The enhancement method of the aluminoborosilicate ultra thin substrate glass of alkali-free
Technical field
The present invention relates to a kind of glass reinforced method, particularly a kind of strengthening preparation method of ultra thin substrate glass, specifically the enhancement method of the aluminoborosilicate ultra thin substrate glass of alkali-free.
Background technology
Ultra-thin glass is relative ordinary plate glass thickness, and general thickness is thin glass at below 3mm, thickness at 1.5 mm hereinafter referred to as ultra-thin glass.But ultrathin also brings apparent drawback, that is exactly the reduction of mechanical strength.While reduction weight, reduction volume, the negative factor of impurity, defect and any reduction strength of glass all can be exaggerated.Such as: a slight crackle or defect for general thickness glass a just inappreciable flaw on the surface, relative to ultra-thin glass, onesize crackle but may go deep into inside glass, its intensity is caused to the destruction that cannot ignore.This directly causes ultra-thin glass and lag significantly behind common sheet glass on the mechanical performance index such as folding strength, surface hardness, and this brings huge obstruction to the practical application of ultra-thin glass.From the sixties in last century Kistler, it is found that the method by chemical tempering (i.e. ion-exchange) by unremitting research, the mechanical property of ultra-thin glass can get a qualitative improvement.Ultra-thin glass after chemical tempering exists: (1) electronics and information industry flat-panel monitor base plate glass; (2) the masked glass of clock and watch, instrument and automobile instrument glass, industrial alike holographic plate-making glass, camera cover sheet glass; (3) solar electrical energy generation base plate glass, protecting solar cell cover plate glass; (4) duplicating machine, facsimile recorder and all kinds of encoder glass; (5) microscope, medical glass; (6) the six large industrial circles such as Industrial materials admixtion scale glass have outstanding economy, scientific research value.
Display device is as the glass substrate of LCD, OLED, touch-screen etc. and protective glass; its performance (as surfaceness, angularity, optical transmittance, thermostability and mechanical strength etc.) requires higher; they should have the ultrathin being less than 1.1mm, because mobile phone, MP3, notebook etc. have the thickness of glass substrate of small-medium size display device generally at below 0.7mm.Require that these portability electronic products have good shock resistance in recent years, use accidentally break display screen to prevent people, this makes tempering enhancement process with regard to needing to the glass substrate of these electronical display products.At present, the tempering of glass mainly contains physical toughened and chemical tempering two class.Chemical tempering is mainly the ion exchange method of Nitrates.Physical toughenedly mainly contain that air is air-cooled, particulate tempering, mist tempering method etc.But with physical toughened glassy phase ratio, the chemically toughened glass production cycle long (swap time reaches tens of hours), efficiency is low and production cost is high, and (fused salt can not recycle, and purity requirement is high), fragment and simple glass similar, poor stability, and its unstable properties (chemical stability is bad), the physicals such as physical strength and resistance to impact shock is easy to disappear, and the decay of intensity time is very fast.The advantage of wind-cooling reinforcing is that cost is lower, and output is comparatively large, has higher physical strength, resistance to sudden heating, and outside Air quench hardening glass decapacitation enhance mechanical strength, can form small shreds when fragmentation, can alleviate the injury to human body.But there is certain requirement (the glass minimum thickness of home equipment institute tempering is generally at about 3 mm) to the thickness of glass and shape, and speed of cooling is slower, energy consumption is high, for thin glass, also there is the problem of glass deformation in toughening process, cannot require to apply in higher field in optical quality.The glass of current air tempering is multiplex on automobile, naval vessel, buildings.Particulate tempering novel process is compared with traditional air hardening steel metallization processes.The cooling of heat-eliminating medium can be large, is suitable for tempering ultra-thin glass.But the heat-eliminating medium cost of particulate steel process is higher.Be suitable for high strength, high-precision thin glass and ultra-thin glass.Mist tempering method heat-eliminating medium is easy to get, and cost is low, free from environmental pollution, also can tempering general gas flow, liquid and particulate tempering can not the thin glass of tempering.But the more difficult control of cooling uniformity, application is less at present.
