CN106365517B - A kind of bionical quartz of radiation proof and preparation method thereof - Google Patents

Abstract

The invention discloses bionical quartz of a kind of radiation proof and preparation method thereof, the preparation method comprises the following steps：Step A, prepares modified resin；Step B, by weight percentage, 80 ~ 90% quartz, 8 ~ 12% modified resins, 0.01 ~ 1% curing agent, 0.01 ~ 1% coupling agent, 1 ~ 5% bamboo charcoal nano, 1 ~ 3% aluminium hydrate powder and 0.1 ~ 2% colorant is stirred, compound is obtained；Step C, carries out first time cloth in template by compound, shakes molded, be stripped, and cutting arranges to obtain semi-finished product by predetermined pattern；Second of cloth is carried out again, is shaken molded, and then drying forming carries out post-processing to obtain finished product.Compare, bionical quartz dispensing science produced by the present invention, it is reasonable to prepare, performance is stable, high mechanical strength, be unlikely to deform and non-aging with existing bionical quartz；And by rational collocation bamboo charcoal nano, deodorant and antibacterial powder so that bionical quartz has excellent antibacterial, deodorization and shielding property, has further widened the application of bionical quartz.

Description

A kind of bionical quartz of radiation proof and preparation method thereof

Technical field

The present invention relates to quartz technical field, the more particularly to a kind of bionical quartz of radiation proof and its preparation side Method.

Background technology

Bacterium, mould has very big harm to the mankind and animals and plants as pathogen, and the health of influence people even jeopardizes life Life, brings great economic loss.Therefore the research of anti-biotic material and its product increasingly causes the concern of people, antibacterial product Demand will constitute huge market.

Bionical quartz, which has, shrinks low, and manufacturing cost is low, it is easy to process and color and luster is abundant, product properties is protruded, hardness High the advantages of, it has been made various industrial and civilian floor and ornament materials, and has been widely used in industrial production and people In daily life, the decorative material material of floor tile, metope etc. is used as.

But, the bionical quartz on uniformity preferably stable antibacterial functions is also rarely reported at present.And it is existing There is the product that bionical quartz is usually simple function, function such as antibacterial, antistatic etc., i.e., a kind of product do not possess multinomial work( Can, this strongly limits its application, it need further raising.

The content of the invention

In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of bionical quartz of radiation proof and its preparation side Method.

The technical problems to be solved by the invention are achieved by the following technical programs：

A kind of bionical quartz of radiation proof and preparation method thereof, the preparation method comprises the following steps：

Step A, prepares modified resin：By weight percentage, by 85 ~ 90% resins, 4 ~ 8% functional agents and 1 ~ 5% dispersant Melting is heated after being well mixed with homogenizer, is 1 using draw ratio：40 double screw extruder extruding pelletizations, it is melted Mixing disperses extrusion temperature：100 DEG C~280 DEG C；The resin is epoxy resin, phenolic resin, acrylic resin, polyurethane One or more in resin；

Step B, by weight percentage, by 80 ~ 90% quartz, 8 ~ 12% modified resins, 0.01 ~ 1% curing agent, 0.01 ~ 1% Coupling agent, 1 ~ 5% bamboo charcoal nano, 1 ~ 3% aluminium hydrate powder and 0.1 ~ 2% colorant stir, and obtain compound；

Step C, carries out first time cloth in template by compound, shakes molded, be stripped, and cutting is arranged by predetermined pattern Arrange to obtain semi-finished product；Second of cloth is carried out again, is shaken molded, and then drying forming carries out post-processing to obtain finished product.

In the present invention, aluminium hydrate powder is used so that quartz has a good fire retardant performance, and can be to prevent Only smoke, generation toxic gas, use safety.

In the present invention, the curing agent is selected from peroxidating（2 ethyl hexanoic acid）The tert-butyl ester, methyl ethyl ketone peroxide, peroxidating One or more in t-butyl perbenzoate and fat polyamine.The silane coupler is gamma-methyl allyl acyloxypropyl three Methoxy silane, γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane, N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxy Base silane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane, Anilinomethyl triethoxysilane, gamma-aminopropyl-triethoxy-silane, VTES, vinyl trimethoxy One or more in silane and γ-chloropropyl triethoxysilane.The colorant is colored pigment.

In the present invention, the bamboo charcoal nano is bamboo charcoal nano of the particle diameter between 100 ~ 500nm.

In the present invention, the functional agent can be made by the following method：

（1）0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fractions are 98% is measured, by C60 powder and dense Sulfuric acid is mixed in beaker, and beaker is placed in ice-water bath, while being stirred with 500 ~ 600rpm speed, obtains mixed liquor；Weigh 1 ~ 3g potassium permanganate powders, are slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, bath temperature 30 ~ 40 is kept DEG C, react 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, then with the bag filter dialysis 3 ~ 5 that molecular cut off is 1000 My god, obtain graphene quantum dot（GQDs）Suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiation 30 ~ 60min, laser irradiation power is 0.5 ~ 2W；It is standby；

（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；By Concentration is added dropwise to for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio be 2 ~ 3:1）, 10 ~ 20min of ultrasonic agitation；Be added dropwise 0.5 ~ 1mol/L sodium hydroxide solutions, regulation pH value to 11, then stand, from The heart, with deionized water and ethanol alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in 80 ~ 120ml aqueous solution；Be added dropwise concentration for 0.005 ~ Concentration is added dropwise after the 0.05mol/L cerous nitrate aqueous solution, 30 ~ 60min for 0.005 ~ 0.05mol/L zinc nitrate aqueous solutions, GQDs/Ag₂The O aqueous solution, the cerous nitrate aqueous solution and zinc nitrate aqueous solution volume ratio are 1:0.1~0.2:0.2~0.4；Continue ultrasound Stirring, regulation mixed solution pH value to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8mL mass fractions are 50%, 30 ~ 0.5 ~ 1h of reduction reaction at 40 DEG C；Afterwards, the hydrazine hydrate that 40 ~ 50mL mass fractions are 50%, the reduction reaction at 85 DEG C are added After 30 ~ 48h；Filtering, is washed with deionized for several times, and vacuum drying obtains GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 3 is added afterwards ~5:1 water and ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂O/Ag-Zn-Ce mass ratio is 3:1~3）, It is 9 ~ 10 to adjust pH value, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；Progress centrifuges and uses acetone and deionized water successively Cleaning is precipitated；This is deposited at 80 ~ 90 DEG C and dries 2 ~ 4h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/ Ag₂O/Ag-Zn-Ce/SiO₂It is placed under argon gas atmosphere and carries out 500 ~ 800 DEG C of 1 ~ 2h of heat treatment, is cooled to after room temperature, is immersed in hydrogen 10 ~ 15min of ultrasound is carried out with 100 ~ 150W of ultrasonic power in fluoric acid, the local silica in surface is removed, centrifuges and dry, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

