CN104194234A - Graphene glassfiber-reinforced plastic plate composite material and preparation method thereof - Google Patents
Graphene glassfiber-reinforced plastic plate composite material and preparation method thereof Download PDFInfo
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- CN104194234A CN104194234A CN201410401677.6A CN201410401677A CN104194234A CN 104194234 A CN104194234 A CN 104194234A CN 201410401677 A CN201410401677 A CN 201410401677A CN 104194234 A CN104194234 A CN 104194234A
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Abstract
The invention provides a graphene glassfiber-reinforced plastic plate composite material which comprises porous graphene, a glassfiber-reinforced plastic resin and glass fibers. By adding the porous graphene into the glassfiber-reinforced plastic plate, the prepared glassfiber-reinforced plastic plate composite material has the advantages of favorable impact resistance, favorable bending resistance, favorable compression strength and favorable wear resistance, and can be better used in the fields of high-speed rails, automobiles, steamships, airplanes and the like.
Description
Technical field
The present invention relates to glass fiber reinforced plastics composite material technical field, relate in particular to a kind of Graphene glass steel board matrix material and preparation method thereof.
Background technology
Reinforced plastic plate is the type material that adopts the fibre products such as novel glass fiber yarn, glass mat, grid cloth and various resin to be made through production technique such as extrusion, molding, hand pastes.
In recent years, many characteristics such as reinforced plastic plate is high-strength, anti-aging, corrosion-resistant, fire-retardant with its light weight, sunshade, heat insulation, insulation, are widely used.
But along with scientific and technological development, train, aircraft, steamer etc. are increasing for the demand of the high-strength matrix material of light weight, also all the more harsh to the requirement of its mechanical property, therefore current reinforced plastic plate is difficult to meet on market day by day harsh requirement.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of Graphene glass steel board matrix material and preparation method thereof, and the reinforced plastic plate of preparation has good mechanical property.
The invention provides a kind of Graphene glass steel board matrix material, comprising: porous graphene, fiber glass resin and glass fibre.
Preferably, described porous graphene is prepared in accordance with the following methods:
1), under the effect of catalyzer, biomass carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), under the condition of protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 ℃～40 ℃, described the second temperature is 300 ℃～400 ℃;
3), under the condition of protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 ℃～900 ℃;
4), under the condition of protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 ℃～1300 ℃;
5), under the condition of protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain porous graphene, described the 5th temperature is 900 ℃～1000 ℃.
Preferably, the mass ratio of described porous graphene and fiber glass resin is 1:(1000～8500); Described glass fibre is the 50wt%～300wt% of described porous graphene and fiber glass resin total amount.
Preferably, described matrix material also comprises whipping agent and thinner.
Preferably, the mass ratio of described fiber glass resin and whipping agent, thinner is 100:(1～80): (50～200).
The present invention also provides a kind of preparation method of Graphene glass steel board matrix material, comprising:
A) porous graphene and fiber glass resin are mixed, obtain glass reinforced plastic prepreg resin;
B) by steps A) the glass reinforced plastic prepreg that obtains mixes with glass fibre with resin, obtains glass reinforced plastic prepreg;
C) by step B) the glass reinforced plastic prepreg that obtains is heating and curing, and obtains Graphene glass steel board matrix material.
Preferably, described steps A) be specially:
By porous graphene, fiber glass resin, whipping agent and mixing diluents, obtain glass reinforced plastic prepreg resin.
Preferably, the mass ratio of described fiber glass resin and whipping agent, thinner is 100:(1～80): (50～200).
Preferably, the mass ratio of described porous graphene and fiber glass resin is 1:(1000～8500); Described glass fibre is the 50wt%～300wt% of described porous graphene and fiber glass resin total amount.
Preferably, described porous graphene is prepared in accordance with the following methods:
1), under the effect of catalyzer, biomass carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), under the condition of protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 ℃～40 ℃, described the second temperature is 300 ℃～400 ℃;
3), under the condition of protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 ℃～900 ℃;
4), under the condition of protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 ℃～1300 ℃;
5), under the condition of protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain porous graphene, described the 5th temperature is 900 ℃～1000 ℃.
Compared with prior art, the invention provides a kind of Graphene glass steel board matrix material, comprising: porous graphene, fiber glass resin and glass fibre.The present invention is by added porous graphene in reinforced plastic plate, and the reinforced plastic plate matrix material of preparation has good shock resistance, counter-bending, compressive strength and wear resistance, can better be applied to the fields such as high ferro, automobile, steamer, aircraft.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skills, do not paying under the prerequisite of creative work, other accompanying drawing can also be provided according to the accompanying drawing providing.
Fig. 1 is the Raman spectrum of the Graphene that obtains of the embodiment of the present invention 4;
Fig. 2 is the transmission electron microscope picture of the Graphene that obtains of the embodiment of the present invention 4;
Fig. 3 is the transmission electron microscope picture of the Graphene that obtains of the embodiment of the present invention 4;
Fig. 4 is the transmission electron microscope picture of the Graphene that obtains of the embodiment of the present invention 4;
Fig. 5 is the transmission electron microscope picture of the Graphene that obtains of the embodiment of the present invention 4.
Embodiment
The invention provides a kind of Graphene glass steel board matrix material, comprising: porous graphene, fiber glass resin and glass fibre.
The present invention is by added porous graphene in reinforced plastic plate, and the reinforced plastic plate matrix material of preparation has good shock resistance, counter-bending, compressive strength and wear resistance, can better be applied to the fields such as high ferro, automobile, steamer, aircraft.
