushed and sieved with pulverizer, obtaining average grain diameter is
56 μm of cladding powder；
(5) the first base with hole, porosity 53.5% are obtained with SLS equipment machining composite materials；Forming parameter is：
Laser power is 10W, sweep speed 2500mm/s, sweep span 0.2mm, and layering thickness is 0.1mm.Preheating temperature is 60
℃.Heating makes the just base solidification of glass/phenolic resin：Sample is placed in 180 DEG C of atmosphere and is incubated 2 hours；
(6) the first base after solidifying carries out the infiltration processing of liquid thermosetting resin again, and the process of processing is as follows：
6.1) epoxy resin E51 and curing agent methyl tetrahydro phthalic anhydride (M-THPA) are heated to 100 DEG C respectively；Then by two
After person is mixed evenly, add after a certain amount of curing accelerator DMP-30 after stirring, quickly by the uniformly mixed of three
Compound is poured into the container equipped with first base sample did not had sample just to liquid level；Ratio is 100:75:0.15；
6.2) the vacuumize process 40min at a temperature of 100 DEG C, the hole of the first base of liquid resin filling is made；By sample from
Take out to be placed in baking oven in liquid resin and solidified, curing process is 120 DEG C 5h+150 DEG C 3h+200 DEG C of 2h；Grinding process is soaked
Product after oozing, make its any surface finish.
Embodiment 3
(1) glass fibre is placed in Muffle furnace under the conditions of 450 DEG C and calcined 1 hour；Cool down standby；The draw ratio of fiber is
4.5:1；
(2) glass fibre is placed in silane coupler with completing to be modified in the mixed liquor of deionized water and absolute ethyl alcohol
Journey, it is modified to be dried for standby at 110 DEG C.Absolute ethyl alcohol and the ratio of deionized water are：95wt%:5wt%, silane coupler is in second
Shared quality is 3wt% in alcohol solution；
(3) the glass fibre 70vol% and resin 30vol% of surface modification are weighed by volume, by stirring resin
Powder is dissolved completely in absolute ethyl alcohol, add surface modification glass fibre in ball mill with 350r/min rotating speed ball
Mill is placed in the baking oven of 50 DEG C of atmosphere after 1.5 hours and dried；Wherein, the mass ratio 3 of organic reagent and resin:1；
(4) mixture of glass fibers of resin-coating after drying is crushed and sieved with pulverizer, obtaining average grain diameter is
35.2 μm of cladding powder；
(5) the first base with hole, porosity 55% are obtained with SLS equipment machining composite materials；Forming parameter is：Swash
Luminous power is 12W, sweep speed 3000mm/s, sweep span 0.3mm, and layering thickness is 0.1mm.Preheating temperature is 60
℃.Heating makes the just base solidification of glass/phenolic resin：Sample is placed under 180 DEG C of atmosphere and is incubated 2 hours；
(6) the first base after solidifying carries out the infiltration processing of liquid thermosetting resin again, and the process of processing is as follows：
6.1) epoxy resin E51 and curing agent methyl tetrahydro phthalic anhydride (M-THPA) are heated to 100 DEG C respectively；Then by two
After person is mixed evenly, add after a certain amount of curing accelerator DMP-30 after stirring, quickly by the uniformly mixed of three
Compound is poured into the container equipped with first base sample did not had sample just to liquid level；Ratio is 100:75:0.15；
6.2) the vacuumize process 40min at a temperature of 100 DEG C, the hole of the first base of liquid resin filling is made；By sample from
Take out to be placed in baking oven in liquid resin and solidified, curing process is 120 DEG C 5h+150 DEG C 3h+200 DEG C of 2h；Grinding process is soaked
Product after oozing, make its any surface finish.
