CN106587656A - Novel high wear-resisting glass and preparation method thereof - Google Patents

Novel high wear-resisting glass and preparation method thereof Download PDF

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Publication number
CN106587656A
CN106587656A CN201611153228.XA CN201611153228A CN106587656A CN 106587656 A CN106587656 A CN 106587656A CN 201611153228 A CN201611153228 A CN 201611153228A CN 106587656 A CN106587656 A CN 106587656A
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glass
diamond alkene
nanometer diamond
cleaning
novel high
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Inventor
郭留希
赵清国
杨晋中
武艳强
刘永奇
刘创勋
邵静茹
李盟
尹维召
穆小娜
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Zhengzhou Synthetic Diamond and Products Engineering Technology Research Center Co Ltd
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Zhengzhou Synthetic Diamond and Products Engineering Technology Research Center Co Ltd
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Priority to CN201611153228.XA priority Critical patent/CN106587656A/en
Publication of CN106587656A publication Critical patent/CN106587656A/en
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/70Properties of coatings
    • C03C2217/78Coatings specially designed to be durable, e.g. scratch-resistant

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

Disclosed is a novel high wear-resisting glass. The novel high wear-resisting glass comprises a glass base material layer and an ETFE layer and a nano diamond alkene layer are arranged on the surface of the glass base material in sequence. The preparation method includes the following steps: (1) firstly, glass base material surface is cleaned; (2) secondly, a layer of ETFE emulsion is sprayed on the surface of the glass base material and is dried and therefore the glass base material with an ETFE layer is obtained; (3) then, nano diamond alkene emulsion is sprayed on the ETFE layer and is dried and therefore the novel high wear-resisting glass is obtained. By the adoption of the nano diamond alkene coating, the glass light transmittance is capable of being increased and the visual effect is good; glass hardness and wear resistance are enhanced and service life is prolonged. Besides, there is no need to paste a layer of organic membrane to protect and therefore environmental pollution is reduced; glass rigidity can be increased and therefore the glass is not prone to deformation, service life is prolonged, original glass basal body thickness is decreased, the manufacturing cost is saved; no toxic side effect on a human body is caused. Application range is wide.

Description

A kind of novel high wear-resistant glass and preparation method thereof
Technical field
The invention belongs to glass surface Wear-resistant Treatment technology field, and in particular to a kind of new containing nanometer diamond alkene High abrasion glass.
Background technology
Glass belongs to silicate nonmetallic materials, and its chemical composition is Na2O·CaO·6SiO2, main component is SiO2, Belong to mixture, be at normal temperatures a kind of transparent solid, melting when formed contiguous network structure, in cooling procedure viscosity by Cumulative big and hardening and do not crystallize.Glass types are various, be such as mixed into some metal-oxides or salt can be made into and manifest color Coloured glass, or by safety glass obtained in specific process, or add some transparent plastics (such as polymethylacrylic acid third Ester) lucite is obtained.The glass-enclosed building of these huge numbers, automotive windshield, mobile phone display screen, computer display screen, electronics The fields such as display screen are widely used.
With the development of information technology and flat panel display technology, a variety of display screens all occupy weight in industry-by-industry The status wanted, being especially even more in the electronic products such as smart mobile phone, panel computer, light-emitting diode display has particularly important work With with the continuous improvement of intelligence degree, touch screen has become the first-selected display screen of various electronic products.With regard to touch screen Speech, touch screen is the outermost protection original paper of glass material display, typically all using the ultra-thin glass of 1 below mm, but people While the benefit that ultra-thin glass brings is enjoyed, be also subjected to the various drawbacks of ultra-thin glass, such as poor mechanical property is held Easily it is scratched, it is not wear-resisting etc., it is that this people often pastes the organic pad pasting of one layer of PE or tempering on Mobile phone screen or various display screen surfaces Film carrys out protect the substrate glass, although can play certain protective effect, but the protecting film is not reproducible to be used, service life It is short, in batches using substantial amounts of solid waste can be caused, pollution is also resulted in environment.
The content of the invention
It is an object of the invention to provide a kind of novel high wear-resistant glass, while it is the another of the present invention to provide its preparation method Goal of the invention.
Based on above-mentioned purpose, following technical scheme is this invention takes:
A kind of novel high wear-resistant glass, including glass substrate layer, the glass substrate surface sets gradually ETFE layers and nanometer is bored Stone alkene layer.
The glass baseplate is the thick corning glasss of 0.7mm, and the thickness of the ETFE layers is 5-10 μm, nanometer diamond alkene layer Thickness be 1-20 μm.