The invention provides a kind of Graphene glass steel board matrix material, comprising: porous graphene, fiber glass resin and glass fibre.
Wherein, the described porous graphene porous graphene that to be preferably based on biological material be raw material production.The preparation method of the described porous graphene that is raw material production based on biological material is preferably:
1), under the effect of catalyzer, biomass carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), under the condition of protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 ℃～40 ℃, described the second temperature is 300 ℃～400 ℃;
3), under the condition of protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 ℃～900 ℃;
4), under the condition of protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 ℃～1300 ℃;
5), under the condition of protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain porous graphene, described the 5th temperature is 900 ℃～1000 ℃.
The present invention, under the effect of catalyzer, carries out catalytic treatment by biomass carbon source, obtains the first intermediate product, and described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese.The present invention preferably mixes catalyzer and biomass carbon source, obtains the first intermediate product.The present invention does not have special restriction to the method for described mixing, adopts hybrid technology scheme well known to those skilled in the art, and described catalyzer and biomass carbon source are stirred.In the present invention, the temperature of described mixing is preferably 20 ℃～180 ℃, more preferably 50 ℃～150 ℃, most preferably is 80 ℃～120 ℃.In the present invention, the time of described mixing is preferably 2 hours～and 10 hours, more preferably 5 hours～7 hours.
In the present invention, described catalyzer comprises one or more in muriate, iron compound, cobalt compounds and the nickel compounds of manganese, is preferably a kind of in muriate, iron compound, cobalt compounds and the nickel compounds of manganese.In the present invention, the muriate of described manganese is preferably Manganous chloride tetrahydrate.In the present invention, described iron compound preferably includes the chlorate of iron, one or more in the prussiate of iron and iron content hydrochlorate, and more preferably iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash and three oxalic acid close one or more in potassium ferrite.In the present invention, described cobalt compounds comprises the chlorate of cobalt and contains one or more in cobaltates, more preferably one or more in cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol and cobaltous acetate.In the present invention, described nickel compounds preferably includes the chlorate of nickel and contains one or more in nickelate, more preferably one or more in nickelous chloride, nickelous nitrate, single nickel salt and nickelous acetate.In the present invention, described catalyzer is preferably iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash, three oxalic acid and closes one or more in potassium ferrite, cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobaltous acetate, nickelous chloride, nickelous nitrate, single nickel salt and nickelous acetate.The present invention does not have special restriction to the source of described catalyzer, adopts the catalyzer of mentioned kind well known to those skilled in the art, can be bought and be obtained by market.
In the present invention, described biomass carbon source is preferably one or both in Mierocrystalline cellulose and xylogen; Mierocrystalline cellulose more preferably; Most preferably be porous cellulose.In the present invention, the preparation method of described porous cellulose preferably includes following steps:
A), biomass resource is hydrolyzed in acid, obtain lignocellulose, described biomass resource comprises one or more in plant and agriculture and forestry organic waste material;
B), described lignocellulose is processed, obtain porous cellulose, described processing comprises that acid treatment, salt are processed or organic solvent is processed.
The present invention is preferably hydrolyzed biomass resource in acid, obtains lignocellulose, and described biomass resource comprises one or more in plant and agriculture and forestry organic waste material.In the present invention, the temperature of described hydrolysis is preferably 90 ℃～180 ℃, more preferably 120 ℃～150 ℃.In the present invention, the time of described hydrolysis is preferably 10min～10h, and more preferably 1h～8h, most preferably is 3h～6h.
In the present invention, the acid of described hydrolysis is preferably one or more in sulfuric acid, nitric acid, hydrochloric acid, formic acid, sulfurous acid, phosphoric acid and acetic acid, and more preferably sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid or acetic acid, most preferably be sulfuric acid, nitric acid or hydrochloric acid.In the present invention, in described hydrolysis, the consumption of acid is preferably the 3wt%～20wt% of described biomass resource, and more preferably 5wt%～15wt%, most preferably is 8wt%～12wt%.
In the present invention, described biomass resource is preferably agriculture and forestry organic waste material, and more preferably one or more in corn stalk, corn cob, kaoliang stalk, beet pulp, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk and reed, most preferably are corn cob.
Obtain after lignocellulose, the present invention preferably processes described lignocellulose, obtains porous cellulose, and described processing comprises that acid treatment, salt are processed or organic solvent is processed; The present invention more preferably carries out salt processing by described lignocellulose, obtains porous cellulose.In the present invention, the method that described salt is processed is preferably acid sulfite process processing or alkali sulfite process is processed.In the present invention, the pH value in described acid sulphite process treating processes is preferably 1～7, and more preferably 2～5, most preferably be 3～4.In the present invention, the temperature that described acid sulfite process is processed is preferably 70 ℃～180 ℃, more preferably 90 ℃～150 ℃, most preferably is 100 ℃～120 ℃.In the present invention, the time that described acid sulfite process is processed is preferably 1 hour～and 6 hours, more preferably 2 hours～5 hours, most preferably be 3 hours～4 hours.
In the present invention, the acid in described acid sulfite process processing is preferably sulfuric acid.In the present invention, in described acid sulfite process treating processes, the consumption of acid is preferably the 4wt%～30wt% of described lignocellulose, and more preferably 8wt%～25wt%, most preferably is 10wt%～20wt%.In the present invention, described acid sulfite process process in the weight percent concentration of acid preferably to make liquid-solid ratio be (2～20): 1, more preferably (4～16): 1, most preferably be (8～12): 1.
