CN103102072A - High brightness glass and preparation method thereof - Google Patents
High brightness glass and preparation method thereof Download PDFInfo
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- CN103102072A CN103102072A CN2011103566385A CN201110356638A CN103102072A CN 103102072 A CN103102072 A CN 103102072A CN 2011103566385 A CN2011103566385 A CN 2011103566385A CN 201110356638 A CN201110356638 A CN 201110356638A CN 103102072 A CN103102072 A CN 103102072A
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- 239000011521 glass Substances 0.000 title claims abstract description 228
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 70
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 47
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 24
- 239000006004 Quartz sand Substances 0.000 claims abstract description 24
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 23
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 23
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 23
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 33
- 239000006063 cullet Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 22
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 21
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010583 slow cooling Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000005357 flat glass Substances 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 36
- 229910052711 selenium Inorganic materials 0.000 abstract description 12
- 239000011669 selenium Substances 0.000 abstract description 12
- 238000002845 discoloration Methods 0.000 abstract description 4
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 abstract 2
- 230000036561 sun exposure Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 12
- 239000010941 cobalt Substances 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 150000003346 selenoethers Chemical class 0.000 description 7
- 230000000295 complement effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229960002594 arsenic trioxide Drugs 0.000 description 4
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229910004762 CaSiO Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 241000220317 Rosa Species 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910021489 α-quartz Inorganic materials 0.000 description 1
- 229910000500 β-quartz Inorganic materials 0.000 description 1
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Abstract
The invention discloses a high brightness glass which comprises the following main raw materials: 510-630 parts by weight of quartz sand, 170-208 parts by weight of soda ash, 130-164 parts by weight of calcite, 18-23 parts by weight of aluminium hydroxide, 0.2-0.25 parts by weight of erbium oxide, and 0.0005-0.0007 parts by weight of cobalt powder. The invention further discloses a preparation method of the high brightness glass. According to the invention, the high brightness glass solves problems of discoloration caused by selenium exposure due to long-time storage of the glasses and strong sun exposure, and simultaneously improves brightness, whiteness and transparency of the glasses.
Description
Technical field
The present invention relates to glass manufacturing area, relate in particular to a kind of high brightness glass and preparation method thereof.
Background technology
Along with the fast development of China's photoelectric technology and the raising of experimental study level, market proposes higher requirement for brightness, whiteness and the transmitance of glass.Meanwhile, due to the problem of the poor stability of discoloring agent, along with " variable color " problem can occur for the prolongation of glassy product shelf-time.Nowadays, high brightness all is badly in need of in the industry such as high-grade glass furniture, ornamental glass, imitative crystal product, fitting glass, top-grade building and field, the glass of high whiteness and high-clarity, therefore, how to improve brightness, whiteness and the transmitance of glass and the important topic that solution " variable color " problem becomes the glass manufacture industry.
Glass production can inevitably contain a certain amount of impurity iron composition because using a large amount of mineral raw materials, makes glass with in various degree yellow-green colour or blue-greenish colour.Mainly contain at present two kinds of methods and solve, first method is with main raw material(s) sandstone, quartzite rod milling, washing, reduces the content of iron in raw material, although can significantly improve the whiteness of glass, cost increases a lot, and fund input is large.Second method is to add discoloring agent in the preparation technology of glass, improves glass colour.Prior art is improved glass colour by adding discoloring agent approach mainly contains:
1, traditional selenium (or selenide), cobalt decolouring: " glass technology " (China Light Industry Press, the 9th printing of the 1st edition calendar year 2001, the 190th page).
It is very unstable that yet traditional selenium or selenide, cobalt decolour, and can change with the variation of kiln melting technology, can reduce the light transmission of glass along with the increase of consumption; In addition, along with the prolongation of glassy product shelf-time, " selenium exposes to the sun " occurs and produces discoloration problem in the meeting of especially being exposed to the sun under the sun, and advantage is that cost is relatively low, and is nontoxic.
2, white arsenic coordinates selenium, cobalt decolouring: " glass technology " (China Light Industry Press, the 9th printing of the 1st edition calendar year 2001, the 190th page).