（5）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In the aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:1~5；10~ 100W 60 ~ 120min of ultrasound, are stood, and deionized water is washed for several times, and centrifugation is placed in confined space, and progress is vacuumized → heated Pressurized circulation 3 ~ 8 times（Pumpdown time is 20 ~ 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, it is forced into 0.3 ~ 0.6Mpa, 20 ~ 30min of pressurize）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, That is antibacterial powder；

（6）Antibacterial powder and deodorant is taken to be scattered in 100 ~ 200ml ultra-pure waters, 2 ~ 3h of ultrasonic agitation obtains uniform stabilization Dispersion liquid, wherein the weight ratio of antibacterial powder and deodorant be 3 ~ 5:2~4；Substrate with carbon nanotube mesh film is placed in about At 8 DEG C, in the substrate that dispersion liquid is added to concave shape, meanwhile, roller is rolled around, the homogeneous dispersion is scattered in the carbon In nanotube reticular membrane, due to having hydrophily when CNT is near 8 DEG C, the dispersion liquid is attracted to carbon nanotube mesh Multiple net holes of film；About 25 DEG C are warming up to, CNT, which has hydrophobicity and drives most of moisture away, leaves absorption in carbon Antibacterial powder and deodorant in multiple net holes of nanotube reticular membrane；Remove moisture, be placed in confined space, progress is vacuumized → added Hot pressurized circulation 3 ~ 5 times（Pumpdown time is 20 ~ 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature For 80 ~ 90 DEG C, 0.3 ~ 0.6Mpa, 20 ~ 30min of pressurize are forced into）, then will be adsorbed with the CNT of antibacterial powder and deodorant Reticular membrane scrapes off the substrate, obtains antibacterial-deodorization functions agent.

In the present invention, the functional agent can also be made by the following method：

（1）0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fractions are 98% is measured, by C60 powder and dense Sulfuric acid is mixed in beaker, and beaker is placed in ice-water bath, while being stirred with 500 ~ 600rpm speed, obtains mixed liquor；Weigh 1 ~ 3g potassium permanganate powders, are slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, bath temperature 30 ~ 40 is kept DEG C, react 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, then with the bag filter dialysis 3 ~ 5 that molecular cut off is 1000 My god, obtain graphene quantum dot（GQDs）Suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiation 30 ~ 60min, laser irradiation power is 0.5 ~ 2W；It is standby；

（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；By Concentration is added dropwise to for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio be 2 ~ 3:1）, 10 ~ 20min of ultrasonic agitation；Be added dropwise 0.5 ~ 1mol/L sodium hydroxide solutions, regulation pH value to 11, then stand, from The heart, with deionized water and ethanol alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise for 0.05 ~ 0.5g/ The 100mlZnO quantum dot aqueous solution, ultrasonic power mixing speed respectively halves；After 60 ~ 90min, stand, filtering is washed with deionized water Wash for several times, vacuum drying obtains GQDs/Ag₂O/ZnO；

（4）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂O/ZnO weight ratio is 1:1~5；10 ~ 100W ultrasounds 60 ~ 120min, it is quiet Put, deionized water is washed for several times, centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 3 ~ 8 times（Vacuumize Time is 20 ~ 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, it is forced into 0.3 ~ 0.6Mpa, 20 ~ 30min of pressurize）, obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder；

（5）Antibacterial powder and deodorant is taken to be scattered in 100 ~ 200ml ultra-pure waters, 2 ~ 3h of ultrasonic agitation obtains uniform stabilization Dispersion liquid, wherein the weight ratio of antibacterial powder and deodorant be 3 ~ 5:2~4；Substrate with carbon nanotube mesh film is placed in about At 8 DEG C, in the substrate that dispersion liquid is added to concave shape, meanwhile, roller is rolled around, the homogeneous dispersion is scattered in the carbon In nanotube reticular membrane, due to having hydrophily when CNT is near 8 DEG C, the dispersion liquid is attracted to carbon nanotube mesh Multiple net holes of film；About 25 DEG C are warming up to, CNT, which has hydrophobicity and drives most of moisture away, leaves absorption in carbon Antibacterial powder and deodorant in multiple net holes of nanotube reticular membrane；Remove moisture, be placed in confined space, progress is vacuumized → added Hot pressurized circulation 3 ~ 5 times（Pumpdown time is 20 ~ 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature For 80 ~ 90 DEG C, 0.3 ~ 0.6Mpa, 20 ~ 30min of pressurize are forced into）, then will be adsorbed with the CNT of antibacterial powder and deodorant Reticular membrane scrapes off the substrate, obtains antibacterial-deodorization functions agent.