In the present invention, the sulphite in described acid sulfite process processing is preferably calcium sulfite, magnesium sulfite, S-WAT or ammonium sulphite, more preferably magnesium sulfite or S-WAT.The present invention does not have special restriction to the consumption of sulphite in described acid sulfite process treating processes, adopts the consumption of sulphite in sulfite pulping process well known to those skilled in the art.
In the present invention, the pH value in described alkaline sulfurous method treating processes is preferably 7～14, and more preferably 8～13, most preferably be 9～12.In the present invention, the temperature that described alkali sulfite process is processed is preferably 70 ℃～180 ℃, more preferably 90 ℃～150 ℃, most preferably is 100 ℃～120 ℃.In the present invention, the time that described alkali sulfite process is processed is preferably 1 hour～and 6 hours, more preferably 2 hours～5 hours, most preferably be 3 hours～4 hours.
In the present invention, the alkali in described alkali sulfite process processing is preferably calcium hydroxide, sodium hydroxide, ammonium hydroxide or magnesium hydroxide, more preferably sodium hydroxide or magnesium hydroxide.In the present invention, in described alkali sulfite process treating processes, the consumption of alkali is preferably the 4wt%～30wt% of described lignocellulose, and more preferably 8wt%～25wt%, most preferably is 10wt%～20wt%.In the present invention, described alkali sulfite process process in the weight percent concentration of alkali preferably to make liquid-solid ratio be (2～20): 1, more preferably (4～16): 1, most preferably be (8～12): 1.
In the present invention, the sulphite in described alkali sulfite process processing is preferably calcium sulfite, magnesium sulfite, S-WAT or ammonium sulphite, more preferably magnesium sulfite or S-WAT.The present invention does not have special restriction to the consumption of sulphite in described alkali sulfite process treating processes, adopts the consumption of sulphite in sulfite pulping process well known to those skilled in the art.
Obtain after porous cellulose, the present invention preferably also comprises:
Described porous cellulose is carried out to bleaching.
The present invention does not have special restriction to the method for described bleaching, adopts bleaching technology scheme well known to those skilled in the art.In the present invention, the method for described bleaching is preferably total chlorine free bleaching (TCF), more preferably hydrogen peroxide bleaching.The present invention does not have special restriction to the concentration of described hydrogen peroxide, adopts the hydrogen peroxide of typical concentrations.In the present invention, the quality optimization of described hydrogen peroxide is 1%～10% of described porous cellulose quality, more preferably 2%～8%.In the present invention, the bleaching temperature of described hydrogen peroxide bleaching is preferably 60 ℃～130 ℃, more preferably 80 ℃～100 ℃; The bleaching time of described hydrogen peroxide bleaching is preferably 1h～10h, more preferably 2h～8h.
In the present invention, the mass ratio of described catalyzer and biomass carbon source is preferably (0.01～2): 1, more preferably (0.1～1): 1, most preferably be (0.3～0.8): 1.In the present invention, the temperature of described catalytic treatment is preferably 20 ℃～180 ℃, more preferably 50 ℃～150 ℃, most preferably is 80 ℃～120 ℃.In the present invention, the time of described catalytic treatment is preferably 2 hours～and 10 hours, more preferably 5 hours～7 hours.
Described biomass carbon source is carried out after catalytic treatment, and the present invention is preferably dried the biomass carbon source after the catalytic treatment obtaining, and obtains the first intermediate product.In the present invention, the temperature of the biomass carbon source after dry described catalytic treatment is preferably 70 ℃～120 ℃, more preferably 90 ℃～100 ℃.In the present invention, the preferred < 10wt% of the water content of described the first intermediate product, more preferably < 5wt%.
Obtain after the first intermediate product, the present invention, under the condition of protective gas, is incubated described the first intermediate product from the first temperature is warming up to the second temperature, obtains the second intermediate product; Described the first temperature is 20 ℃～40 ℃, and described the second temperature is 300 ℃～400 ℃.In the present invention, the temperature rise rate that described the first intermediate product is warming up to the second temperature from the first temperature is preferably 5 ℃/min～20 ℃/min, more preferably 10 ℃/min～15 ℃/min.In the present invention, described the first temperature is preferably 25 ℃～35 ℃, more preferably 28 ℃～32 ℃.In the present invention, described the second temperature is preferably 320 ℃～380 ℃, more preferably 340 ℃～360 ℃.In the present invention, the soaking time of described the first intermediate product from the first temperature is warming up to the second temperature be preferably 4 hours～and 8 hours, more preferably 5 hours～6 hours.
In the present invention, described protective gas is preferably one or more in nitrogen and rare gas element, more preferably nitrogen.In the present invention, the intake of described protective gas is preferably 200mL/min～800mL/min, more preferably 400mL/min～600mL/min.
Obtain after the second intermediate product, the present invention, under the condition of protective gas, is incubated described the second intermediate product from the second temperature is warming up to the 3rd temperature, obtains the 3rd intermediate product; Described the 3rd temperature is 800 ℃～900 ℃.In the present invention, the temperature rise rate that described the second intermediate product is warming up to the 3rd temperature from the second temperature is preferably 20 ℃/min～50 ℃/min, more preferably 30 ℃/min～40 ℃/min.In the present invention, described the 3rd temperature is preferably 820 ℃～880 ℃, more preferably 840 ℃～860 ℃.In the present invention, the soaking time of described the second intermediate product from the second temperature is warming up to the 3rd temperature be preferably 3.5 hours～and 7 hours, more preferably 5 hours～6 hours.
In the present invention, the kind of described protective gas is consistent with kind and the intake of protective gas described in technique scheme with intake, does not repeat them here.In the present invention, described protective gas can be identical with the protective gas described in technique scheme, also can be different.