At present, the domestic and international patent about the strengthening of glass is less.CN1843988 relates to a kind of production technique of physical toughened thin glass, belongs to toughened glass processing technique field.Pretreated thin parison is mainly placed in film releasing section by it, then heating zone heating is entered, enter sectional type quenching section fast and carry out instantaneous pressure air chilling, again by low-power fan with blower fan air grid carries out reciprocating cooling until normal temperature after high pressure chilling, obtain toughened glass finished product.The type of heating of tempering of the present invention can realize homogeneity, and it is full and uniform that the application of steel watt heat balance device in process furnace can realize furnace temperature; The type of drive of thin glass tempering is steadily reliable, can guarantee the steady, flexible, reliable of transmission; Can realize thin thickness of glass is: the tempering of 2mm ~ 3mm; Energy-conservation (economize on electricity) more than 2/3rds can be reached; 4/5ths are reduced than the noise of conventional steel gasifying device, can not be affected by noise when workman operates at the scene, be conducive to environmental protection.CN1843989 relates to a kind of quenching unit for physical toughened thin glass, specifically produces the thin glass of 2 ~ 3mm for horizontal roller formula tempering unit, belongs to toughened glass processing technique field.It mainly adopts high pressure air grid, blower fan air grid connects quenching section, air compressor machine connecting tube respectively, is connected, fan connecting tube road, is connected by pipeline with blower fan air grid by pipeline with high pressure air grid.This invention structure is simple, compact; Owing to adopting the sectional type quenching section of high-pressure air, high pressure air grid and blower fan air grid segmentation composition, first quenching is continued until normal temperature by low-power fan air grid again to hot glass instantaneous pressure quenching by high pressure air grid, the tempering of thin glass can be realized; Energy-conservation (economize on electricity) more than 2/3rds of energy; Reduce 4/5ths than the noise of conventional steel gasifying device, workman operates at the scene can not be affected by noise, is conducive to environmental protection.CN1935715 discloses a kind of method of producing thin tempering glass, and it is that dry ice particle and pressurized air are entered air grid as heat-eliminating medium by mixing tank, the glass surface then after jet impact to heating.The features such as dry ice used in this invention has lower, the easy distillation of temperature, thermal capacitance is high, security is good, which overcome liquid medium tempering method and particulate tempering method operationally with the difficult point of economic aspect, it is simple, convenient and economical, pollution-free to use, the gaseous state CO produced due to heat exchange in toughening process
2can be disposed in air by negative pressure device.Dry ice particle used can be produced with carbon dioxide ice maker, does not need a large amount of deposit.It is the thin glass reinforced of 2-3mm that above patent only can be used for thickness, also cannot strengthen for the ultra-thin glass of thickness at about 0.5mm.
Make a general survey of above document, according to the service requirements of ultra-thin glass, if adopt chemical enhanced method to strengthen, the high aluminium borosilicate glass this method for the widespread use of alkali-free metal in glass composition to realize; Simultaneously, if strengthened with the thin glass of chemical enhanced method to alkali metal containing, because " jammed " is to the large radius ion of glass surface, compromise glass surface on the one hand, cause certain influence to the chemical stability of glass on the other hand, the glass applications of this method strengthening is restricted.If adopt the method for conventional air-cooled strengthening to strengthen ultra-thin glass, according to reinforcement theory, it is invalid that the glass surface that will be less than 0.7mm at thickness forms stress, and particulate tempering has major injury to glass surface.At present, the correlative study about the strengthening of the aluminoborosilicate ultra thin substrate glass to alkali-free is not reported.
Summary of the invention
The present invention, in order to overcome the defect of above-mentioned prior art, devises the method for strengthening aluminiu-boron silicate glass without alkali, and the toughened glass stress distribution utilizing present method obtained is even, and excellent in cushion effect, glass surface is in good condition, tempering excellent effect.
