CN1018634B - Blue discolouration glass - Google Patents

Abstract

The present invention relates to blue discoloration glass which is pure blue in a non-darkening state; the blue discoloration glass darkens and is blue or bluish grey when radiated in a photochemical mode, and especially irradiated by short-wave visible light and ultraviolet rays. The blue discoloration glass uses an aluminum borosilicate system and introduces various additives, such as silver halide, metal oxides, etc.; the blue discoloration glass can be produced by common optical glass melting equipment and a common melting method. When ground into sheets, the blue discoloration glass can be used as optical filters of video display terminals, sunglasses, near-sighted glasses, presbyopic glasses, etc. so as to make people comfortable and beautiful. The present invention has the advantages of high color change speed, favorable color deterioration effect, favorable absorption to short-wave visible light and ultraviolet rays, and positive protection effect on human eyes.

Description

Blue discolouration glass

The invention belongs to the photo chromic glass field.Be pure blueness under non-deepening state, accepting actinic radiation, particularly the irradiation deepening of short wave ultraviolet is blue or bluish grey photo chromic glass product and production method.

Photo chromic glass has following properties usually: photochromic glass places actinic radiation, particularly deepening under the radiation of short wave ultraviolet, and behind the removal actinic radiation, glass is recovered lost eyesight or is return original tone.United States Patent (USP) u.s.p3208860 reports at first; U.s.p4,190,451 have set forth and have improved deepening, and express silver halide photo chromic glass fades; U.s.p3892582 and 3920463 the explanation with thermal treatment reach the permanent table face colouring and under reducing atmosphere heat treated variable color goods, can obtain upper layers such as pink, yellow, dark brown; U.s.p4240836 has introduced thermal treatment under reducing atmosphere, can obtain from indigo plant to the orange photochromic glass goods of the surface colour from red to purplish red; U.s.p4537612 has introduced photo chromic glass after 16 hours ion exchange treatment, handles down through reducing atmosphere again, can obtain purple, only handles under reducing atmosphere without ion exchange treatment, can obtain the orange of surface colour.

Photo chromic glass and production that above-mentioned patent document is introduced, the method that obtains specific color under non-deepening state is very complicated, and the production cycle is long, and the cost height also needs special equipment and heat-treats under reducing atmosphere, and is difficult to obtain pure blueness.

Task of the present invention is the deficiency at above-mentioned photo chromic glass, and a kind of blue discolouration glass is provided, and presents pure blueness under non-deepening state, is dark blue or pewter after the deepening.It is good that this blue discolouration glass has color shifting properties, and it is worn into thin slice, can be used for the spectral filter of video display terminal (VDT) and camera gun, not only improves contrast gradient, can also reduce reflection, reduces the staff's of long-term observation display terminal visual fatigue; Also can be made into the needs of optics aspects such as sun glasses, near-sighted glasses and old light microscopic.

Blue discolouration glass provided by the invention is the aluminium borosilicate system, introduces its recipe ingredients of multiple additives (by weight) such as silver halide and metal oxide to be:

SiO ₂(available quartz sand is crossed 40～80 orders) 30-65 part

B ₂O ₃(available boric acid is crossed 40～20 orders) 12-32 part

Al ₂O ₃(the available hydrogen aluminum oxide is crossed 40～80 orders) 3-15 part

BaO(can cross 10～20 orders with nitrate of baryta) 1-10 part

ZrO ₂(available zirconium white is crossed 80 orders) 0.5-8 part

R ₂O(Li ₂O+Na ₂O+K ₂O 5-20 part

Ag(can use Silver Nitrate) 0.2-0.8 part

Halogen (Cl+Br) (available sodium oxide, Potassium Bromide) 1-3 part

CuO 0.001-0.2 part

CoO(can use cobalt sesquioxide) 0.001-0.2 part

CeO ₂(available cerium dioxide) 0.2-3 part

NiO(can be with three oxygen, two nickel) 0-0.5 part

Optimum formula component (by weight) is:

SiO ₂57.10 part

B ₂O ₃15.20 part

Al ₂O ₃8.04 part

7.15 parts of BaO

ZrO ₂6.5 part

R ₂O(Li ₂O+Na ₂O+K ₂5.65 parts of O=0.30+0.2+5.15

0.3 part of Ag

Halogen (Cl+Br) 0.4+0.1=0.5

CuO 0.01

CoO 0.09

CeO ₂0.35

NiO 0.08

The production technique of blue discolouration glass:

1. prepare burden

Take by weighing starting material after pulverizing, sieve and measuring moisture by above-mentioned recipe ingredient, place in the hopper to mix, add silver nitrate aqueous solution again, fully mix thoroughly, standby.