Wherein, the three-dimensional sponge shape graphene preparation method is as follows：By 3g graphite powders, 1g NaNO3 are in ice-water bath It is well mixed with the concentrated sulfuric acids of 250ml 98%, is slowly added to 6g KMnO4.Then heat at 35 DEG C, after stirring 40min, add 95ml deionized waters, are warming up to 98 DEG C of reaction 20min；The dilution of 270ml water is added, and it is many with the H2O2 of 5ml 30% neutralizations Remaining KMnO4, the color of mixed solution is brown color, is filtered while hot, with deionized water cyclic washing to neutrality, ultrasonic disperse is obtained GO；The graphene oxide solution for taking 200ml mass fractions to be 5mg/ml pours into diameter 25cm, high 2cm discoid reaction utensil In, adding ascorbic acid (VC) 0.5g stirrings is sufficiently mixed it；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reaction 15h, Graphene oxide Spontaneous Contraction in reaction utensil is cross-linked into three-dimensional sponge structure, freeze-drying, obtains the three-dimensional sponge shape of flexibility Graphene.

The present invention has the advantages that：

Compared with existing bionical quartz, bionical quartz dispensing science produced by the present invention, it is reasonable to prepare, and performance is steady It is fixed, high mechanical strength, it is unlikely to deform and non-aging；And by rational collocation deodorant, bamboo charcoal nano and antibacterial powder, three Person acts synergistically so that bionical quartz has excellent antibacterial, deodorization and shielding property, has further widened bionical quartz The application of stone；

This method is loaded and fixed antiseptic on three-dimensional grapheme, is not only prevented it from reuniting, is significantly improved metal nano The stability of the antiseptics such as particle, can more preferably be dispersed in bionical quartz, and with more efficient antibacterial activity and Silver ion will not overflow oxidation stain；The anti-microbial property of a variety of antiseptics is compounded with simultaneously, compared to single silver nano antibacterial Agent has more preferable antibacterial effect, and antibacterial is lasting；Inorganic oxide main component has more than 10 kinds of magnesium, aluminium, iron etc. favourable to human body Trace element, because it is a kind of special polarity crystalline solid of structure, itself can produce electron ion for a long time, and forever discharge empty Gas anion, reaches that deodorization purifies the effect of air；Bamboo charcoal nano contains the multiple beneficial element such as charcoal, hydrogen, oxygen, fine and closely woven porous, The erosion for the harm ray that various electrical equipment are produced can be blocked and absorbed, human body is thoroughly exempted the harm of harm ray, nanometer Bamboo charcoal can also produce anion, adsorb and decompose various free harmful substances, automatically adjust humidity, can also produce most suitable The far infrared of human body.

Embodiment

Technical scheme is further illustrated below by specific preferred embodiment.

Embodiment 1

A kind of bionical quartz of radiation proof and preparation method thereof, the preparation method comprises the following steps：

Step A, prepares modified resin：By weight percentage, by 87% resin, 8% antibacterial powder and 5% dispersant at a high speed Melting is heated after mixer is well mixed, is 1 using draw ratio：40 double screw extruder extruding pelletizations, its melting mixing point Scattered extrusion temperature is：100 DEG C~280 DEG C；The resin is epoxy resin, phenolic resin, acrylic resin, polyurethane resin are pressed Weight compares 3:2:2:1 mixing；

Step B, by weight percentage, weighs 82% quartz（Quartz sand presses 3 with silica flour：1 mixing）, 13% be modified tree Fat, 0.5% methyl ethyl ketone peroxide, 0.5% VTES, 1% bamboo charcoal nano（Particle diameter is between 100 ~ 500nm）, 2% hydrogen Alumina powder and 1% colorant；Quartz sand, aluminium hydrate powder, bamboo charcoal nano are placed in and stirs and must be pre-mixed in the first mixer Material, mixing speed 1000r/min, mixing time 20min；Silica flour, modified resin, curing agent, coupling agent and colorant are placed in Stirred in second mixer, mixing speed 1000r/min, mixing time 20min；Premix is added into the second mixer Inside stir, mixing speed 250r/min, mixing time 30min obtain compound；

Step C, C01, by compound carry out first time cloth in template, i.e., compound is paved in mould by material distributing machine On plate；

C02, carry out by press shaking molded for the first time, obtain idiosome；Wherein, vibration frequency is 45Hz, time of vibration 200s；

C03, gained idiosome is stripped and cut by cutter device, semi-finished product are obtained by predetermined pattern arrangement；

C04, by gained semi-finished product carry out second of cloth；

C07, shaken for the second time by press molded, vibration frequency is 50Hz, time of vibration 240s；

C08, shake for the second time it is molded after, carry out drying forming, drying temperature be 92 DEG C, drying time 1.5h；

C09, the semi-finished product to drying forming are post-processed, such as fixed thick processing, polishing, obtain finished product.

Wherein, the preparation method of the functional agent is as follows：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.001mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.1mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 1gGQDs/Ag₂O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise for 0.05mol/L nitre Concentration is added dropwise after the sour cerium aqueous solution, 30min for 0.005mol/L zinc nitrate aqueous solutions, GQDs/Ag₂The O aqueous solution, cerous nitrate The aqueous solution is 1 with zinc nitrate aqueous solution volume ratio:0.1:0.4；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Bian Chao Sound is stirred, and side adds the hydrazine hydrate that 6mL mass fractions are 50%, the reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL matter is added The hydrazine hydrate that fraction is 50% is measured, at 85 DEG C after reduction reaction 36h；Filtering, is washed with deionized for several times, and vacuum drying is obtained GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 Water and ammoniacal liquor, are stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂O/Ag-Zn-Ce mass ratio is 3:2）, adjust pH value For 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 30min；Progress, which is centrifuged and cleaned successively with acetone and deionized water, is sunk Form sediment；This is deposited at 90 DEG C and dries 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂It is placed under argon gas atmosphere and carries out 600 DEG C of heat treatment 1h, is cooled to after room temperature, is immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 10min is carried out, the local silica in surface is removed, centrifuges and dry, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

（5）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In the aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:5；50W ultrasounds 100min, is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 3 times （Pumpdown time is 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