The preparation method of described novel high wear-resistant glass, comprises the following steps:
1) first to glass substrate surface cleaning treatment;
2) again in glass substrate surface one layer of ETFE emulsion of spraying, drying obtains the glass baseplate containing ETFE layers;
3) after again on ETFE layers spray nanometer diamond alkene emulsion, drying novel high wear-resistant glass.
Step 1) in the concrete operations of cleaning treatment be:
I) first adopt the impregnated absorbent cotton cleaning glass window substrate surface in the mixed liquor of Chalk, ethanol and ammonia;
II) glass baseplate ultrasound to be washed, supersonic frequency is 45-60KHz, and washing time is 1-5min;
III) glass baseplate after ultrasonic cleaning is put into in the NaOH solution that concentration is 10% ultrasonic alkali cleaning, supersonic frequency is 45- 60KHz, alkali cleaning temperature is 50-60 DEG C, and the alkali cleaning time is 1-5min;
IV) the glass baseplate twice ultrasonic after alkali cleaning to be washed, supersonic frequency is 45-60KHz, and washing time is 1-5min, water Temperature is 50-60 DEG C;
V) ultrasound washing again, supersonic frequency is 45-60KHz, and washing time is 1-5min, and water temperature is room temperature;
VI) glass baseplate after ultrasound washing again to be inserted in acetone soln and supersound process, supersonic frequency is 45-60KHz, Take out after process time 1-5min and remove acetone.
Step 2) and step 3) in drying temperature be 100 DEG C, the time is 4-12h.
Step 3) in the percentage by weight of nanometer diamond alkene emulsion consist of:Politef concentrated solution 90-95%, polyphenyl Ester 4.9-9.9%, modified Nano diamond alkene 0.1-5%;Also include sodium lauryl sulphate in the nanometer diamond alkene emulsion and disappear Infusion 7010, the consumption of the sodium lauryl sulphate is politef concentrated solution and modified Nano diamond alkene consumption sum 0-2%, the consumption of defoamer 7010 is the 0-0.2% of politef concentrated solution and modified Nano diamond alkene consumption sum, described The solid content of politef concentrated solution is 60%, and 25 DEG C of kinematic viscositys are 6-15mm2/ s, 20 DEG C of density are 1.5-1.55g/cm3, Granularity 20-30 μm of polybenzoate;
The preparation process of nanometer diamond alkene emulsion is:First politef concentrated solution is poured in beaker, starts stirring, stirring turns Speed is 10-20rpm, sequentially adds load weighted polybenzoate, modified Nano diamond alkene, sodium lauryl sulphate and stirs, it Beaker is put in the water-bath that water temperature is 50 DEG C afterwards continues to stir 30min, and it is outer to add defoamer 7010 to be mixed to get therewith It is uniform without stratification state in sight state.
The modified Nano diamond alkene is specifically obtained by nanometer diamond alkene through pre-treatment and modification, pre-treatment Method is
I) stir mixing
Varigrained nanometer diamond alkene is poured in three-dimensional material mixer carries out batch mixing, and mixing time is controlled in 5min~30min;
II) ultrasound wave alkali cleaning
Nanometer diamond alkene is put into in alkali wash water ultrasonic alkali cleaning and Stirring, supersonic frequency is 30~40KHz, and alkali wash water is dense Degree 10%-15% NaOH solution, alkali cleaning liquid temp be 45~55 DEG C, rotary rpm be 25~35rpm, scavenging period be 25~ 35min;
III) ultrasound wave cleaning
Nanometer diamond alkene after alkali cleaning is placed in deionized water the washing of room temperature ultrasound and Stirring, and supersonic frequency is 30~ 35KHz, rotary rpm is 15~25rpm, and mixing time is 20~25min, measures supernatant pH value, and repeatedly cleaning is until upper Layer clear liquid pH=7;
IV) acid-wash activation
Nanometer diamond alkene after ultrasonic cleaning is put into into room temperature ultrasound pickling and Stirring in pickle, pickle is volume ratio 1:10 concentrated hydrochloric acid and concentrated sulphuric acid mixed liquor, rotary rpm is 10~15rpm, and mixing time is 10~15min;
V) ultrasonic wave water washing
Nanometer diamond alkene after acid-wash activation is placed in in deionized water the washing of room temperature ultrasound and Stirring again, supersonic frequency For 30~35KHz, rotary rpm is 15~25rpm, and mixing time is 10~15min, and repeatedly cleaning is until supernatant pH=7;
VI) drying