2. found

Select conventional tank furnace or globars electric furnace for use, platinum crucible and platinum agitator (electric furnace heats up with 50-60 ℃/hour speed) are housed, begin to add the material of mixing thoroughly at 1400 ℃, because the powder specific volume is big, add several times, add 1/2nd of crucible for the first time, add 2/3rds of crucible for the second time, add to flat crucible later on, until adding at every turn.Note material not being sprinkling upon outside the crucible, in the intensification clarification stage, temperature does not rise too suddenly, allows the abundant slaking of material, in order to avoid send out cylinder.The homogenizing clarifying temp is 14.50 ± 15 ℃, and high temperature stirred 6～13 hours with (with 60～70 rev/mins), generally can eliminate bubble.Can the sampling correction specific refractory power in the stokehold, observe striped, bubble.Bubble can or improve mixing speed and adjust by the proper extension settling time.1400 ℃ of bottom discharges, glass is poured into iron plate go up moulding, be pressed into 5～6 millimeters thick sheet glass again.

3. thermal treatment

Above-mentioned sheet glass is placed in the heat treatment box, be incubated 0.5-6 hour down at 620-680 ℃, outage cools the temperature to the room temperature discharging then, is blue discolouration glass product of the present invention.

The discoloration of blue discolouration glass and physical and chemical performance

With the sheet glass after the thermal treatment, become 1.8 ± 0.1 millimeters sample through attrition process, at room temperature test:

1 discoloration (seeing Table)

2 physical and chemical performances

Average coefficient of linear expansion α _20-120=61 * 10 ^-7/ ℃

Softening temperature T _f=575 ℃

Water-fast A level

Acidproof 2-3 class

Proportion 2.37

Specific refractory power η _b=1.4975

Advantage of the present invention:

1. production technique is simple, adopts general opticglass melting equipment and melting method all can produce blue discolouration glass, need not heat-treat under reducing atmosphere, does not also need ion exchange treatment just can make aforesaid blue discolouration glass.

2. because technology is simple, reduce energy consumption, saved man-hour, reduced cost.The also available tank furnace scale operation of photo chromic glass of the present invention realizes the commercialization of product.

3. blue discolouration glass is worn into thin slice, can be used as the spectral filter of video display terminal (VDT), not only can improve contrast gradient, can also reduce white picture reflection, thereby alleviate display terminal office worker's eyeball fatigue.Before being installed on the colour TV screen, can reduce of the stimulation of colored high light, prevent to watch for a long time people's visual deterioration of colour TV human eye.

4. glass of the present invention also can be made sun glasses, near-sighted glasses and old light microscopic, gives the wearer with comfortable and beautiful enjoyment.Particularly the near-sighted glasses wearer comes under the intensive sunlight from indoor, need not change glasses, light-sensitive glasses of the present invention just rapidly deepening be dark blue tone or pewter, good to shortwave light and UV absorbing properties, human eye is played positive protective effect.

5. it is fast that blue discolouration glass of the present invention has variable color speed, and it is effective to fade, the characteristics of tone gracefulness.

Embodiment

1. press the recipe ingredient of above-mentioned blue discolouration glass, calculate weighing according to introducing purity of raw materials, with 61.762 kilograms of silica powders, 28.459 kilograms of boric acid, 13.060 kilograms of aluminium hydroxides, 12.865 kilogram nitrate of baryta, 7.043 the kilogram zirconium white, 0.498 kilogram of Silver Nitrate, 0.0106 kilogram of cupric oxide, 0.1034 kilogram cobalt sesquioxide, 0.368 the kilogram cerium dioxide, 0.0772 kilogram of nickel sesquioxide, 8.18 kilograms of salt of wormwood, 0.379 kilogram yellow soda ash, 0.786 the kilogram Quilonum Retard, 0.697 kilogram of sodium oxide, 0.156 kilogram of Potassium Bromide, place the interior thorough mixing of mixing tank for coating colors even, standby.