Embodiment 4
(1) glass fibre is placed in Muffle furnace under the conditions of 450 DEG C and calcined 1 hour；Cool down standby；The draw ratio of fiber is
4.5:1；
(2) glass fibre is placed in silane coupler with completing to be modified in the mixed liquor of deionized water and absolute ethyl alcohol
Journey, it is modified to be dried for standby at 110 DEG C.Absolute ethyl alcohol and the ratio of deionized water are：95wt%:5wt%, silane coupler is in second
Shared quality is 3wt% in alcohol solution；
(3) the glass fibre 80vol% and resin 20vol% of surface modification are weighed by volume, by stirring resin
Powder is dissolved completely in organic solvent, add surface modification glass fibre in ball mill with 350r/min rotating speed ball
Mill is placed in the baking oven of 50 DEG C of atmosphere after 1.5 hours and dried；Wherein, the mass ratio 3 of organic reagent and resin:1；
(4) mixture of glass fibers of resin-coating after drying is crushed and sieved with pulverizer, obtaining average grain diameter is
37.3 μm of cladding powder；
(5) with the first base of SLS equipment shaping, the porosity of first base is 58.8%；Forming parameter is：Laser power is 14W, is swept
It is 3500mm/s to retouch speed, and sweep span 0.3mm, layering thickness is 0.1mm.Preheating temperature is 60 DEG C.Heating makes glass/phenol
Urea formaldehyde just base solidification：2 hours are incubated at 180 DEG C；
(6) the first base after solidifying carries out the infiltration processing of liquid thermosetting resin again, and the process of processing is as follows：
6.1) epoxy resin E51 and curing agent methyl tetrahydro phthalic anhydride (M-THPA) are heated to 100 DEG C respectively；Then by two
After person is mixed evenly, add after a certain amount of curing accelerator DMP-30 after stirring, quickly by the uniformly mixed of three
Compound is poured into the container equipped with first base sample did not had sample just to liquid level；Ratio is 100:75:0.15；
6.2) the vacuumize process 40min at a temperature of 100 DEG C, the hole of the first base of liquid resin filling is made；By sample from
Take out to be placed in baking oven in liquid resin and solidified, curing process is 120 DEG C 5h+150 DEG C 3h+200 DEG C of 2h；Grinding process is soaked
Product after oozing, make its any surface finish.
Embodiment 5
(1) glass fibre is placed in Muffle furnace under the conditions of 400 DEG C and calcined 1.5 hours；Cool down standby；The draw ratio of fiber
For 15:1；
(2) glass fibre is placed in silane coupler with completing to be modified in the mixed liquor of deionized water and absolute ethyl alcohol
Journey, it is modified to be dried for standby at 80 DEG C.Absolute ethyl alcohol and the ratio of deionized water are：95wt%:5wt%, silane coupler is in second
Shared quality is 5wt% in alcohol solution；
(3) the glass fibre 90vol% and phenolic resin 10vol% of surface modification are weighed by volume, will by stirring
Toner is dissolved completely in organic solvent, and the glass fibre for adding surface modification is turned in ball mill with 400r/min
Fast ball milling is placed in the baking oven of 30 DEG C of atmosphere after 2 hours and dried；Wherein, the mass ratio 2 of organic reagent and resin:1；
(4) mixture of glass fibers of resin-coating after drying is crushed and sieved with pulverizer, obtaining average grain diameter is
150 μm of cladding powder；
(5) with the first base of SLS equipment shaping, the porosity of first base is 60%；Forming parameter is：Laser power is 20W, scanning
Speed is 3500mm/s, and sweep span 0.4mm, layering thickness is 0.2mm.Preheating temperature is 45 DEG C.Heating makes glass/phenolic aldehyde
Resin just base solidification：Sample is placed under 170 DEG C of atmosphere and is incubated 3 hours；
(6) the first base after solidifying carries out the infiltration processing of liquid thermosetting resin again, and the process of processing is as follows：
6.1) epoxy resin E51 and curing agent methyl tetrahydro phthalic anhydride (M-THPA) are heated to 90 DEG C respectively；Then by two
After person is mixed evenly, add after a certain amount of curing accelerator DMP-30 after stirring, quickly by the uniformly mixed of three
Compound is poured into the container equipped with first base sample did not had sample just to liquid level；Ratio is epoxy resin E51 and curing agent methyl four
Hydrogen phthalic anhydride (M-THPA)=100:90；
6.2) the vacuumize process 50min at a temperature of 90 DEG C, the hole of the first base of liquid resin filling is made；By sample from liquid
Take out to be placed in baking oven in state resin and solidified, curing process is 120 DEG C of 15h；Product after grinding process infiltration, makes its table
Face is bright and clean.