Obtain after the 3rd intermediate product, the present invention, under the condition of protective gas, is incubated described the 3rd intermediate product from the 3rd temperature is warming up to the 4th temperature, obtains the 4th intermediate product; Described the 4th temperature is 1100 ℃～1300 ℃.In the present invention, the temperature rise rate that described the 3rd intermediate product is warming up to the 4th temperature from the 3rd temperature is preferably 50 ℃/min～60 ℃/min, more preferably 54 ℃/min～58 ℃/min.In the present invention, described the 4th temperature is preferably 1150 ℃～1250 ℃, more preferably 1200 ℃.In the present invention, the soaking time of described the 3rd intermediate product from the 3rd temperature is warming up to the 4th temperature be preferably 6 hours～and 8 hours, more preferably 7 hours.
In the present invention, the kind of described protective gas is consistent with kind and the intake of protective gas described in technique scheme with intake, does not repeat them here.In the present invention, described protective gas can be identical with the protective gas described in technique scheme, also can be different.
Obtain after the 4th intermediate product, the present invention, under the condition of protective gas, is incubated described the 4th intermediate product from the 4th greenhouse cooling to the five temperature, obtains porous graphene; Described the 5th temperature is 900 ℃～1000 ℃.In the present invention, described the 4th intermediate product is preferably 30 ℃/min～50 ℃/min from the rate of temperature fall of the 4th greenhouse cooling to the five temperature, more preferably 35 ℃/min～45 ℃/min.In the present invention, described the 5th temperature is preferably 920 ℃～980 ℃, more preferably 940 ℃～960 ℃.In the present invention, the soaking time of described the 4th intermediate product from the 4th greenhouse cooling to the five temperature be preferably 2 hours～and 4 hours, more preferably 3 hours.
In the present invention, the kind of described protective gas is consistent with kind and the intake of protective gas described in technique scheme with intake, does not repeat them here.In the present invention, described protective gas can be identical with the protective gas described in technique scheme, also can be different.
After described the 4th insulation is finished dealing with, the product that the present invention preferably obtains described the 4th insulation processing carries out cooling, obtains porous graphene.In the present invention, 100 ℃ of the preferred < of described cooling temperature,, most preferably are 30 ℃～40 ℃ by more preferably 20 ℃～60 ℃.The present invention preferably carries out described cooling under the condition of protective gas.In the present invention, the kind of described protective gas is consistent with kind and the intake of protective gas described in technique scheme with intake, does not repeat them here.In the present invention, described protective gas can be identical with the protective gas described in technique scheme, also can be different.In the present invention, described cooling method is preferably naturally cooling.
After described cooling completing, the present invention preferably washs the cooled product obtaining, and obtains porous graphene.In the present invention, the method for described washing is preferably:
Described cooled product is carried out in alkaline aqueous solution to the first washing, obtain the first washed product;
Described the first washed product is carried out to the second washing in acidic aqueous solution, obtain the second washed product;
Described the second washed product is carried out to the 3rd washing in water, obtain porous graphene.
The present invention preferably carries out described cooled product the first washing in basic solution, obtains the first washed product.In the present invention, the mass concentration of described alkaline aqueous solution is preferably 3%～55%, and more preferably 10%～40%, most preferably be 20%～30%.In the present invention, the temperature of described the first washing is preferably 60 ℃～120 ℃, more preferably 80 ℃～100 ℃.In the present invention, described first washing time be preferably 4 hours～24 hours, more preferably 8 hours～16 hours, most preferably be 10 hours～14 hours.In the present invention, described alkaline aqueous solution is preferably aqueous sodium hydroxide solution or ammoniacal liquor.
Obtain after the first washed product, the present invention preferably carries out the second washing by described the first washed product in acidic aqueous solution, obtains the second washed product.In the present invention, the mass concentration of described acidic aqueous solution is preferably 4%～10%, and more preferably 6%～8%.In the present invention, the temperature of described the second washing is preferably 70 ℃～150 ℃, more preferably 90 ℃～120 ℃.In the present invention, described second washing time be preferably 4 hours～24 hours, more preferably 8 hours～16 hours, most preferably be 10 hours～14 hours.In the present invention, described acidic aqueous solution is preferably aqueous hydrochloric acid.
Obtain after the second washed product, the present invention preferably carries out the 3rd washing by described the second washed product in water, obtains porous graphene.In the present invention, described water is preferably distilled water.The present invention does not have special restriction to the method for described the 3rd washing, after described the 3rd washing, obtains neutral porous graphene.
After described washing completes, the present invention is preferably dried the washed product obtaining, and obtains porous graphene.The present invention does not have special restriction to the method for dry described washed product, adopts dry technology scheme well known to those skilled in the art.
The porous graphene that above method prepares has good conductivity, and lamella is thin, Sp
2hydridization degree is high.
The present invention there is no particular determination to described fiber glass resin, can be fiber glass resin well known to those skilled in the art, can be bought and be obtained by market.
The present invention there is no particular determination to described glass fibre, can be glass fibre well known to those skilled in the art, and the present invention is preferably alkali-free short glass fiber, and the diameter of described glass fibre is preferably 10 μ m～30 μ m, more preferably 15 μ m～25 μ m.
In the present invention, the mass ratio of described porous graphene and fiber glass resin is preferably 1:(1000～8500), 1:(2000～8000 more preferably), most preferably be 1:(2500～7000).
The present invention is preferred, and described glass fibre is the 50wt%～300wt% of described porous graphene and fiber glass resin total amount, more preferably 100wt%～200wt%.