（6）Prepare deodorant：Mix the raw material of following percentage by weight：ZrO₂2%, TiO₂15%, SiO₂20%, V₂O₅ 5%, K₂O 1%, SnO₂5%, Cr₂O₃2%, Al₂O₃12%, Fe₂O₃15%, MgO 12%, Na₂O10%, MnO₂ 1%, put into It is ground in the big flow circulation horizontal sand mill of PUHLER companies exploitation, control particle diameter obtains inorganic between 10 ~ 300nm Oxide；Diatomite is dispersed in the 100 ~ 200ml aqueous solution, add inorganic oxide, wherein the diatomite with it is inorganic The weight ratio of oxide is 1:1,150W ultrasound 150rpm stirs 2h, allows nano material well into diatom soil pores, repeatedly Suction filtration is cleaned；It is placed in confined space, progress vacuumizes → heated pressurized circulation 5 times（Pumpdown time is 30min；Heating adds Press to be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain deodorant；

（7）Antibacterial powder and deodorant is taken to be scattered in 150ml ultra-pure waters, ultrasonic agitation 2h obtains the scattered of uniform stabilization The weight ratio of liquid, wherein antibacterial powder and deodorant is 3:4；When substrate with carbon nanotube mesh film is placed in into about 8 DEG C, it will divide Dispersion liquid is added in the substrate of concave shape, meanwhile, roller is rolled around, the homogeneous dispersion is scattered in the carbon nanotube mesh In film, due to having hydrophily when CNT is near 8 DEG C, the dispersion liquid is attracted to multiple nets of carbon nanotube mesh film Hole；About 25 DEG C are warming up to, CNT, which has hydrophobicity and drives most of moisture away, leaves absorption in carbon nanotube mesh Antibacterial powder and deodorant in multiple net holes of film；Remove moisture, be placed in confined space, progress vacuumize → heat pressurized circulation 4 times（Pumpdown time is 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, the carbon nanotube mesh film for being adsorbed with antibacterial powder and deodorant is then scraped off into the substrate, resisted Bacterium-deodorization functions agent.

Embodiment 2

A kind of bionical quartz of radiation proof and preparation method thereof, the preparation method comprises the following steps：

Step A, prepares modified resin：By weight percentage, by 90% resin, 6% antibacterial powder and 4% dispersant at a high speed Melting is heated after mixer is well mixed, is 1 using draw ratio：40 double screw extruder extruding pelletizations, its melting mixing point Scattered extrusion temperature is：100 DEG C~280 DEG C；The resin is epoxy resin, phenolic resin, acrylic resin, polyurethane resin are pressed Weight compares 3:2:2:1 mixing；

Step B, by weight percentage, weighs 80% quartz（Quartz sand presses 3 with silica flour：1 mixing）, 12% be modified tree Fat, 0.5% methyl ethyl ketone peroxide, 0.5% VTES, 3% bamboo charcoal nano（Particle diameter is between 100 ~ 500nm）, 3% hydrogen Alumina powder and 1% colorant；Quartz sand, aluminium hydrate powder, bamboo charcoal nano are placed in and stirs and must be pre-mixed in the first mixer Material, mixing speed 1000r/min, mixing time 20min；Silica flour, modified resin, curing agent, coupling agent and colorant are placed in Stirred in second mixer, mixing speed 1000r/min, mixing time 20min；Premix is added into the second mixer Inside stir, mixing speed 250r/min, mixing time 30min obtain compound；

Step C, C01, by compound carry out first time cloth in template, i.e., compound is paved in mould by material distributing machine On plate；

C02, carry out by press shaking molded for the first time, obtain idiosome；Wherein, vibration frequency is 45Hz, time of vibration 200s；

C03, gained idiosome is stripped and cut by cutter device, semi-finished product are obtained by predetermined pattern arrangement；

C04, by gained semi-finished product carry out second of cloth；

C07, shaken for the second time by press molded, vibration frequency is 50Hz, time of vibration 240s；

C08, shake for the second time it is molded after, carry out drying forming, drying temperature be 92 DEG C, drying time 1.5h；

C09, the semi-finished product to drying forming are post-processed, such as fixed thick processing, polishing, obtain finished product.

Wherein, the preparation method of the functional agent is as follows：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.005mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.2mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 2gGQDs/Ag₂O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise for 0.03mol/L nitre Concentration is added dropwise after the sour cerium aqueous solution, 30min for 0.03mol/L zinc nitrate aqueous solutions, GQDs/Ag₂The O aqueous solution, cerous nitrate The aqueous solution is 1 with zinc nitrate aqueous solution volume ratio:0.2:0.3；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Bian Chao Sound is stirred, and side adds the hydrazine hydrate that 6mL mass fractions are 50%, the reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL matter is added The hydrazine hydrate that fraction is 50% is measured, at 85 DEG C after reduction reaction 36h；Filtering, is washed with deionized for several times, and vacuum drying is obtained GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.3gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 Water and ammoniacal liquor, are stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂O/Ag-Zn-Ce mass ratio is 3:2）, adjust pH value For 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 45min；Progress, which is centrifuged and cleaned successively with acetone and deionized water, is sunk Form sediment；This is deposited at 90 DEG C and dries 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂It is placed under argon gas atmosphere and carries out 600 DEG C of heat treatment 1h, is cooled to after room temperature, is immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 12min is carried out, the local silica in surface is removed, centrifuges and dry, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

（5）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In the aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:3；50W ultrasounds 100min, is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 5 times （Pumpdown time is 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

（6）Prepare deodorant：Mix the raw material of following percentage by weight：ZrO₂6%, TiO₂8%, SiO₂15%, V₂O₅ 3%, K₂O 2%, SnO₂3%, Cr₂O₃4%, Al₂O₃15%, Fe₂O₃10%, MgO 20%, Na₂O 6%, MnO₂ 8%, put into It is ground in the big flow circulation horizontal sand mill of PUHLER companies exploitation, control particle diameter obtains inorganic between 10 ~ 300nm Oxide；Diatomite is dispersed in the 100 ~ 200ml aqueous solution, add inorganic oxide, wherein the diatomite with it is inorganic The weight ratio of oxide is 1:3,150W ultrasound 150rpm stir 2h, allow nano material well into diatom soil pores, repeatedly Suction filtration is cleaned；It is placed in confined space, progress vacuumizes → heated pressurized circulation 5 times（Pumpdown time is 30min；Heating adds Press to be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain deodorant；