Stoving process is carried out using staged baking process, and room temperature is warming up to 70 DEG C, and constant temperature insulation 30min is warming up to 90 DEG C, perseverance Temperature insulation 30min, is warming up to 120 DEG C, and constant temperature insulation 3h naturally cools to room temperature stand-by;Adopt when heating up in whole process Heating rate is 2 DEG C/min;
The method of modification is:
A) pH value of ethanol water is adjusted with glacial acetic acid to 4-4.5, the KH550 that mass fraction is 3% is added under stirring condition Silane coupler, speed of agitator is 10-20rpm, and mixing time is 35-45min, obtains KH550 silane coupler pre-hydrolyzed solutions, institute It is 9 to state ethanol and the mass ratio of water in ethanol water:1, mass fraction is 3% KH550 silane couplers and ethanol water Amount ratio be 1:1;
B) under 55-65 DEG C, speed of agitator are for 30-50rpm, the nanometer diamond alkene to the pre-treatment that mass fraction is 15% is suspended Deca KH550 silane coupler pre-hydrolyzed solution in liquid, then stirs 25-35min, then ultrasonic disperse 5-15min, stands 25- 35min;The dripping quantity of KH550 silane coupler pre-hydrolyzed solutions is the 5% of the weight of nanometer diamond alkene;
C) vacuum filtration, dry, grind to obtain modified Nano diamond alkene, drying temperature is 100 DEG C, and drying time is 24h.
Compared with prior art, the beneficial effects of the present invention is:
1st, nanometer diamond ene coatings can improve the light transmittance of glass, and visual perception's effect is good;
2nd, nanometer diamond ene coatings can improve the hardness and wearability of glass, increase the service life, and without the need in its surface patch One layer of organic membrane protection, so as to reduce the pollution to environment;
3rd, nanometer diamond ene coatings can improve the rigidity of glass so that be unlikely to deform, and increase the service life, can be with thinning original glass The thickness of glass matrix, saves production cost;
4th, nanometer diamond alkene has no toxic side effect to the person, and use range is wide, can be applicable to handset touch panel, computer display screen, Electronic displayss etc..
Description of the drawings
Fig. 1 is the structural representation of novel high wear-resistant glass in the present invention;
Fig. 2 is impact of the nanometer diamond ene coatings thickness to light transmittance;
Fig. 3 is impact of the different nanometer diamond ene coatings thickness to hardness;
Fig. 4 is impact of the different nanometer diamond ene coatings thickness to elastic modelling quantity.
Specific embodiment
Hereinafter the present invention will be illustrated by embodiment, but these specific embodiments limit never in any form this Bright protection domain.
Embodiment 1
A kind of novel high wear-resistant glass, including glass substrate layer 1, the surface of the glass baseplate 1 sets gradually ETFE layers 2 and nanometer Diamond alkene layer 3.The glass baseplate 1 is the thick corning glasss of 0.7mm, and the thickness of the ETFE layers 2 is 8 μm, nanometer diamond alkene The thickness of layer 3 is 10 μm.
The preparation method of described novel high wear-resistant glass, comprises the following steps:
1) first to glass substrate surface cleaning treatment;
2) again in glass substrate surface one layer of ETFE emulsion (commercially available) of spraying, drying obtains the glass baseplate containing ETFE layers;
3) after again on ETFE layers spray nanometer diamond alkene emulsion, drying novel high wear-resistant glass.
Step 1) in the concrete operations of cleaning treatment be:
I) first adopt the impregnated absorbent cotton cleaning glass window substrate surface in the mixed liquor of Chalk, ethanol and ammonia;
II) glass baseplate ultrasound to be washed, supersonic frequency is 50KHz, and washing time is 3min;
III) glass baseplate after ultrasonic cleaning is put into in the NaOH solution that concentration is 10% ultrasonic alkali cleaning, supersonic frequency is 50KHz, alkali cleaning temperature is 55 DEG C, and the alkali cleaning time is 3min;
IV) the glass baseplate twice ultrasonic after alkali cleaning to be washed, supersonic frequency is 55KHz, and washing time is 3min, and water temperature is 55 ℃;
V) ultrasound washing again, supersonic frequency is 55KHz, and washing time is 3min, and water temperature is 25 DEG C of room temperature;
VI) glass baseplate after ultrasound washing again to be inserted in acetone soln and supersound process, supersonic frequency is 55KHz, place Take out after reason time 3min and remove acetone.