The technical solution used in the present invention is: the enhancement method of the aluminoborosilicate ultra thin substrate glass of alkali-free, and for being strengthened by the base plate glass after annealed technique, key is: described method steps comprises:
A, the base plate glass after annealing is carried out cutting according to design requirements successively, edging, cleaning, after oven dry, put on specimen mounting, stand-by;
B, the base plate glass on specimen mounting pushed be warming up to 700 ~ 750 DEG C electric furnace in, be incubated 3 ~ 30 minutes;
C, base plate glass is fallen into the methyl-silicone oil forced fluid that temperature is 50 ~ 350 DEG C, when liquid temp to be fortified is down to below 50 DEG C, take out base plate glass;
D, base plate glass surface is cleaned, dry the glass that can be strengthened.
The invention has the beneficial effects as follows: 1, the present invention is using methyl-silicone oil as forced fluid and cooling fluid, need not add any additive again, preparation technology is simple, the toughened glass that application the present invention produces, and have intensity high, cost is low, yield rate advantages of higher; 2, the equipment designed by present method is simple, invests less, and the toughened glass stress distribution obtained according to the inventive method is even, and excellent in cushion effect, glass surface is in good condition, tempering excellent effect.
Accompanying drawing explanation
Fig. 1 is the light transmittance curve figure of the strengthening base plate glass utilizing embodiment 1 method to prepare,
Fig. 2 is the light transmittance curve figure of the strengthening base plate glass utilizing embodiment 2 method to prepare,
In accompanying drawing, X-coordinate is incident light wave length, and ordinate zou is transmittance.
Embodiment
The enhancement method of the aluminoborosilicate ultra thin substrate glass of alkali-free, for the base plate glass after annealed technique is strengthened, importantly: described method steps comprises:
A, prepare forced fluid: take methyl-silicone oil as major ingredient, be aided with quartz sand and allocate according to following weight percent,
Methyl-silicone oil 80 ~ 99%,
Quartz sand 1 ~ 20%,
It is by allocating forced fluid homogeneous heating to 50 ~ 350 DEG C obtained, for subsequent use,
B, the base plate glass after annealing is carried out cutting according to design requirements successively, edging, cleaning, after oven dry, put on specimen mounting, stand-by;
C, the base plate glass on specimen mounting pushed be warming up to 700 ~ 750 DEG C electric furnace in, be incubated 3 ~ 30 minutes;
D, base plate glass fallen into the forced fluid of 50 ~ 350 DEG C, when liquid temp to be fortified is down to below 50 DEG C, take out base plate glass;
E, base plate glass surface is cleaned, dry the glass that can be strengthened.
The grain graininess of described quartz sand is greater than 300 orders.
Described forced fluid homogeneous heating carries out in an oven, and uses magnetic stirrer in the process of heating.
The weight percent of described methyl-silicone oil is 85 ~ 95%.
The weight percent of described quartz sand is 5 ~ 15%.
The present invention, when implementing, see table 1, provides the formula rate example (measuring by weight percentage) of forced fluid in table 1.
Table 1
Provide several embodiments that application the inventive method prepares base plate glass below:
Embodiment 1: first, by the base plate glass after annealing as requested, after cutting edging, cleaning, oven dry, puts on specimen mounting stand-by; Then, the base plate glass specimen mounting of cleaning, drying is pushed in the electric furnace being warming up to 700 DEG C, be incubated 10 minutes; Then, base plate glass is fallen into rapidly the forced fluid (allocating with example 1 formula rate of table 1) of 150 DEG C, when liquid to be fortified is cooled to below 50 DEG C, take out base plate glass; Finally, thoroughly wash the impurity such as the silicone oil on base plate glass surface, dry the glass that namely strengthened.Adopt the shock resistance of GB9963-88 shock resistance measuring sample, falling sphere weight is 5.6 grams, and the shock resistance recording sample is 0.8m, impact three times not broken.By the light transmittance curve of spectrophotometer test sample as shown in Figure 1.
See accompanying drawing 1, be the light transmittance curve after prepared base plate glass is strengthened in visible-range, wherein X-coordinate is lambda1-wavelength, and ordinate zou is transmittance.As seen from Figure 1, after prepared base plate glass strengthening, in 380-780nm wavelength region, base plate glass transmittance is greater than 90.5%.