The platinum crucible and the platinum agitator of 50 liters are housed in the globars electric furnace,,, add several times because the powder specific volume is big at 1400 ℃ of material that begin to add mixing.In the intensification clarification stage, temperature does not rise too soon, allows the abundant slaking of material.The homogenizing clarifying temp is 14.50 ± 15 ℃, and high temperature stirred 6 hours down, and the sampling correction specific refractory power is observed striped, bubble.1400 ℃ of bottom discharges, glass is poured into iron plate go up moulding.

Sheet glass after the moulding is placed in the heat treatment box, be incubated 0.5～6 hour down at 620～680 ℃ and heat-treat.Outage cools the temperature to the room temperature discharging then, is blue discolouration glass product of the present invention.

2. according to the recipe ingredient of above-mentioned blue discolouration glass, calculate weighing according to the material purity of introducing, with 61.765 kilograms of silica powders, 34.076 kilogram boric acid, 11.436 kilogram aluminium hydroxide, 11.695 kilograms of nitrate of baryta, 4.876 kilograms of zirconium whites, 0.498 kilogram Silver Nitrate, 0.00634 the kilogram cupric oxide, 0.0875 kilogram of cobalt sesquioxide, 0.421 kilogram of cerium dioxide, 0.0772 kilogram nickel sesquioxide, 8.18 kilogram salt of wormwood, 0.379 kilogram of yellow soda ash, 0.786 kilogram of Quilonum Retard, 0.610 kilogram sodium-chlor, 0.315 kilogram of Potassium Bromide.After mixing, press the melting of embodiment 1 preparation blue discolouration glass, thermal treatment process is produced, and promptly obtains the patented product.

3. with 60.141 kilograms of silica powders, 34.076 kilograms of boric acid, 10.768 kilograms of aluminium hydroxides, 12.865 the kilogram nitrate of baryta, 4.334 kilograms of zirconium whites, 0.663 kilogram of Silver Nitrate, 0.0158 the kilogram cupric oxide, 0.0875 kilogram of cobalt sesquioxide, 0.421 kilogram of cerium dioxide, 0.0772 kilogram nickel sesquioxide, 11.357 kilogram salt of wormwood, 0.379 kilogram of yellow soda ash, 2.096 kilograms of Quilonum Retards, 1.046 kilogram sodium-chlor, 0.315 kilogram of Potassium Bromide.After mixing, press the melting of embodiment 1 preparation blue discolouration glass, thermal treatment process is produced, and promptly obtains product of the present invention.

Original transmitance impinge actinic radiation half bleaching time fades and reaches to transmitance

Transmitance after 5 minutes

τ ₀% τ ₅% T _hf60% time T_（60）

71.69 26.26 1 minutes and 23 seconds 8 minutes 25 seconds

Claims (2)

1, a kind of blue discolouration glass is by the aluminoborosilicate system and contain additives such as silver halide and it is characterized in that the recipe ingredient (by weight) of this photo chromic glass is:

SiO ₂30-65 part

B ₂O ₃12-32 part

Al ₂O ₃3-15 part

BaO 1-10 part

ZrO ₂0.5-8 part

R ₂O (Li ₂O+Na ₂O+K ₂O) 5-20 part

Ag 0.2-0.8 part

Halogen (Cl+Br) 1-3 part

CuO 0.001-0.2 part

CoO 0.001-0.2 part

CeO ₂0.2-3 part

NiO 0-0.5 part

2, it is characterized in that according to the described blue discolouration glass of claim 1 the optimum formula component (by weight) of this photo chromic glass is:

SiO ₂57.10 part

B ₂O ₃15.20 part

Al ₂O ₃8.04 part

7.15 parts of BaO

ZrO ₂6.5 part

R ₂O(Li ₂O+Na ₂O+K ₂5.65 parts of O

0.3 part of Ag

Halogen (Cl+Br) 0.4+0.1=0.5 part