Step 2) and step 3) in drying temperature be 100 DEG C, the time is 8h.
Step 3) in the percentage by weight of nanometer diamond alkene emulsion consist of:Politef concentrated solution 95%, polybenzoate 4.9%th, modified Nano diamond alkene 0.1%;Also include sodium lauryl sulphate and defoamer 7010 in the nanometer diamond alkene emulsion, The consumption of the sodium lauryl sulphate is politef concentrated solution and the 1% of modified Nano diamond alkene consumption sum, defoamer 7010 consumption is the 0.1% of politef concentrated solution and modified Nano diamond alkene consumption sum, the politef concentration The solid content of liquid is 60%, and 25 DEG C of kinematic viscositys are 8mm2/ s, 20 DEG C of density are 1.5-1.55g/cm3, granularity 20-30 of polybenzoate μm;
The preparation process of nanometer diamond alkene emulsion is:First politef concentrated solution is poured in beaker, starts stirring, stirring turns Speed is 10rpm, sequentially adds load weighted polybenzoate, modified Nano diamond alkene, sodium lauryl sulphate and stirs, and afterwards will Beaker is put in the water-bath that water temperature is 50 DEG C and continues to stir 30min, and adds defoamer 7010 to be mixed to get outward appearance shape therewith It is uniform without stratification state in state.
The modified Nano diamond alkene is specifically obtained by nanometer diamond alkene through pre-treatment and modification, pre-treatment Method is
I) stir mixing
Varigrained nanometer diamond alkene is poured in three-dimensional material mixer carries out batch mixing, and mixing time is controlled in 5min;
II) ultrasound wave alkali cleaning
Nanometer diamond alkene is put into in alkali wash water ultrasonic alkali cleaning and Stirring, supersonic frequency is 30KHz, and alkali wash water is concentration 10% NaOH solution, alkali cleaning liquid temp is 45 DEG C, and rotary rpm is 25rpm, and scavenging period is 25min;
III) ultrasound wave cleaning
Nanometer diamond alkene after alkali cleaning is placed in the washing of room temperature ultrasound and Stirring in deionized water, and supersonic frequency is 30KHz, rotation Speed walk around for 15rpm, mixing time is 20min, supernatant pH value is measured, repeatedly cleaning is until supernatant pH=7;
IV) acid-wash activation
Nanometer diamond alkene after ultrasonic cleaning is put into into room temperature ultrasound pickling and Stirring in pickle, pickle is volume ratio 1:10 concentrated hydrochloric acid and concentrated sulphuric acid mixed liquor, rotary rpm is 10rpm, and mixing time is 10min;
V) ultrasonic wave water washing
Nanometer diamond alkene after acid-wash activation is placed in in deionized water the washing of room temperature ultrasound and Stirring again, supersonic frequency For 30KHz, rotary rpm is 15rpm, and mixing time is 10min, and repeatedly cleaning is until supernatant pH=7;
VI) drying
Stoving process is carried out using staged baking process, and room temperature is warming up to 70 DEG C, and constant temperature insulation 30min is warming up to 90 DEG C, perseverance Temperature insulation 30min, is warming up to 120 DEG C, and constant temperature insulation 3h naturally cools to room temperature stand-by;Adopt when heating up in whole process Heating rate is 2 DEG C/min;
The method of modification is:
A) pH value of ethanol water is adjusted to 4, the KH550 silane that mass fraction is 3% is added under stirring condition with glacial acetic acid Coupling agent, speed of agitator is 10rpm, and mixing time is 35min, obtains KH550 silane coupler pre-hydrolyzed solutions, and the ethanol is water-soluble Ethanol and the mass ratio of water are 9 in liquid:1, mass fraction is 3% KH550 silane couplers and the amount ratio of ethanol water is 1:1;
B) it is under 30rpm, to drip in the nanometer diamond alkene suspension of the pre-treatment that mass fraction is 15% in 55 DEG C, speed of agitator Plus KH550 silane coupler pre-hydrolyzed solutions, 25-35min, then ultrasonic disperse 5min are then stirred, stand 25min;KH550 silane The dripping quantity of coupling agent pre-hydrolyzed solution is the 5% of the weight of nanometer diamond alkene;
C) vacuum filtration, dry, grind to obtain modified Nano diamond alkene, drying temperature is 100 DEG C, and drying time is 24h.
Embodiment 2
A kind of novel high wear-resistant glass, including glass substrate layer, the glass substrate surface sets gradually ETFE layers and nanometer is bored Stone alkene layer.The glass baseplate is the thick corning glasss of 0.7mm, and the thickness of the ETFE layers is 10 μm, nanometer diamond alkene layer Thickness is 1 μm.