Embodiment 6
(1) glass fibre is placed in Muffle furnace under the conditions of 400 DEG C and calcined 1 hour；Cool down standby；The draw ratio of fiber is
10:1；
(2) glass fibre is placed in silane coupler with completing to be modified in the mixed liquor of deionized water and absolute ethyl alcohol
Journey, it is modified to be dried for standby at 110 DEG C.Absolute ethyl alcohol and the ratio of deionized water are：92wt%:8wt%, silane coupler is in second
Shared weight is 4wt% in alcohol solution；
(3) the glass fibre 65vol% and resin 35vol% of surface modification are weighed by volume, by stirring resin
Powder is dissolved completely in absolute ethyl alcohol, add surface modification glass fibre in ball mill with 320r/min rotating speed ball
Mill is placed in the baking oven of 50 DEG C of atmosphere after 1.5 hours and dried；Wherein, the mass ratio 4 of organic reagent and resin:1；
(4) mixture of glass fibers of resin-coating after drying is crushed and sieved with pulverizer, obtaining average grain diameter is
70 μm of cladding powder；
(5) the first base with hole is obtained with SLS equipment machining composite materials；Forming parameter is：Laser power is 14W,
Sweep speed is 3000mm/s, and sweep span 0.25mm, layering thickness is 0.1mm.Preheating temperature is 70 DEG C.Heating makes glass
The just base solidification of fibre/phenolic resin：Sample is placed under 160 DEG C of atmosphere and is incubated 5 hours；
(6) the first base after solidifying carries out the infiltration processing of liquid thermosetting resin again, and the process of processing is as follows：
6.1) epoxy resin E51 and curing agent methyl tetrahydro phthalic anhydride (M-THPA) are heated to 100 DEG C respectively；Then by two
After person is mixed evenly, add after a certain amount of curing accelerator DMP-30 after stirring, quickly by the uniformly mixed of three
Compound is poured into the container equipped with first base sample did not had sample just to liquid level；Ratio is 100:80:0.20；
6.2) the vacuumize process 35min at a temperature of 100 DEG C, the hole of the first base of liquid resin filling is made；By sample from
Take out to be placed in baking oven in liquid resin and solidified, curing process is 130 DEG C 3h+160 DEG C 2h+200 DEG C of 1h；Grinding process is soaked
Product after oozing, make its any surface finish.