The present invention is preferred, and described Graphene glass steel board matrix material also comprises whipping agent and thinner.The mass ratio of described fiber glass resin and whipping agent, thinner is preferably 100:(1～80): (50～200), more preferably 100:(10～60): (80～150).
The present invention there is no particular determination to described whipping agent, it can be the applicable whipping agent of reinforced plastic plate well known to those skilled in the art, the present invention is preferably any one or a few in calcium carbonate, magnesiumcarbonate, sodium bicarbonate, water glass, silicon carbide, sodium lauryl sulphate, polyoxyethylenated alcohol sodium sulfate, polyurethane foams, Foaming of phenolic resin agent and Cellmic C 121, more preferably Cellmic C 121.
The present invention there is no particular determination to described thinner, can be the applicable thinner of reinforced plastic plate well known to those skilled in the art, and the present invention is preferably any one or a few in water, methyl alcohol, ethanol, acetone and butanone, more preferably ethanol.
Through performance detects and shows that glass light sheet material matrix material provided by the invention has good mechanical property.
The present invention also provides a kind of preparation method of Graphene glass steel board matrix material, comprising:
A) porous graphene and fiber glass resin are mixed, obtain glass reinforced plastic prepreg resin;
B) by steps A) the glass reinforced plastic prepreg that obtains mixes with glass fibre with resin, obtains glass reinforced plastic prepreg;
C) by step B) the glass reinforced plastic prepreg that obtains is heating and curing, and obtains Graphene glass steel board matrix material.
First the present invention mixes porous graphene and fiber glass resin.
In the present invention, the preparation method of described porous graphene is identical with the preparation method of the porous graphene of above-mentioned record, does not repeat them here.
The present invention there is no particular determination to described fiber glass resin, can be fiber glass resin well known to those skilled in the art, can be bought and be obtained by market.
In the present invention, the mass ratio of described porous graphene and fiber glass resin is preferably 1:(1000～8500), 1:(2000～8000 more preferably), most preferably be 1:(2500～7000).
The present invention is preferred, described steps A) be specially:
By porous graphene, fiber glass resin, whipping agent and mixing diluents, obtain glass reinforced plastic prepreg resin.
The present invention there is no particular determination to described whipping agent, it can be the applicable whipping agent of reinforced plastic plate well known to those skilled in the art, the present invention is preferably any one or a few in calcium carbonate, magnesiumcarbonate, sodium bicarbonate, water glass, silicon carbide, sodium lauryl sulphate, polyoxyethylenated alcohol sodium sulfate, polyurethane foams, Foaming of phenolic resin agent and Cellmic C 121, more preferably Cellmic C 121.
The present invention there is no particular determination to described thinner, can be the applicable thinner of reinforced plastic plate well known to those skilled in the art, and the present invention is preferably any one or a few in water, methyl alcohol, ethanol, acetone and butanone, more preferably ethanol.
The mass ratio of described fiber glass resin and whipping agent, thinner is preferably 100:(1～80): (50～200), more preferably 100:(10～60): (80～150).
The present invention there is no particular determination to the mode of described mixing, can be hybrid mode well known to those skilled in the art, and the present invention preferably adopts the mode being uniformly mixed with ultrasonic mixing.
Preferably, first porous graphene and fiber glass resin are mixed, sonic oscillation, the temperature of described sonic oscillation is preferably 40 ℃～70 ℃, more preferably 50 ℃～60 ℃; The time of described sonic oscillation is preferably 12h～36h, more preferably 20h～28h.Then in system, add whipping agent and thinner, be uniformly mixed, the temperature of described stirring is preferably 40 ℃～70 ℃, more preferably 50 ℃～60 ℃; The time of described stirring is preferably 0.5h～2h, more preferably 0.8h～1.2h; The speed of described stirring is preferably 3000r/min～6000r/min, more preferably 4000r/min～5000r/min.
In the present invention, after described porous graphene, fiber glass resin, whipping agent and mixing diluents, can obtain glass reinforced plastic prepreg resin, preferably, the viscosity of described prepreg resin is 10cp/25 ℃～50cp/25 ℃, more preferably 15cp/25 ℃～40cp/25 ℃, most preferably is 20cp/25 ℃-30cp/25 ℃.
Obtain glass reinforced plastic prepreg with after resin, it is mixed with glass fibre, obtain glass reinforced plastic prepreg.
The present invention there is no particular determination to described glass fibre, can be glass fibre well known to those skilled in the art, and the present invention is preferably alkali-free short glass fiber, and the diameter of described glass fibre is preferably 10 μ m～30 μ m, more preferably 15 μ m～25 μ m.
The present invention is preferred, and described glass fibre is the 50wt%～300wt% of described porous graphene and fiber glass resin total amount, more preferably 100wt%～200wt%.
The present invention, to the mode of described mixing indefinite, can be hybrid mode well known to those skilled in the art, and the present invention is preferably the mode being uniformly mixed, and the temperature of described stirring is preferably room temperature, more preferably 20 ℃～25 ℃; The time of described stirring is preferably 0.5h～2h, more preferably 0.8h～1.2h; The speed of described stirring is preferably 3000r/min～6000r/min, more preferably 4000r/min～5000r/min.
After being uniformly mixed, system is carried out to heating, drying, can obtain glass reinforced plastic prepreg.The temperature of described heating, drying is preferably 60 ℃～120 ℃, more preferably 70 ℃～100 ℃; The time of described heating, drying is preferably 0.5h～2h, more preferably 0.8h～1.2h.