The preparation method of described novel high wear-resistant glass, with embodiment 1, difference is:
Step 1) in the concrete operations of cleaning treatment be:
I) first glass substrate surface is wiped using the impregnated absorbent cotton in the mixed liquor of Chalk, ethanol and ammonia;
II) glass baseplate ultrasound to be washed, supersonic frequency is 60KHz, and washing time is 1min;
III) glass baseplate after ultrasonic cleaning is put into in the NaOH solution that concentration is 10% ultrasonic alkali cleaning, supersonic frequency is 60KHz, alkali cleaning temperature is 60 DEG C, and the alkali cleaning time is 1min;
IV) the glass baseplate twice ultrasonic after alkali cleaning to be washed, supersonic frequency is 60KHz, and washing time is 1min, and water temperature is 60 ℃;
V) ultrasound washing again, supersonic frequency is 60KHz, and washing time is 1min, and water temperature is 25 DEG C of room temperature;
VI) glass baseplate after ultrasound washing again to be inserted in acetone soln and supersound process, supersonic frequency is 45KHz, place Take out after reason time 1min and remove acetone.
Step 2) and step 3) in drying temperature be 100 DEG C, the time is 4h.
Step 3) in the percentage by weight of nanometer diamond alkene emulsion consist of:Politef concentrated solution 90%, polybenzoate 5%th, modified Nano diamond alkene 5%;Also include sodium lauryl sulphate and defoamer 7010 in the nanometer diamond alkene emulsion, it is described The consumption of sodium lauryl sulphate is politef concentrated solution and the 2% of modified Nano diamond alkene consumption sum, defoamer 7010 Consumption be the 0.2% of politef concentrated solution and modified Nano diamond alkene consumption sum, the politef concentrated solution Solid content is 60%, and 25 DEG C of kinematic viscositys are 6-15mm2/ s, 20 DEG C of density are 1.5-1.55g/cm3, the granularity 20-30 μ of polybenzoate m;
The preparation process of nanometer diamond alkene emulsion is:First politef concentrated solution is poured in beaker, starts stirring, stirring turns Speed is 20rpm, sequentially adds load weighted polybenzoate, modified Nano diamond alkene, sodium lauryl sulphate and stirs, and afterwards will Beaker is put in the water-bath that water temperature is 50 DEG C and continues to stir 30min, and adds defoamer 7010 to be mixed to get outward appearance shape therewith It is uniform without stratification state in state.
The modified Nano diamond alkene is specifically obtained by nanometer diamond alkene through pre-treatment and modification, pre-treatment Method is
I) stir mixing
Varigrained nanometer diamond alkene is poured in three-dimensional material mixer carries out batch mixing, and mixing time is controlled in 30min;
II) ultrasound wave alkali cleaning
Nanometer diamond alkene is put into in alkali wash water ultrasonic alkali cleaning and Stirring, supersonic frequency is 40KHz, and alkali wash water is concentration 15% NaOH solution, alkali cleaning liquid temp is 55 DEG C, and rotary rpm is 35rpm, and scavenging period is 35min;
III) ultrasound wave cleaning
Nanometer diamond alkene after alkali cleaning is placed in the washing of room temperature ultrasound and Stirring in deionized water, and supersonic frequency is 35KHz, rotation Speed walk around for 25rpm, mixing time is 25min, supernatant pH value is measured, repeatedly cleaning is until supernatant pH=7;
IV) acid-wash activation
Nanometer diamond alkene after ultrasonic cleaning is put into into room temperature ultrasound pickling and Stirring in pickle, pickle is volume ratio 1:10 concentrated hydrochloric acid and concentrated sulphuric acid mixed liquor, rotary rpm is 15rpm, and mixing time is 15min;
V) ultrasonic wave water washing
Nanometer diamond alkene after acid-wash activation is placed in in deionized water the washing of room temperature ultrasound and Stirring again, supersonic frequency For 35KHz, rotary rpm is 25rpm, and mixing time is 15min, and repeatedly cleaning is until supernatant pH=7;
VI) drying
Stoving process is carried out using staged baking process, and room temperature is warming up to 70 DEG C, and constant temperature insulation 30min is warming up to 90 DEG C, perseverance Temperature insulation 30min, is warming up to 120 DEG C, and constant temperature insulation 3h naturally cools to room temperature stand-by;Adopt when heating up in whole process Heating rate is 2 DEG C/min;
The method of modification is:
A) pH value of ethanol water is adjusted to 4.5, the KH550 silicon that mass fraction is 3% is added under stirring condition with glacial acetic acid Alkane coupling agent, speed of agitator is 20rpm, and mixing time is 45min, obtains KH550 silane coupler pre-hydrolyzed solutions, the ethanol water Ethanol and the mass ratio of water are 9 in solution:1, mass fraction is the amount ratio of 3% KH550 silane couplers and ethanol water For 1:1;
B) it is under 50rpm, to drip in the nanometer diamond alkene suspension of the pre-treatment that mass fraction is 15% in 65 DEG C, speed of agitator Plus KH550 silane coupler pre-hydrolyzed solutions, 35min, then ultrasonic disperse 15min are then stirred, stand 35min;KH550 silane idols The dripping quantity of connection agent pre-hydrolyzed solution is the 5% of the weight of nanometer diamond alkene;
C) vacuum filtration, dry, grind to obtain modified Nano diamond alkene, drying temperature is 100 DEG C, and drying time is 24h.