Utilize white arsenic to coordinate selenium, cobalt decolouring in order to improve in the process of founding selenium, cobalt decolouring stability, to mention in " glass technology ", increase substantially brightness and the whiteness of glassy product, and in the process of founding selenium, the cobalt decolouring is stable also is significantly increased.But the shortcoming of this technology is white arsenic has toxicity, and batching operates dangerous and has the food safety potential problem.Simultaneously, the consumption of selenium powder will increase by more original formula, improves production cost.When white arsenic also can impel selenium, cobalt as discoloring agent, the metachromatism of glass in annealing and the process of being exposed to the sun appearred.
3, cerium oxide coordinates selenium, cobalt decolouring: " international glass " Chinese edition, in April, 2002.The shortcoming of this technology is that the selenium powder consumption is relatively also more, and glass colour takes on a new look very little.Advantage is to improve the refining quality of glass.
In addition, Chinese patent 102092941A discloses a kind of ultra-clear glasses, and comprehensive glass chemistry decolouring and physical decolorization method add La in white float glass batch materials
2(CO
3)
3, Ce
2(CO
3)
3, Nd
2(CO
3)
3, MnO
2, CoO, CuSO
4, at first make the stronger Fe of tinting strength in glass
2+Change into the weak Fe of tinting strength
3+, then add discoloring agent, and utilize the complementarity of light, eliminate glass colour, improved the transmitance of glass visible light, reduce whiteness.It is very unstable that but traditional discoloring agent cobalt, cerium decolour, and can change with the variation of kiln melting technology, can reduce the light transmission of glass along with the increase of consumption; In addition, along with the prolongation of glassy product shelf-time, " selenium exposes to the sun " occurs and produces discoloration problem in the meeting of especially being exposed to the sun under the sun.
Therefore, cause producing discoloration problem in order to solve be exposed to the sun " selenium exposes to the sun " of generation of the long-time and sun of glassy product, the present invention will use a kind of new method and technology, brightness and the whiteness of glassy product had both been improved, simultaneously also improve the problems referred to above, satisfying the market is for the demand of high brightness and whiteness glassy product.
Summary of the invention
Embodiment of the present invention technical problem to be solved is, a kind of high brightness glass and preparation method thereof is provided.The discoloring agent selenium powder that described high brightness glass use Erbium trioxide is alternative traditional or selenide, cobalt, cerium, because the Erbium trioxide thermal characteristics is stable, its consumption is not subjected to the impact of melting conditions substantially, and glassy product metachromatism can not occur because the shelf-time is long.Brightness and the whiteness of glassy product of Erbium trioxide of having adulterated simultaneously reaches high requirement, greatly improved the quality of glassy product.
In order to solve the problems of the technologies described above, the embodiment of the present invention provides a kind of high brightness glass, and the total raw material formula of described production high brightness glass comprises admixtion, and described admixtion is as follows in the main raw material formula of weight part:
Quartz sand 510 ~ 630
Soda ash 170 ~ 208
Calcite 130 ~ 164
Aluminium hydroxide 18 ~ 23
Erbium trioxide 0.2 ~ 0.25
Cobalt powder 0.0005 ~ 0.0007.
Preferably, the total raw material formula of described production high brightness glass comprises admixtion, and described admixtion is as follows in the main raw material formula of weight part:
Quartz sand 610 ~ 630
Soda ash 190 ~ 208
Calcite 150 ~ 164
Aluminium hydroxide 20 ~ 23
Erbium trioxide 0.22 ~ 0.25
Cobalt powder 0.0006 ~ 0.0007.
Preferably, described admixtion also comprises in the main raw material formula of weight part:
Finings saltcake 7 ~ 9.
Preferably, the total raw material formula of described production high brightness glass also comprises glass cullet, and the composition of described glass cullet is consistent with the composition of described admixtion;
Described admixtion accounts for 85% of total raw material, and described glass cullet account for 15% of total raw material.
Preferably, this kind 40mm heavy sheet glass has visible light transmissivity at 380 ~ 780nm wavelength greater than 94.3 ~ 95.3, and whiteness is less than 0.04 ~ 0.05.