Embodiment 7
(1) glass fibre is placed in Muffle furnace under the conditions of 300 DEG C and calcined 1.5 hours；Cool down standby；The draw ratio of fiber
For 10:1；
(2) glass fibre is placed in silane coupler with completing to be modified in the mixed liquor of deionized water and absolute ethyl alcohol
Journey, it is modified to be dried for standby at 100 DEG C.Absolute ethyl alcohol and the ratio of deionized water are：90wt%:10wt%, silane coupler exist
Shared weight is 5wt% in ethanol water；
(3) the glass fibre 75vol% and resin 25vol% of surface modification are weighed by volume, by stirring resin
Powder is dissolved completely in absolute ethyl alcohol, add surface modification glass fibre in ball mill with 300r/min rotating speed ball
Mill is placed in the baking oven of 45 DEG C of atmosphere after 1.5 hours and dried；Wherein, the mass ratio 4 of organic reagent and resin:1；
(4) mixture of glass fibers of resin-coating after drying is crushed and sieved with pulverizer, obtaining average grain diameter is
80 μm of cladding powder；
(5) the first base with hole is obtained with SLS equipment machining composite materials；Forming parameter is：Laser power is 16W,
Sweep speed is 3000mm/s, and sweep span 0.3mm, layering thickness is 0.2mm.Preheating temperature is 65 DEG C.Heating make glass/
Phenolic resin just base solidification：Sample is placed under 180 DEG C of atmosphere and protected 1 hour；
(6) the first base after solidifying carries out the infiltration processing of liquid thermosetting resin again, and the process of processing is as follows：
6.1) epoxy resin E51 and curing agent methyl tetrahydro phthalic anhydride (M-THPA) are heated to 100 DEG C respectively；Then by two
After person is mixed evenly, add after a certain amount of curing accelerator DMP-30 after stirring, quickly by the uniformly mixed of three
Compound is poured into the container equipped with first base sample did not had sample just to liquid level；Ratio is 100:85:0.10；
6.2) the vacuumize process 35min at a temperature of 100 DEG C, the hole of the first base of liquid resin filling is made；By sample from
Take out to be placed in baking oven in liquid resin and solidified, curing process is 120 DEG C 3h+150 DEG C 3h+180 DEG C of 2h；Grinding process is soaked
Product after oozing, make its any surface finish.
It is as follows to the results of property of the embodiment 1-5 product tests obtained below, pass through the present invention by can be seen that in table
The product mechanical property and electric property of acquisition are excellent.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of glass fiber resin compound material, it is characterised in that the preparation method comprises the following steps：
(a) it is 4.5~15 by draw ratio：1 glass fibre is modified so that glass fibre can be combined with phenolic resin, weigh phenol
Urea formaldehyde and the modified glass fibre, and the two dissolving is formed into solution in organic solvent；
(b) the modified glass fibre, and ball milling are added again in the solution obtained in step (a), after ball milling
Product is dried, and is derived from the glass fibre powder of dry resin-coating；
(c) by the glass fibre powder grinding and sieving of the resin-coating of the drying, it is 35 μm~150 μm to choose wherein particle diameter
Powder, the powder is then configured to just base by selective laser sintering, and the first base is subjected to first time curing process；
(d) the first base after solidification is infiltrated in liquid-state epoxy resin, answering for required glass fibre and resin is obtained after infiltration
Condensation material.
2. a kind of preparation method of glass fiber resin compound material as claimed in claim 1, it is characterised in that in step
(a) in, the glass fibre modifying process is carried out according to the following steps, is first mixed to form coupling agent and ethanol water mixed
Liquid is closed, then calcines glass fibre, the glass fibre after calcining is added in the mixed liquor and reacted, thus completes the glass
The modification of glass fiber, wherein, the temperature of the calcining is 300 DEG C~450 DEG C, and calcination time be 1h~2h, the coupling agent and
The mass fraction percentage of the ethanol water is 2%~5%：1.
3. a kind of preparation method of glass fiber resin compound material as claimed in claim 1, it is characterised in that in step
(d) in, the infiltration comprises the following steps：
(d1) liquid-state epoxy resin and curing agent needed for infiltration are chosen, and the two is heated respectively, then after the heating
Curing accelerator is added in liquid-state epoxy resin and curing agent, is mixed and stirred for being formed uniformly infiltration liquid；
(d2) the first base after the solidification that will be obtained by step (c) is placed in the infiltration liquid, is then heated to 90 DEG C~110 DEG C,
30min~50min is infiltrated under vacuum so that first after the liquid-state epoxy resin filling solidification in the infiltration liquid
The hole of base, thus completes infiltration process；
(d3) the first base for completing infiltration to be taken out from the infiltration liquid, and carries out second and solidify, solidification temperature is 90 DEG C~
200 DEG C, hardening time is 3h~15h.
A kind of 4. preparation method of glass fibre and resin composite materials as claimed in claim 2, it is characterised in that the idol
Connection agent is the one or more in silane coupler, aluminate coupling agent or titanate coupling agent.