Obtain, after glass reinforced plastic prepreg, it being heating and curing, can obtain Graphene glass steel board matrix material.
In the present invention, described in the temperature that is heating and curing be preferably 80 ℃～180 ℃, more preferably 100 ℃～160 ℃; The described time being heating and curing is preferably 60min～180min, more preferably 80min～140min.
Prepare after Graphene glass steel board matrix material, it is carried out to Performance Detection, result shows that glass light sheet material matrix material provided by the invention has good mechanical property.
The invention provides a kind of Graphene glass steel board matrix material, comprising: porous graphene, fiber glass resin and glass fibre.The present invention is by added porous graphene in reinforced plastic plate, and the reinforced plastic plate matrix material of preparation has good shock resistance, counter-bending, compressive strength and wear resistance, can better be applied to the fields such as high ferro, automobile, steamer, aircraft.
In order to further illustrate the present invention, below in conjunction with embodiment, Graphene glass steel board matrix material provided by the invention is described in detail.
Embodiment 1
At 90 ℃, corn cob is carried out in sulfuric acid to the hydrolysis of 10min, obtain lignocellulose, the quality of described sulfuric acid is 3% of described corn cob quality;
At 70 ℃, the acid sulfite process that described lignocellulose is carried out 1 hour is processed, obtain porous cellulose, pH value in described acid sulfite process treating processes is 1, acid is sulfuric acid, sulphite is magnesium sulfite, and the quality of described sulfuric acid is 4% of described lignocellulose quality, and liquid-solid ratio is 2:1.
The porous cellulose obtaining is carried out to hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is 5% of described porous cellulose quality, and the bleaching temperature of described hydrogen peroxide bleaching is 100 ℃, and bleaching time is 5h.
Embodiment 2
At 180 ℃, corn cob is carried out in nitric acid to the hydrolysis of 10h, obtain lignocellulose, the quality of described nitric acid is 20% of described corn cob quality;
At 180 ℃, the acid sulfite process that described lignocellulose is carried out 6 hours is processed, obtain porous cellulose, pH value in described acid sulfite process treating processes is 7, acid is sulfuric acid, sulphite is S-WAT, and the quality of described sulfuric acid is 30% of described lignocellulose quality, and liquid-solid ratio is 20:1.
Described porous cellulose is carried out to hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is 5% of described porous cellulose quality, and the bleaching temperature of described hydrogen peroxide bleaching is 100 ℃, and bleaching time is 5h.
Embodiment 3
At 130 ℃, corn cob is carried out in hydrochloric acid to the hydrolysis of 5h, obtain lignocellulose, the quality of described hydrochloric acid is 10% of described corn cob quality;
At 120 ℃, the acid sulfite process that described lignocellulose is carried out 4 hours is processed, obtain porous cellulose, pH value in described acid sulfite process treating processes is 3, acid is sulfuric acid, sulphite is ammonium sulphite, and the quality of described sulfuric acid is 18% of described lignocellulose quality, and liquid-solid ratio is 10:1.
Described porous cellulose is carried out to hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is 5% of described porous cellulose quality, and the bleaching temperature of described hydrogen peroxide bleaching is 100 ℃, and bleaching time is 5h.
Embodiment 4
The porous cellulose that embodiment 1 is obtained and Manganous chloride tetrahydrate stir and within 2 hours, carry out catalytic treatment at 20 ℃, and the mass ratio of described Manganous chloride tetrahydrate and porous cellulose is 0.01:1; Product after the catalytic treatment obtaining is dry at 70 ℃, obtain water content lower than the first intermediate product of 10wt%.
Described the first intermediate product is placed in to charring furnace, using the gas intake of 200mL/min to passing into nitrogen in described carbide furnace as protection gas, described the first intermediate product is warming up to 300 ℃ with the speed of 5 ℃/min from 25 ℃, is incubated 4 hours, obtain the second intermediate product; Described the second intermediate product is warming up to 800 ℃ with the speed of 20 ℃/min from 300 ℃, is incubated 3.5 hours, obtain the 3rd intermediate product; Described the 3rd intermediate product is warming up to 1100 ℃ with the speed of 50 ℃/min from 800 ℃, is incubated 6 hours, obtain the 4th intermediate product; Described the 4th intermediate product is cooled to 900 ℃ with the speed of 30 ℃/min from 1100 ℃, is incubated 2 hours; The 4th intermediate product after described cooling is cooled to 60 ℃.
At 60 ℃, in the aqueous sodium hydroxide solution that is 3% in mass concentration by above-mentioned cooled the 4th intermediate product, wash 4 hours, obtain the first washed product; At 70 ℃, in the aqueous hydrochloric acid that is 4% in mass concentration by described the first washed product, wash 4 hours, obtain the second washed product; Described the second washed product is washed with distilled water to neutral rear being dried, obtains Graphene.
The Graphene that the embodiment of the present invention 4 is prepared carries out Raman spectrum test, and as shown in Figure 1, Fig. 1 is the Raman spectrum of the Graphene that obtains of the embodiment of the present invention 4 to test result, as shown in Figure 1, and the Graphene Sp that the method that the embodiment of the present invention 4 provides prepares
2hydridization degree is high.The Graphene that the embodiment of the present invention 4 is prepared carries out transmissioning electric mirror test, test result is as shown in Fig. 2～Fig. 5, Fig. 2～Fig. 5 is the transmission electron microscope picture of the Graphene that obtains of the embodiment of the present invention 4, by Fig. 2～Fig. 5, can be found out, the lamella of the Graphene that the method that the embodiment of the present invention 4 provides prepares is thinner, below 10 layers, it is porous graphene.Adopt conducting performance test instrument, the electroconductibility of the porous graphene that the test embodiment of the present invention 4 prepares, test result is that the conductivity of the porous graphene that the method that the embodiment of the present invention 4 provides prepares is 40000S/m.