Correspondingly, the embodiment of the present invention also provides a kind of preparation method of high brightness glass, comprises the following steps successively:
With the quartz sand of 510 ~ 630 weight parts, the soda ash of 170 ~ 208 weight parts, the calcite of 130 ~ 164 weight parts, the aluminium hydroxide of 18 ~ 23 weight parts, the Erbium trioxide of 0.2 ~ 0.25 weight part, the cobalt powder of 0.0005 ~ 0.0007 weight part is with the weight proportion weighing, enter mixing machine and mix, obtain admixtion;
Described admixtion with 85% and 15% described glass cullet mix, and obtain mixing raw material;
Described mixing raw material is entered melting furnaces, is to found under the condition of 1500 ℃ ~ 1650 ℃ to obtain glass metal in temperature;
At 1400 ℃ ~ 1450 ℃ temperature, the finings saltcake of 7 ~ 9 weight parts is joined the glass metal that described process is founded;
To add the glass metal of finings saltcake to pour in forming mould, slow cooling to 1200 ℃ ~ 1250 ℃ of cooling formings, annealing obtains high brightness glass.
Preferably, described preparation method comprises the following steps successively:
Quartz sand with 610 ~ 630 weight parts, the soda ash of 190 ~ 208 weight parts, the calcite of 150 ~ 164 weight parts, the aluminium hydroxide of 20 ~ 23 weight parts, 0.22 the Erbium trioxide of ~ 0.25 weight part, mix 0.0006 the cobalt powder of ~ 0.0007 weight part with the weight proportion weighing, enters mixing machine, obtain admixtion;
Described admixtion with 85% and 15% described glass cullet mix, and obtain mixing raw material;
Described mixing raw material is entered melting furnaces, is to found under the condition of 1550 ℃ ~ 1560 ℃ to obtain glass metal in temperature;
At 1420 ℃ ~ 1430 ℃ temperature, the finings saltcake of 7 ~ 9 weight parts is joined the glass metal that described process is founded;
To add the glass metal of finings saltcake to pour in forming mould, slow cooling to 1200 ℃ ~ 1250 ℃ of cooling formings, annealing obtains high brightness glass.
Preferably, the described admixtion with 85% and 15% described glass cullet mix, and before obtaining the step of mixing raw material, also comprise:
With described glass cullet surface cleaning.
Preferably, the composition of described glass cullet is consistent with the composition of described admixtion.
Preferably, this kind 40mm heavy sheet glass has visible light transmissivity at 380 ~ 780nm wavelength greater than 94.3 ~ 95.3, and whiteness is less than 0.04 ~ 0.05.
Implement the embodiment of the present invention, have following beneficial effect:
The present invention is about a kind of high brightness glass and preparation method thereof, combine chemical decolorization and the physical decolorization method of glass, at first make the ferrous iron that in glass, tinting strength is stronger be converted into the weak ferric iron of tinting strength, the complementarity of recycling light, the color of glass is disappeared, reach best effect.Compared with prior art, its improvement is to use Erbium trioxide to substitute traditional discoloring agent selenium powder or selenide, cobalt, cerium.Oxidation bait (Er
20
3) add on a small quantity can reinforcing glass to the reflection of ultraviolet light, and make ultraviolet transmission than reducing.Because the Erbium trioxide thermal characteristics is stable, its consumption is not subjected to the impact of melting conditions substantially in addition, and glassy product metachromatism can not occur because the shelf-time is long.Simultaneously, Erbium trioxide can obviously improve brightness, whiteness and the transmitance of glass, improves the quality of glassy product.
Secondly, adopt Erbium trioxide to substitute selenium powder as discoloring agent, need not to improve other quality requirements of raw materials of glass production again, just can reach the brightness that increases substantially product and the purpose of whiteness, fund input changes little, and the while has also been satisfied the requirement in market.
Again, adopt Erbium trioxide to substitute selenium powder as discoloring agent, thermal characteristics is stable, does not affect because it is not subjected to melting conditions substantially, and after substituting, the consumption of raw material is stable, and product colour quality stability is good; And prior art adopts selenium powder as discoloring agent, and is larger because affected by melting conditions, and the consumption fluctuation of raw material is large, and product colour quality stability is also poor.