（7）Antibacterial powder and deodorant is taken to be scattered in 150ml ultra-pure waters, ultrasonic agitation 2h obtains the scattered of uniform stabilization The weight ratio of liquid, wherein antibacterial powder and deodorant is 4:3；When substrate with carbon nanotube mesh film is placed in into about 8 DEG C, it will divide Dispersion liquid is added in the substrate of concave shape, meanwhile, roller is rolled around, the homogeneous dispersion is scattered in the carbon nanotube mesh In film, due to having hydrophily when CNT is near 8 DEG C, the dispersion liquid is attracted to multiple nets of carbon nanotube mesh film Hole；About 25 DEG C are warming up to, CNT, which has hydrophobicity and drives most of moisture away, leaves absorption in carbon nanotube mesh Antibacterial powder and deodorant in multiple net holes of film；Remove moisture, be placed in confined space, progress vacuumize → heat pressurized circulation 4 times（Pumpdown time is 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, the carbon nanotube mesh film for being adsorbed with antibacterial powder and deodorant is then scraped off into the substrate, resisted Bacterium-deodorization functions agent.

Embodiment 3

A kind of bionical quartz of radiation proof and preparation method thereof, the preparation method comprises the following steps：

Step A, prepares modified resin：By weight percentage, by 92% resin, 4% antibacterial powder and 4% dispersant at a high speed Melting is heated after mixer is well mixed, is 1 using draw ratio：40 double screw extruder extruding pelletizations, its melting mixing point Scattered extrusion temperature is：100 DEG C~280 DEG C；The resin is epoxy resin, phenolic resin, acrylic resin, polyurethane resin are pressed Weight compares 3:2:2:1 mixing；

Step B, by weight percentage, weighs 80% quartz（Quartz sand presses 3 with silica flour：1 mixing）, 12% be modified tree Fat, 0.5% methyl ethyl ketone peroxide, 0.5% VTES, 5% bamboo charcoal nano（Particle diameter is between 100 ~ 500nm）, 1% hydrogen Alumina powder and 1% colorant；Quartz sand, aluminium hydrate powder, bamboo charcoal nano are placed in and stirs and must be pre-mixed in the first mixer Material, mixing speed 1000r/min, mixing time 20min；Silica flour, modified resin, curing agent, coupling agent and colorant are placed in Stirred in second mixer, mixing speed 1000r/min, mixing time 20min；Premix is added into the second mixer Inside stir, mixing speed 250r/min, mixing time 30min obtain compound；

Step C, C01, by compound carry out first time cloth in template, i.e., compound is paved in mould by material distributing machine On plate；

C02, carry out by press shaking molded for the first time, obtain idiosome；Wherein, vibration frequency is 45Hz, time of vibration 200s；

C03, gained idiosome is stripped and cut by cutter device, semi-finished product are obtained by predetermined pattern arrangement；

C04, by gained semi-finished product carry out second of cloth；

C07, shaken for the second time by press molded, vibration frequency is 50Hz, time of vibration 240s；

C08, shake for the second time it is molded after, carry out drying forming, drying temperature be 92 DEG C, drying time 1.5h；

C09, the semi-finished product to drying forming are post-processed, such as fixed thick processing, polishing, obtain finished product.

Wherein, the preparation method of the functional agent is as follows：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.01mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.5mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 3gGQDs/Ag₂O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise for 0.005mol/L Concentration is added dropwise after the cerous nitrate aqueous solution, 30min for 0.05mol/L zinc nitrate aqueous solutions, GQDs/Ag₂The O aqueous solution, nitric acid The cerium aqueous solution is 1 with zinc nitrate aqueous solution volume ratio:0.2:0.4；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Side Ultrasonic agitation, side adds the hydrazine hydrate that 6mL mass fractions are 50%, the reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL is added Mass fraction is 50% hydrazine hydrate, at 85 DEG C after reduction reaction 36h；Filtering, is washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.1gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 Water and ammoniacal liquor, are stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂O/Ag-Zn-Ce mass ratio is 3:2）, adjust pH value For 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 60min；Progress, which is centrifuged and cleaned successively with acetone and deionized water, is sunk Form sediment；This is deposited at 90 DEG C and dries 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂It is placed under argon gas atmosphere and carries out 600 DEG C of heat treatment 1h, is cooled to after room temperature, is immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 15min is carried out, the local silica in surface is removed, centrifuges and dry, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

（5）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In the aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:1；50W ultrasounds 100min, is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 8 times （Pumpdown time is 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

（6）Prepare deodorant：Mix the raw material of following percentage by weight：ZrO₂8%, TiO₂10%, SiO₂18%, V₂O₅ 2%, K₂O 5%, SnO₂1%, Cr₂O₃5%, Al₂O₃10%, Fe₂O₃12%, MgO 16%, Na₂O 3%, MnO₂ 10%, put into It is ground in the big flow circulation horizontal sand mill of PUHLER companies exploitation, control particle diameter obtains inorganic between 10 ~ 300nm Oxide；Diatomite is dispersed in the 100 ~ 200ml aqueous solution, add inorganic oxide, wherein the diatomite with it is inorganic The weight ratio of oxide is 1:6,150W ultrasound 150rpm stir 2h, allow nano material well into diatom soil pores, repeatedly Suction filtration is cleaned；It is placed in confined space, progress vacuumizes → heated pressurized circulation 5 times（Pumpdown time is 30min；Heating adds Press to be passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain deodorant；

（7）Antibacterial powder and deodorant is taken to be scattered in 150ml ultra-pure waters, ultrasonic agitation 2h obtains the scattered of uniform stabilization The weight ratio of liquid, wherein antibacterial powder and deodorant is 5:2；When substrate with carbon nanotube mesh film is placed in into about 8 DEG C, it will divide Dispersion liquid is added in the substrate of concave shape, meanwhile, roller is rolled around, the homogeneous dispersion is scattered in the carbon nanotube mesh In film, due to having hydrophily when CNT is near 8 DEG C, the dispersion liquid is attracted to multiple nets of carbon nanotube mesh film Hole；About 25 DEG C are warming up to, CNT, which has hydrophobicity and drives most of moisture away, leaves absorption in carbon nanotube mesh Antibacterial powder and deodorant in multiple net holes of film；Remove moisture, be placed in confined space, progress vacuumize → heat pressurized circulation 4 times（Pumpdown time is 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, the carbon nanotube mesh film for being adsorbed with antibacterial powder and deodorant is then scraped off into the substrate, resisted Bacterium-deodorization functions agent.