5. a kind of preparation method of glass fiber resin compound material as claimed in claim 2, it is characterised in that in step
(a) in, the organic solvent is absolute ethyl alcohol or acetone.
6. a kind of preparation method of glass fiber resin compound material as claimed in claim 2, it is characterised in that in step
(b) in, the temperature of the drying is 30 DEG C~55 DEG C.
7. a kind of preparation method of glass fiber resin compound material as claimed in claim 1, it is characterised in that in step
(c) in, technological parameter is respectively during the selective laser sintering：Laser power is 6W~20W, and sweep speed is
2000mm/s~3500mm/s, sweep span are 0.2mm~0.4mm, and layering thickness is 0.1mm~0.2mm, preheating temperature 45
DEG C~70 DEG C.
8. a kind of preparation method of glass fiber resin compound material as claimed in claim 1, it is characterised in that in step
(c) in, the temperature of the first time curing process is 160 DEG C~180 DEG C, and hardening time is 2h~4h.
A kind of 9. preparation method of glass fiber resin compound material as claimed in claim 3, it is characterised in that the liquid
The mass ratio of epoxy resin, curing agent and curing accelerator is 100:(60~90):(0~0.30).
A kind of 10. glass fiber resin compound material product obtained by preparation method according to any one of claim 1-9.
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| CN112351966A (en) * | 2018-07-02 | 2021-02-09 | 巴斯夫欧洲公司 | Method for producing sintered powder particles (SP) comprising at least one reinforcing fiber |
| CN112537921A (en) * | 2020-12-17 | 2021-03-23 | 中国科学院上海硅酸盐研究所 | Phenolic resin coated chopped carbon fiber composite powder for laser 3D printing and preparation method thereof |
| CN116023694A (en) * | 2022-12-14 | 2023-04-28 | 华东理工大学 | Post-treatment enhancement method for TPU (thermoplastic polyurethane) product |
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| CN105985632A (en) * | 2015-10-28 | 2016-10-05 | 合肥学院 | Powder material for selective laser sintering and preparation method thereof |
| CN106589419A (en) * | 2015-10-13 | 2017-04-26 | 中国石油化工股份有限公司 | Glass fiber reinforced polypropylene resin powder for selective laser sintering and preparation thereof |
| CN107163559A (en) * | 2017-06-27 | 2017-09-15 | 陕西恒通智能机器有限公司 | A kind of SLS strengthens nylon powder preparation technology with glass fiber powder |
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|---|---|---|---|---|
| CN104647760A (en) * | 2015-02-12 | 2015-05-27 | 华中科技大学 | 3D printing and manufacturing method of short-fiber reinforced thermosetting resin composite product |
| CN106589419A (en) * | 2015-10-13 | 2017-04-26 | 中国石油化工股份有限公司 | Glass fiber reinforced polypropylene resin powder for selective laser sintering and preparation thereof |
| CN105985632A (en) * | 2015-10-28 | 2016-10-05 | 合肥学院 | Powder material for selective laser sintering and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112351966A (en) * | 2018-07-02 | 2021-02-09 | 巴斯夫欧洲公司 | Method for producing sintered powder particles (SP) comprising at least one reinforcing fiber |
| CN112537921A (en) * | 2020-12-17 | 2021-03-23 | 中国科学院上海硅酸盐研究所 | Phenolic resin coated chopped carbon fiber composite powder for laser 3D printing and preparation method thereof |
| CN112537921B (en) * | 2020-12-17 | 2021-11-02 | 中国科学院上海硅酸盐研究所 | Phenolic resin coated chopped carbon fiber composite powder for laser 3D printing and preparation method thereof |
| CN116023694A (en) * | 2022-12-14 | 2023-04-28 | 华东理工大学 | Post-treatment enhancement method for TPU (thermoplastic polyurethane) product |
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Application publication date: 20180223 |