Embodiment 3
A kind of novel high wear-resistant glass, including glass substrate layer, the glass substrate surface sets gradually ETFE layers and nanometer is bored Stone alkene layer.The glass baseplate is the thick corning glasss of 0.7mm, and the thickness of the ETFE layers is 5 μm, the thickness of nanometer diamond alkene layer Spend for 20 μm.
The preparation method of described novel high wear-resistant glass, difference from Example 1 is:
Step 1) in the concrete operations of cleaning treatment be:
I) first adopt the impregnated absorbent cotton cleaning glass window substrate surface in the mixed liquor of Chalk, ethanol and ammonia;
II) glass baseplate ultrasound to be washed, supersonic frequency is 45KHz, and washing time is 5min;
III) glass baseplate after ultrasonic cleaning is put into in the NaOH solution that concentration is 10% ultrasonic alkali cleaning, supersonic frequency is 45KHz, alkali cleaning temperature is 50 DEG C, and the alkali cleaning time is 5min;
IV) the glass baseplate twice ultrasonic after alkali cleaning to be washed, supersonic frequency is 45KHz, and washing time is 5min, and water temperature is 50 ℃;
V) ultrasound washing again, supersonic frequency is 45KHz, and washing time is 5min, and water temperature is room temperature;
VI) glass baseplate after ultrasound washing again to be inserted in acetone soln and supersound process, supersonic frequency is 45KHz, place Take out after reason time 5min and remove acetone.
Step 2) and step 3) in drying temperature be 100 DEG C, the time is 12h.
Step 3) in the percentage by weight of nanometer diamond alkene emulsion consist of:Politef concentrated solution 90%, polybenzoate 9.9%th, modified Nano diamond alkene 0.1%;Remaining is with embodiment 1.
The performance detection of embodiment 4:
4.1 prepare sample and test:The high abrasion glass of different nanometer diamond ene coatings thickness is prepared, preparation method is with reference to enforcement Example 1.The test of light transmittance test, hardness test and elastic modelling quantity is carried out to obtained sample.Concrete outcome is shown in Fig. 2, Fig. 3 and Fig. 4.
Transmission measurement:Tested with UV, visible light near infrared spectrometer, its principle is to send certain light intensity Light after medium, the intensity of the light of Detection wavelength, it can thus be appreciated that the wavelength has a few percent through the light of this medium.
Hardness test:Tested using micro-vickers hardness, test philosophy is the pointed solid with hard rule, not Know and pressed on solid, when vestige size and pressure that testee after hardness, pressure, the pressure of known pressure object is stayed Between can just calculate the hardness of testee,, wherein P is pressure pressure, and d is that vestige is diagonal Line length.
Elastic modelling quantity is tested:Tested with elasticity modulus test machine, with the thickness L of miking sheet glass, and counted The area S at sheet glass two ends is calculated, sheet glass two ends are fixed, apply certain pressure F, the pressure is greater than 50N, is less than 1000N, is then read out changes delta L of now length, using formula:E=(F/S)/(Δ L/L) calculates elastic modelling quantity.Elasticity Modulus is used to characterize the rigidity of material, and the bigger material that represents of elastic modelling quantity is less susceptible to deformation.