Embodiment 2: first, by the base plate glass after annealing as requested, after cutting, edging, cleaning, oven dry, puts on specimen mounting stand-by; Then, the base plate glass specimen mounting after cleaning, drying is pushed in the electric furnace being warming up to 730 DEG C, be incubated 15 minutes; Then, base plate glass is fallen into rapidly the forced fluid (allocating with example 2 formula rate of table 1) of 160 DEG C, when liquid to be fortified is cooled to below 50 DEG C, take out base plate glass; Finally, thoroughly wash the impurity such as the silicone oil on base plate glass surface, dry the glass that namely strengthened.Adopt the shock resistance of GB9963-88 shock resistance measuring sample, falling sphere weight is 5.6 grams, and the shock resistance recording sample is 0.82m, impact three times not broken.By the light transmittance curve of spectrophotometer test board glass as shown in Figure 2.
See accompanying drawing 2, be the light transmittance curve after prepared base plate glass is strengthened in visible-range, wherein X-coordinate is lambda1-wavelength, and ordinate zou is transmittance.As seen from Figure 2, after prepared base plate glass strengthening, in 380-780nm wavelength region, base plate glass transmittance is greater than 90.3%.
Embodiment 3, first, by the base plate glass after annealing as requested, after cutting, edging, cleaning, oven dry, puts on specimen mounting stand-by; Then, the base plate glass specimen mounting of cleaning, drying is pushed in the electric furnace being warming up to 740 DEG C, be incubated 30 minutes; Then, base plate glass is fallen into rapidly the forced fluid (allocating with example 3 formula rate of table 1) of 350 DEG C, when liquid to be fortified is cooled to below 50 DEG C, take out base plate glass; Finally, thoroughly wash the impurity such as the silicone oil on base plate glass surface, dry the glass that namely strengthened.Adopt the shock resistance of GB9963-88 shock resistance measuring sample, falling sphere weight is 5.6 grams, and the shock resistance recording sample is 0.9m, impact three times not broken.
Embodiment 4, first, by the base plate glass after annealing as requested, after cutting, edging, cleaning, drying, puts on specimen mounting stand-by; Then, the base plate glass specimen mounting of cleaning, drying is pushed in the electric furnace being warming up to 750 DEG C, be incubated 3 minutes; Then, base plate glass is fallen into rapidly the forced fluid (allocating with example 4 formula rate of table 1) of 250 DEG C, when liquid to be fortified is cooled to below 50 DEG C, take out base plate glass; Finally, thoroughly wash the silicone oil on base plate glass surface, dry the glass that namely strengthened.Adopt the shock resistance of GB9963-88 shock resistance measuring sample, falling sphere weight is 5.6 grams, and the shock resistance recording sample is 0.95m, impact three times not broken.
Embodiment 5, first, by the base plate glass after annealing as requested, after cutting, edging, cleaning, oven dry, puts on specimen mounting stand-by; Then, the base plate glass specimen mounting of cleaning, drying is pushed in the electric furnace being warming up to 720 DEG C, be incubated 10 minutes; Then, base plate glass is fallen into rapidly the forced fluid (allocating with example 5 formula rate of table 1) of 50 DEG C, when liquid to be fortified is cooled to below 50 DEG C, take out base plate glass; Finally, thoroughly wash the impurity such as the silicone oil on base plate glass surface, dry the glass that namely strengthened.Adopt the shock resistance of GB9963-88 shock resistance measuring sample substrate glass, falling sphere weight is 5.6 grams, and the shock resistance recording sample is 0.92m, impact three times not broken.
The present invention, using methyl-silicone oil as strengthening cooling fluid, need not add any additive again, and preparation technology is simple, the toughened glass that application the present invention produces, and have intensity high, cost is low, yield rate advantages of higher.And equipment is simple, invests less.The alkali-free aluminoborosilicate chilled glass stress distribution obtained according to the inventive method is even, and excellent in cushion effect, glass surface is in good condition, tempering excellent effect.Therefore, the high strength slim alkali-free aluminoborosilicate base plate glass prepared by the method has considerable economic and social benefit, and application prospect is very wide.