Embodiment 4

Based on the preparation method of embodiment 1, it the difference is that only：The antibacterial powder is made by the following method：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.001mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.1mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 1gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise for 0.5g/100mlZnO amounts The son point aqueous solution, ultrasonic power mixing speed respectively halves；After 60min, stand, filtering is washed with deionized for several times, and vacuum is done It is dry, obtain GQDs/Ag₂O/ZnO；

（4）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂O/ZnO weight ratio is 1:5；50W ultrasound 100min, stand, deionized water For several times, centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 3 times for washing（Pumpdown time is 25min；Plus Heat, which is pressurised into, is passed through high temperature and high pressure gas, and gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Embodiment 5

Based on the preparation method of embodiment 2, it the difference is that only：The antibacterial powder is made by the following method：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.005mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.2mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 2gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise for 0.2g/100mlZnO amounts The son point aqueous solution, ultrasonic power mixing speed respectively halves；After 80min, stand, filtering is washed with deionized for several times, and vacuum is done It is dry, obtain GQDs/Ag₂O/ZnO；

（4）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂O/ZnO weight ratio is 1:3；50W ultrasound 100min, stand, deionized water For several times, centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 5 times for washing（Pumpdown time is 25min；Plus Heat, which is pressurised into, is passed through high temperature and high pressure gas, and gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Embodiment 6

Based on the preparation method of embodiment 3, it the difference is that only：The antibacterial powder is made by the following method：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.01mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.5mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 3gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise for 0.05g/100mlZnO amounts The son point aqueous solution, ultrasonic power mixing speed respectively halves；After 90min, stand, filtering is washed with deionized for several times, and vacuum is done It is dry, obtain GQDs/Ag₂O/ZnO；

（4）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂O/ZnO weight ratio is 1:1；50W ultrasound 100min, stand, deionized water For several times, centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 8 times for washing（Pumpdown time is 25min；Plus Heat, which is pressurised into, is passed through high temperature and high pressure gas, and gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Comparative example 1

Based on the preparation method of embodiment 1, difference is：The antibacterial powder is metal antibacterial agent；The deodorant By ZrO₂8%, TiO₂10%, SiO₂18%, V₂O₅2%, K₂O 5%, SnO₂1%, Cr₂O₃5%, Al₂O₃10%, Fe₂O₃12%, MgO 16%, Na₂O 3%, MnO₂ 10%（Percentage by weight）Mix；Without bamboo charcoal nano.

Comparative example 2

Based on the preparation method of embodiment 4, difference is：The antibacterial powder is zinc oxide antiseptic；Without except Smelly dose.

Performance test is carried out to embodiment 1 ~ 6, comparative example 1 ~ 2, test result is as follows：

Wear testing：From the abrasive material that Mohs' hardness is 3~4, rubbed on bionical quartz for 1000 times and imitate paving Using the effect after 2 years, its sterilization rate is tested.

Heat stability testing：Bionical quartz is placed in electric furnace, 200 DEG C are raised to from room temperature, 20min is incubated, it is rapid to throw Enter in 25 DEG C of water, take out and dry after 10min, test its sterilization rate.

Sterilize Evaluation for Uniformity：100 regions are chosen on same bionical quartz and carry out sterilizing test, to the number measured According to Uniformity Analysis is carried out, pass through the uniformity=100* (1- standard deviations/average value).When the uniformity is more than 97%, then it is labeled as ▲；When the uniformity is more than 90% and less than 97%, then labeled as ☆；When the uniformity is less than 90%, then Biao Ji Wei ╳.

Deodorizing test：Prepare two 51PVF resin airbags, one piece of sample print is put into an air bag, another tree Fat air bag not setting-out piece.Then 500ppmNH3- air gas mixtures are blown into respectively in two air bags and are sealed, 120min makes The concentration of NH3 in air bag is measured with gas detecting tube, deodorizing rate is calculated.

Air purification effect experiment is as follows：Contrast is using front and rear indoor concentration of formaldehyde and electromagnetic radiation etc., to characterize it Adsorption capacity.Between one in 10 square metres of vacant room, following article is placed：1. make furniture 10, clamping plate, surface without Packaging；2. 5 barrels are painted, bung is opened；3. television set 1, opening；4. electric fan 1, opening.

Radiate performance：Detection indicate that, quartz prepared by the present invention meets GB6566-2001《Construction material is radiated Property radionuclides limitation》Middle A classes finishing material requirement.

Embodiment described above only expresses embodiments of the present invention, and it describes more specific and detailed, but can not Therefore the limitation to the scope of the claims of the present invention is interpreted as, as long as the skill obtained using the form of equivalent substitution or equivalent transformation Art scheme, all should fall within the scope and spirit of the invention.