4.2 test results and analysis
4.2.1 impact of the nanometer diamond ene coatings thickness to light transmittance
Fig. 2 is impact of the different nanometer diamond ene coatings thickness to light transmittance, a in figure:0μm;b:5μm;c:10μm;d:15μm; e:20μm.It is clear from figure 2 that its light transmittance of different nanometer diamond ene coatings thickness is different, in visible wavelength model In enclosing, when within 10 μm, light transmittance increases the thickness of nanometer diamond ene coatings with the increase of nanometer diamond ene coatings thickness Plus, 90% or so is can reach, as nanometer diamond ene coatings thickness further increases, light transmittance declines, or even light transmittance is not less than Light transmittance containing nanometer diamond ene coatings, only 70% or so.
4.2.2 impact of the nanometer diamond ene coatings thickness to hardness
Fig. 3 is impact of the different nanometer diamond ene coatings thickness to hardness, from figure 3, it can be seen that with nanometer diamond ene coatings The increase of thickness its hardness also gradually increases, compared with nanometer diamond ene coatings (its hardness is about 6.8) are not contained, when nanometer is bored When the thickness of stone ene coatings reaches 10 μm, its hardness reaches 7.8, about 14.7% is improved, when nanometer diamond ene coatings thickness reaches 20 μm when, its hardness is 8.2, improves about 20.5%, and this shows to add the hardness of glass and resistance to is remarkably improved after nanometer diamond alkene layer Grit so that material is unlikely to deform in use, increases the service life.
4.2.3 impact of the nanometer diamond ene coatings thickness to elastic modelling quantity
Fig. 4 is impact of the different nanometer diamond ene coatings thickness to elastic modelling quantity.
Figure 4, it is seen that its elastic modelling quantity gradually increases with the increase of nanometer diamond ene coatings thickness, and do not contain Nanometer diamond ene coatings (its elastic modelling quantity is about 71.5) are compared, when nanometer diamond ene coatings thickness reaches 10 μm, its elasticity Modulus about 80, improves about 12%, and when the thickness of nanometer diamond ene coatings reaches 20 μm, its elastic modelling quantity is 88, is improve about 23%, this shows, nanometer diamond ene coatings can improve the rigidity of glass, extends the rub proofness of glass, improves wearability, extends Service life, it is not necessary to paste one layer of organic protective film in its surface again.

Claims (7)

1. a kind of novel high wear-resistant glass, it is characterised in that including glass substrate layer, the glass substrate surface sets gradually ETFE layers and nanometer diamond alkene layer.
2. novel high wear-resistant glass as claimed in claim 1, it is characterised in that the glass baseplate is thick healthy and free from worry of 0.7mm Glass, the thickness of the ETFE layers is 5-10 μm, and the thickness of nanometer diamond alkene layer is 1-20 μm.
3. the preparation method of the novel high wear-resistant glass described in claim 1 or 2, it is characterised in that comprise the following steps:
1) first to glass substrate surface cleaning treatment;
2) again in glass substrate surface one layer of ETFE emulsion of spraying, drying obtains the glass baseplate containing ETFE layers;
3) after again on ETFE layers spray nanometer diamond alkene emulsion, drying novel high wear-resistant glass.
4. the preparation method of novel high wear-resistant glass as claimed in claim 3, it is characterised in that step 1) in cleaning treatment Concrete operations are:
I) first adopt the impregnated absorbent cotton cleaning glass window substrate surface in the mixed liquor of Chalk, ethanol and ammonia;
II) glass baseplate ultrasound to be washed, supersonic frequency is 45-60KHz, and washing time is 1-5min;
III) glass baseplate after ultrasonic cleaning is put into in the NaOH solution that concentration is 10% ultrasonic alkali cleaning, supersonic frequency is 45- 60KHz, alkali cleaning temperature is 50-60 DEG C, and the alkali cleaning time is 1-5min;
IV) the glass baseplate twice ultrasonic after alkali cleaning to be washed, supersonic frequency is 45-60KHz, and washing time is 1-5min, water Temperature is 50-60 DEG C;
V) ultrasound washing again, supersonic frequency is 45-60KHz, and washing time is 1-5min, and water temperature is room temperature;
VI) glass baseplate after ultrasound washing again to be inserted in acetone soln and supersound process, supersonic frequency is 45-60KHz, Take out after process time 1-5min and remove acetone.
5. the preparation method of novel high wear-resistant glass as claimed in claim 3, it is characterised in that step 2)With step 3)Middle baking Dry temperature is 100 DEG C, and the time is 4-12h.