Embodiment 5
The porous cellulose that embodiment 2 is prepared and iron nitrate stir and within 10 hours, carry out catalytic treatment at 180 ℃, and the mass ratio of described iron nitrate and porous cellulose is 2:1; Product after the catalytic treatment obtaining is dry at 120 ℃, obtain water content lower than the first intermediate product of 5wt%.
Described the first intermediate product is placed in to charring furnace, using the gas intake of 800mL/min to passing into argon gas in described carbide furnace as protection gas, described the first intermediate product is warming up to 400 ℃ with the speed of 20 ℃/min from 20 ℃, is incubated 8 hours, obtain the second intermediate product; Described the second intermediate product is warming up to 900 ℃ with the speed of 50 ℃/min from 400 ℃, is incubated 7 hours, obtain the 3rd intermediate product; Described the 3rd intermediate product is warming up to 1300 ℃ with the speed of 60 ℃/min from 900 ℃, is incubated 8 hours, obtain the 4th intermediate product; Described the 4th intermediate product is cooled to 1000 ℃ with the speed of 50 ℃/min from 1300 ℃, is incubated 4 hours; The 4th intermediate product after described cooling is cooled to 20 ℃.
At 120 ℃, in the aqueous sodium hydroxide solution that is 55% in mass concentration by above-mentioned cooled the 4th intermediate product, wash 24 hours, obtain the first washed product; At 150 ℃, in the aqueous hydrochloric acid that is 10% in mass concentration by described the first washed product, wash 24 hours, obtain the second washed product; Described the second washed product is washed with distilled water to neutral rear being dried, obtains Graphene.
According to the method described in embodiment 4, the Graphene that the embodiment of the present invention 5 is obtained detects, and detected result is, the Graphene Sp that the method that the embodiment of the present invention 5 provides prepares
2hydridization degree is high; The lamella of Graphene is thinner, below 10 layers, is porous graphene; The conductivity of porous graphene is 38000S/m.
Embodiment 6
The porous cellulose that embodiment 3 is prepared and rose vitriol stir and within 5 hours, carry out catalytic treatment at 50 ℃, and the mass ratio of described rose vitriol and porous cellulose is 0.1:1; Product after the catalytic treatment obtaining is dry at 90 ℃, obtain water content lower than the first intermediate product of 8wt%.
Described the first intermediate product is placed in to charring furnace, using the gas intake of 400mL/min to passing into nitrogen in described carbide furnace as protection gas, described the first intermediate product is warming up to 320 ℃ with the speed of 10 ℃/min from 40 ℃, is incubated 5 hours, obtain the second intermediate product; Described the second intermediate product is warming up to 820 ℃ with the speed of 30 ℃/min from 320 ℃, is incubated 5 hours, obtain the 3rd intermediate product; Described the 3rd intermediate product is warming up to 1150 ℃ with the speed of 54 ℃/min from 820 ℃, is incubated 7 hours, obtain the 4th intermediate product; Described the 4th intermediate product is cooled to 920 ℃ with the speed of 35 ℃/min from 1150 ℃, is incubated 3 hours; The 4th intermediate product after described cooling is cooled to 30 ℃.
At 80 ℃, in the ammoniacal liquor that is 10% in mass concentration by above-mentioned cooled the 4th intermediate product, wash 8 hours, obtain the first washed product; At 90 ℃, in the aqueous hydrochloric acid that is 6% in mass concentration by described the first washed product, wash 8 hours, obtain the second washed product; Described the second washed product is washed with distilled water to neutral rear being dried, obtains Graphene.
According to the method described in embodiment 4, the Graphene that the embodiment of the present invention 6 is obtained detects, and detected result is, the Graphene Sp that the method that the embodiment of the present invention 6 provides prepares
2hydridization degree is high; The lamella of Graphene is thinner, below 10 layers, is porous graphene; The conductivity of porous graphene is 39000S/m.
Embodiment 7
The porous graphene of 1g embodiment 4 preparations is mixed with resin PF-7215 with the glass reinforced plastic of 1000g Shandong holy well group, be warming up to 50 degree, sonic oscillation 24h, then add 100g Cellmic C 121,500g ethanol, adjustment viscosity is 50cp/25 ℃, with rotating speed 3000r/min, stir 1 hour, obtain glass reinforced plastic prepreg resin.
Then get glass reinforced plastic prepreg resin prepared by 100g, mix with 300g diameter 10 μ m alkali-free short glass fibers, 25 ℃ are stirred 1 hour with rotating speed 3000r/min, and 60 degree are dried 1 hour, obtain glass reinforced plastic prepreg.
Then the prepreg obtaining is put into 80 degree moulds and be heating and curing 180 minutes, obtain Graphene glass steel board matrix material.
It is carried out to performance test, the results are shown in Table 1, table 1 is that the performance measurement result of the embodiment of the present invention 7～9 and comparative example 1 gathers.
The performance measurement result of table 1 embodiment 7～9 and comparative example 1 gathers
Embodiment 8
The porous graphene of 1g embodiment 5 preparations is mixed with resin EXP0440 with the glass reinforced plastic of 4000g Shandong holy well group, be warming up to 55 degree, sonic oscillation 24h, then add 1200g Cellmic C 121,4000g ethanol, adjustment viscosity is 38cp/25 ℃, with rotating speed 4000r/min, stir 1 hour, obtain glass reinforced plastic prepreg resin.