Claims (3)

1. a kind of preparation method of the bionical quartz of radiation proof, it comprises the following steps：

Step A, prepares modified resin：By weight percentage, it is 85 ~ 90% resins, 4 ~ 8% functional agents and 1 ~ 5% dispersant is high Melting is heated after fast mixer is well mixed, using double screw extruder extruding pelletization, its melting mixing disperses extrusion temperature and is： 100 DEG C~280 DEG C；The functional agent includes deodorant and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder；

Step B, by weight percentage, by 80 ~ 90% quartz, 8 ~ 12% modified resins, 0.01 ~ 1% curing agent, 0.01 ~ 1% coupling Agent, 1 ~ 5% bamboo charcoal nano, 1 ~ 3% aluminium hydrate powder and 0.1 ~ 2% colorant stir, and obtain compound；The bamboo charcoal nano is grain Bamboo charcoal nano of the footpath between 100 ~ 500nm；

Step C, carries out first time cloth in template by compound, shakes molded, be stripped, and cutting is arranged by predetermined pattern Semi-finished product；Second of cloth is carried out again, is shaken molded, and then drying forming carries out post-processing to obtain finished product；

The preparation method of the functional agent is as follows：

（1）0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 500 ~ 600rpm speed, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, instead Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, is then dialysed 3 ~ 5 days, obtained for 1000 bag filter with molecular cut off GQDs suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiates 30 ~ 60min, laser irradiation power is 0.5~2W；It is standby；

（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；Dropwise plus Enter concentration for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates, 10 ~ 20min of ultrasonic agitation；0.5 ~ 1mol/L hydroxides are added dropwise Sodium solution, regulation pH value to 11 is then stood, centrifuged, and with deionized water and ethanol alternately washing three times, vacuum drying is obtained GQDs/Ag₂O；

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in 80 ~ 120ml aqueous solution；Be added dropwise concentration for 0.005 ~ Concentration is added dropwise after the 0.05mol/L cerous nitrate aqueous solution, 30 ~ 60min for 0.005 ~ 0.05mol/L zinc nitrate aqueous solutions；After Continuous ultrasonic agitation, regulation mixed solution pH value to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8mL mass fractions are 50%, 0.5 ~ 1h of reduction reaction at 30 ~ 40 DEG C；Afterwards, the hydrazine hydrate that 40 ~ 50mL mass fractions are 50% is added, at 85 DEG C also After 30 ~ 48h of original reaction；Filtering, is washed with deionized for several times, and vacuum drying obtains GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 3 ~ 5 is added afterwards:1 Water and ammoniacal liquor, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reaction 30 ~ 60min；Progress is centrifuged and cleaned successively with acetone and deionized water and precipitated；This is deposited at 80 ~ 90 DEG C and dries 2 ~ 4h, To obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Be placed under argon gas atmosphere carry out 500 ~ 800 DEG C heat treatment 1 ~ 2h, be cooled to after room temperature, be immersed in hydrofluoric acid with 100 ~ 150W of ultrasonic power carry out ultrasound 10 ~ 15min, removes the local silica in surface, centrifuges and dry, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

（5）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn-Ce/ SiO₂In the aqueous solution；10 ~ 100W, 60 ~ 120min of ultrasound, are stood, and deionized water is washed for several times, and centrifugation is placed in confined space, Progress vacuumizes → heated pressurized circulation 3 ~ 8 times, obtains GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder；

（6）Antibacterial powder and deodorant is taken to be scattered in 100 ~ 200ml ultra-pure waters, 2 ~ 3h of ultrasonic agitation obtains point of uniform stabilization The weight ratio of dispersion liquid, wherein antibacterial powder and deodorant is 3 ~ 5:2~4；When substrate with carbon nanotube mesh film is placed in into 8 DEG C, In the substrate that dispersion liquid is added to concave shape, meanwhile, roller is rolled around, the homogeneous dispersion is scattered in the CNT In reticular membrane, due to having hydrophily when CNT is near 8 DEG C, the dispersion liquid is attracted to many of carbon nanotube mesh film Individual net hole；25 DEG C are warming up to, CNT, which has hydrophobicity and drives most of moisture away, leaves absorption in carbon nano-tube network Antibacterial powder and deodorant in multiple net holes of shape film；Remove moisture, be placed in confined space, progress vacuumizes → heated pressurization and follows Ring 3 ~ 5 times, then scrapes off the substrate by the carbon nanotube mesh film for being adsorbed with antibacterial powder and deodorant, obtains antibacterial-deodorization work( Can agent；

The preparation method of the deodorant is as follows：Mix the raw material of following percentage by weight：ZrO₂2 ~ 8%, TiO₂5 ~ 15%, SiO₂10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 5%, Al₂O₃10 ~ 15%, Fe₂O₃10 ~ 15%, MgO 10 ~ 20%, Na₂O 1 ~ 10%, MnO₂ 1 ~ 10%, put into the big flow circulation horizontal sand mill of PUHLER companies exploitation and carry out Grinding, control particle diameter obtains inorganic oxide between 10 ~ 300nm；Diatomite is dispersed in the 100 ~ 200ml aqueous solution, plus Enter inorganic oxide, wherein the weight ratio of the diatomite and inorganic oxide is 1:100 ~ 300rpm of 1 ~ 6,100 ~ 200W ultrasound 1 ~ 2h is stirred, allows nano material well into diatom soil pores, multiple suction filtration is cleaned；It is placed in confined space, progress is taken out true Sky → heating pressurized circulation 3 ~ 8 times, obtains deodorant；

The three-dimensional sponge shape graphene preparation method is as follows：By 3g graphite powders, 1g NaNO₃With 250ml 98% in ice-water bath The concentrated sulfuric acid is well mixed, and is slowly added to 6g KMnO₄；Then heat at 35 DEG C, after stirring 40min, add 95ml deionizations Water, is warming up to 98 DEG C of reaction 20min；The dilution of 270ml water is added, and with the H of 5ml 30%₂O₂Neutralize unnecessary KMnO₄, mixing The color of solution is brown color, is filtered while hot, with deionized water cyclic washing to neutrality, ultrasonic disperse obtains GO；Take 200ml Mass fraction is poured into diameter 25cm, high 2cm discoid reaction utensil for 5mg/ml graphene oxide solution, adds Vitamin C Acid (VC) 0.5g stirrings are sufficiently mixed it；Then confined reaction ware is placed in the oxidation in 80 DEG C of hydro-thermal reaction 15h, reaction utensil Graphene Spontaneous Contraction is cross-linked into three-dimensional sponge structure, freeze-drying, obtains the three-dimensional sponge shape graphene of flexibility.