6. the preparation method of novel high wear-resistant glass as claimed in claim 3, it is characterised in that step 3)Middle nanometer diamond alkene The percentage by weight of emulsion is consisted of:Politef concentrated solution 90-95%, polybenzoate 4.9-9.9%, modified Nano diamond alkene 0.1-5%;Also include sodium lauryl sulphate and defoamer 7010, the lauryl sulphate acid in the nanometer diamond alkene emulsion The consumption of sodium is the 0-2% of politef concentrated solution and modified Nano diamond alkene consumption sum, and the consumption of defoamer 7010 is poly- The 0-0.2% of tetrafluoroethene concentrated solution and modified Nano diamond alkene consumption sum, the solid content of the politef concentrated solution is 60%, 25 DEG C of kinematic viscositys are 6-15mm2/ s, 20 DEG C of density are 1.5-1.55g/cm3, granularity 20-30 μm of polybenzoate;
The preparation process of nanometer diamond alkene emulsion is:First politef concentrated solution is poured in beaker, starts stirring, stirring turns Speed is 10-20rpm, sequentially adds load weighted polybenzoate, modified Nano diamond alkene, sodium lauryl sulphate and stirs, it Beaker is put in the water-bath that water temperature is 50 DEG C afterwards continues to stir 30min, and it is outer to add defoamer 7010 to be mixed to get therewith It is uniform without stratification state in sight state.
7. the preparation method of novel high wear-resistant glass as claimed in claim 6, it is characterised in that the modified Nano diamond alkene Specifically obtained through pre-treatment and modification by nanometer diamond alkene,
The method of pre-treatment is:
I) stir mixing
Varigrained nanometer diamond alkene is poured in three-dimensional material mixer carries out batch mixing, and mixing time is controlled in 5min~30min;
II) ultrasound wave alkali cleaning
Nanometer diamond alkene is put into in alkali wash water ultrasonic alkali cleaning and Stirring, supersonic frequency is 30~40KHz, and alkali wash water is dense Degree 10%-15% NaOH solution, alkali cleaning liquid temp be 45~55 DEG C, rotary rpm be 25~35rpm, scavenging period be 25~ 35min;
III) ultrasound wave cleaning
Nanometer diamond alkene after alkali cleaning is placed in deionized water the washing of room temperature ultrasound and Stirring, and supersonic frequency is 30~ 35KHz, rotary rpm is 15~25rpm, and mixing time is 20~25min, measures supernatant pH value, and repeatedly cleaning is until upper Layer clear liquid pH=7;
IV) acid-wash activation
Nanometer diamond alkene after ultrasonic cleaning is put into into room temperature ultrasound pickling and Stirring in pickle, pickle is volume ratio 1:10 concentrated hydrochloric acid and concentrated sulphuric acid mixed liquor, rotary rpm is 10~15rpm, and mixing time is 10~15min;
V) ultrasonic wave water washing
Nanometer diamond alkene after acid-wash activation is placed in in deionized water the washing of room temperature ultrasound and Stirring again, supersonic frequency For 30~35KHz, rotary rpm is 15~25rpm, and mixing time is 10~15min, and repeatedly cleaning is until supernatant pH=7;
VI) drying
Stoving process is carried out using staged baking process, and room temperature is warming up to 70 DEG C, and constant temperature insulation 30min is warming up to 90 DEG C, perseverance Temperature insulation 30min, is warming up to 120 DEG C, and constant temperature insulation 3h naturally cools to room temperature stand-by;Adopt when heating up in whole process Heating rate is 2 DEG C/min;
The method of modification is:
A) pH value of ethanol water is adjusted with glacial acetic acid to 4-4.5, the KH550 that mass fraction is 3% is added under stirring condition Silane coupler, speed of agitator is 10-20rpm, and mixing time is 35-45min, obtains KH550 silane coupler pre-hydrolyzed solutions, institute It is 9 to state ethanol and the mass ratio of water in ethanol water:1, mass fraction is 3% KH550 silane couplers and ethanol water Amount ratio be 1:1;
B) under 55-65 DEG C, speed of agitator are for 30-50rpm, the nanometer diamond alkene to the pre-treatment that mass fraction is 15% is suspended Deca KH550 silane coupler pre-hydrolyzed solution in liquid, then stirs 25-35min, then ultrasonic disperse 5-15min, stands 25- 35min;The dripping quantity of KH550 silane coupler pre-hydrolyzed solutions is the 5% of the weight of nanometer diamond alkene;
C) vacuum filtration, dry, grind to obtain modified Nano diamond alkene.
CN201611153228.XA 2016-12-14 2016-12-14 Novel high wear-resisting glass and preparation method thereof Pending CN106587656A (en)

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