Then get glass reinforced plastic prepreg resin prepared by 100g, mix with 230g diameter 20 μ m alkali-free short glass fibers, 25 ℃ are stirred 1 hour with rotating speed 4000r/min, and 75 degree are dried 1 hour, obtain glass reinforced plastic prepreg.
Then the prepreg obtaining is put into 95 degree moulds and be heating and curing 90 minutes, obtain Graphene glass steel board matrix material.
It is carried out to performance test, the results are shown in Table 1, table 1 is that the performance measurement result of the embodiment of the present invention 7～9 and comparative example 1 gathers.
Embodiment 9
The porous graphene of 1g embodiment 6 preparations is mixed with resin EXP0440-1 with the glass reinforced plastic of 8500g Shandong holy well group, be warming up to 60 degree, sonic oscillation 24h, then add 6800g Cellmic C 121,17000g ethanol, adjustment viscosity is 15cp/25 ℃, with rotating speed 6000r/min, stir 1 hour, obtain glass reinforced plastic prepreg resin.
Then get glass reinforced plastic prepreg resin prepared by 100g, mix with the alkali-free short glass fiber of 20 microns of 80g diameters, 25 ℃ are stirred 1 hour with rotating speed 6000r/min, and 120 degree are dried 1 hour, obtain glass reinforced plastic prepreg.
Then the prepreg obtaining is put into 180 degree moulds and be heating and curing 60 minutes, obtain Graphene glass steel board matrix material.
It is carried out to performance test, the results are shown in Table 1, table 1 is that the performance measurement result of the embodiment of the present invention 7～9 and comparative example 1 gathers.
Comparative example 1
By resin EXP0440-1 fiber glass resin and 6800g Cellmic C 121,17000g methanol mixed for the glass reinforced plastic of 8500g Shandong holy well group, adjustment viscosity is 15cp/25 ℃, with rotating speed 6000r/min stirring 1 hour, obtains glass reinforced plastic prepreg resin.10 microns of alkali-free short glass fibers mix, and 25 ℃ are stirred 1 hour with rotating speed 6000r/min, and 120 degree are dried 1 hour, obtain glass reinforced plastic prepreg.
Then the prepreg obtaining is put into 180 degree moulds and be heating and curing 60 minutes, obtain Graphene glass steel board matrix material.
It is carried out to performance test, the results are shown in Table 1, table 1 is that the performance measurement result of the embodiment of the present invention 7～9 and comparative example 1 gathers.
From above-described embodiment and comparative example, the present invention be take porous graphene as raw material, and the reinforced plastic plate of preparation has good mechanical property.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a Graphene glass steel board matrix material, comprising: porous graphene, fiber glass resin and glass fibre.
2. matrix material according to claim 1, is characterized in that, described porous graphene is prepared in accordance with the following methods:
1), under the effect of catalyzer, biomass carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), under the condition of protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 ℃～40 ℃, described the second temperature is 300 ℃～400 ℃;
3), under the condition of protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 ℃～900 ℃;
4), under the condition of protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 ℃～1300 ℃;
5), under the condition of protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain porous graphene, described the 5th temperature is 900 ℃～1000 ℃.
3. matrix material according to claim 1, is characterized in that, the mass ratio of described porous graphene and fiber glass resin is 1:(1000～8500); Described glass fibre is the 50wt%～300wt% of described porous graphene and fiber glass resin total amount.
4. matrix material according to claim 1, is characterized in that, also comprises whipping agent and thinner.
5. matrix material according to claim 4, is characterized in that, the mass ratio of described fiber glass resin and whipping agent, thinner is 100:(1～80): (50～200).
6. a preparation method for Graphene glass steel board matrix material, comprising:
A) porous graphene and fiber glass resin are mixed, obtain glass reinforced plastic prepreg resin;
B) by steps A) the glass reinforced plastic prepreg that obtains mixes with glass fibre with resin, obtains glass reinforced plastic prepreg;
C) by step B) the glass reinforced plastic prepreg that obtains is heating and curing, and obtains Graphene glass steel board matrix material.
7. preparation method according to claim 6, is characterized in that, described steps A) be specially:
By porous graphene, fiber glass resin, whipping agent and mixing diluents, obtain glass reinforced plastic prepreg resin.
8. preparation method according to claim 7, is characterized in that, the mass ratio of described fiber glass resin and whipping agent, thinner is 100:(1～80): (50～200).
9. preparation method according to claim 6, is characterized in that, the mass ratio of described porous graphene and fiber glass resin is 1:(1000～8500); Described glass fibre is the 50wt%～300wt% of described porous graphene and fiber glass resin total amount.
10. preparation method according to claim 6, is characterized in that, described porous graphene is prepared in accordance with the following methods:
1), under the effect of catalyzer, biomass carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), under the condition of protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 ℃～40 ℃, described the second temperature is 300 ℃～400 ℃;
3), under the condition of protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 ℃～900 ℃;
4), under the condition of protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 ℃～1300 ℃;
5), under the condition of protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain porous graphene, described the 5th temperature is 900 ℃～1000 ℃.
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Denomination of invention: Graphene glassfiber-reinforced plastic plate composite material and preparation method thereof Effective date of registration: 20181228 Granted publication date: 20170606 Pledgee: China Co truction Bank Corp Ji'nan Zhangqiu sub branch Pledgor: Shengquan Group Co., Ltd., Ji'nan City Registration number: 2018370000239 |