2. a kind of preparation method of the bionical quartz of radiation proof, it comprises the following steps：

Step A, prepares modified resin：By weight percentage, it is 85 ~ 90% resins, 4 ~ 8% functional agents and 1 ~ 5% dispersant is high Melting is heated after fast mixer is well mixed, using double screw extruder extruding pelletization, its melting mixing disperses extrusion temperature and is： 100 DEG C~280 DEG C；The functional agent includes deodorant and GQDs/Ag₂O/ZnO/ Graphene antibiosis powder；

Step B, by weight percentage, by 80 ~ 90% quartz, 8 ~ 12% modified resins, 0.01 ~ 1% curing agent, 0.01 ~ 1% coupling Agent, 1 ~ 5% bamboo charcoal nano, 1 ~ 3% aluminium hydrate powder and 0.1 ~ 2% colorant stir, and obtain compound；The bamboo charcoal nano is flat 100 ~ 500nm of equal particle diameter bamboo charcoal nano；

Step C, carries out first time cloth in template by compound, shakes molded, be stripped, and cutting is arranged by predetermined pattern Semi-finished product；Second of cloth is carried out again, is shaken molded, and then drying forming carries out post-processing to obtain finished product；

The preparation method of the functional agent is as follows：

（1）0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 500 ~ 600rpm speed, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, instead Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, is then dialysed 3 ~ 5 days, obtained for 1000 bag filter with molecular cut off GQDs suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiates 30 ~ 60min, laser irradiation power is 0.5~2W；It is standby；

（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；Dropwise plus Enter concentration for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates, 10 ~ 20min of ultrasonic agitation；0.5 ~ 1mol/L hydroxides are added dropwise Sodium solution, regulation pH value to 11 is then stood, centrifuged, and with deionized water and ethanol alternately washing three times, vacuum drying is obtained GQDs/Ag₂O；

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise for 0.05 ~ 0.5g/100mlZnO The quantum dot aqueous solution, ultrasonic power mixing speed respectively halves；After 60 ~ 90min, stand, filtering is washed with deionized for several times, Vacuum drying, obtains GQDs/Ag₂O/ZnO；

（4）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂In the O/ZnO aqueous solution； 10 ~ 100W, 60 ~ 120min of ultrasound, are stood, and deionized water is washed for several times, and centrifugation is placed in confined space, and progress is vacuumized → added Hot pressurized circulation 3 ~ 8 times, obtains GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder；

（5）Antibacterial powder and deodorant is taken to be scattered in 100 ~ 200ml ultra-pure waters, 2 ~ 3h of ultrasonic agitation obtains point of uniform stabilization The weight ratio of dispersion liquid, wherein antibacterial powder and deodorant is 3 ~ 5:2~4；When substrate with carbon nanotube mesh film is placed in into 8 DEG C, In the substrate that dispersion liquid is added to concave shape, meanwhile, roller is rolled around, the homogeneous dispersion is scattered in the CNT In reticular membrane, due to having hydrophily when CNT is near 8 DEG C, the dispersion liquid is attracted to many of carbon nanotube mesh film Individual net hole；25 DEG C are warming up to, CNT, which has hydrophobicity and drives most of moisture away, leaves absorption in carbon nano-tube network Antibacterial powder and deodorant in multiple net holes of shape film；Remove moisture, be placed in confined space, progress vacuumizes → heated pressurization and follows Ring 3 ~ 5 times, then scrapes off the substrate by the carbon nanotube mesh film for being adsorbed with antibacterial powder and deodorant, obtains antibacterial-deodorization work( Can agent；

The preparation method of the deodorant is as follows：Mix the raw material of following percentage by weight：ZrO₂2 ~ 8%, TiO₂5 ~ 15%, SiO₂10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 5%, Al₂O₃10 ~ 15%, Fe₂O₃10 ~ 15%, MgO 10 ~ 20%, Na₂O 1 ~ 10%, MnO₂ 1 ~ 10%, put into the big flow circulation horizontal sand mill of PUHLER companies exploitation and carry out Grinding, control particle diameter obtains inorganic oxide between 10 ~ 300nm；Diatomite is dispersed in the 100 ~ 200ml aqueous solution, plus Enter inorganic oxide, wherein the weight ratio of the diatomite and inorganic oxide is 1:100 ~ 300rpm of 1 ~ 6,100 ~ 200W ultrasound 1 ~ 2h is stirred, allows nano material well into diatom soil pores, multiple suction filtration is cleaned；It is placed in confined space, progress is taken out true Sky → heating pressurized circulation 3 ~ 8 times, obtains deodorant；

The three-dimensional sponge shape graphene preparation method is as follows：By 3g graphite powders, 1g NaNO₃With 250ml 98% in ice-water bath The concentrated sulfuric acid is well mixed, and is slowly added to 6g KMnO₄；Then heat at 35 DEG C, after stirring 40min, add 95ml deionizations Water, is warming up to 98 DEG C of reaction 20min；The dilution of 270ml water is added, and with the H of 5ml 30%₂O₂Neutralize unnecessary KMnO₄, mixing The color of solution is brown color, is filtered while hot, with deionized water cyclic washing to neutrality, ultrasonic disperse obtains GO；Take 200ml Mass fraction is poured into diameter 25cm, high 2cm discoid reaction utensil for 5mg/ml graphene oxide solution, adds Vitamin C Acid (VC) 0.5g stirrings are sufficiently mixed it；Then confined reaction ware is placed in the oxidation in 80 DEG C of hydro-thermal reaction 15h, reaction utensil Graphene Spontaneous Contraction is cross-linked into three-dimensional sponge structure, freeze-drying, obtains the three-dimensional sponge shape graphene of flexibility.

3. a kind of bionical quartz of radiation proof, it is characterised in that be made by preparation method as claimed in claim 1 or 2.