At last, the present invention only adopts Erbium trioxide and cobalt powder just can reach high brightness and high whiteness, thereby does not need and lanthanum trioxide and cerium oxide, has saved rare earth element.
Description of drawings
Fig. 1 is the preparation method's of a kind of high brightness glass of the present invention schema;
Fig. 2 is complementary colors look and wavelength corresponding diagram;
Fig. 3 is glassy product color transmittance curve figure.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, the present invention is described in further detail below in conjunction with accompanying drawing.
The embodiment of the present invention provides the embodiment of the present invention that a kind of high brightness glass is provided, and the total raw material formula of described production high brightness glass comprises admixtion, and described admixtion is as follows in the main raw material formula of weight part:
Quartz sand 510 ~ 630
Soda ash 170 ~ 208
Calcite 130 ~ 164
Aluminium hydroxide 18 ~ 23
Erbium trioxide 0.2 ~ 0.25
Cobalt powder 0.0005 ~ 0.0007.
Preferably, the total raw material formula of described production high brightness glass comprises admixtion, and described admixtion is as follows in the main raw material formula of weight part:
Quartz sand 610 ~ 630
Soda ash 190 ~ 208
Calcite 150 ~ 164
Aluminium hydroxide 20 ~ 23
Erbium trioxide 0.22 ~ 0.25
Cobalt powder 0.0006 ~ 0.0007.
The quartz sand main component is S i O
2, S i O
2Be the main component that consists of the glass skeleton, can reduce the thermal expansivity of glass, improve thermostability, chemical stability, softening temperature, thermotolerance, hardness, physical strength and the viscosity etc. of glass.Content is too low, and the various performances of glass can descend, too high levels, and raw material is difficult to fusing.
The calcite main component is calcium carbonate mineral CaCO
3
Oxidation bait (Er
20
3) add on a small quantity can reinforcing glass to the reflection of ultraviolet light, and make ultraviolet transmission than reducing, but the large colour developing of amount.Er in the present invention
20
3Suitable amount be 0.2 ~ 0.25 weight part.
Cobalt powder CoO may have CoO in glass
6And CoO
4Two kinds of co-ordination states, the former absorption band is near 550nm, and color is partially purple, energy and Fe
3+Yellow-green colour complementary, latter's absorption band is near 620nm, color is partially blue, can and Fe
2+Dark green complementation.
Described admixtion also comprises in the main raw material formula of weight part:
Finings saltcake 7 ~ 9.
The present invention uses traditional saltcake finings, and is nontoxic, and clarifying effect is good, and cost compare is low.
Because a large amount of gas is separated out in the decomposition of each component of admixtion and volatilization etc., exist portion gas not overflow fully from glass melt, remain in glass metal with the form of bubble, have a strong impact on the quality of glassy product.Thereby need to add the finings saltcake, glass metal is clarified, eliminate the bubble of glass metal.
The total raw material formula of described production high brightness glass also comprises glass cullet, and the composition of described glass cullet is consistent with the composition of described admixtion;
Described admixtion accounts for 85% of total raw material, and described glass cullet account for 15% of total raw material.
This kind 40mm heavy sheet glass has visible light transmissivity at 380 ~ 780nm wavelength greater than 94.3 ~ 95.3, and whiteness is less than 0.04 ~ 0.05.
Correspondingly, as shown in Figure 1, the embodiment of the present invention also provides a kind of preparation method of high brightness glass, comprises the following steps successively:
S101, quartz sand with 510 ~ 630 weight parts, the soda ash of 170 ~ 208 weight parts, the calcite of 130 ~ 164 weight parts, the aluminium hydroxide of 18 ~ 23 weight parts, the Erbium trioxide of 0.2 ~ 0.25 weight part, the cobalt powder of 0.0005 ~ 0.0007 weight part is with the weight proportion weighing, enter mixing machine and mix, obtain admixtion.
Preferably, quartz sand with 610 ~ 630 weight parts, the soda ash of 190 ~ 208 weight parts, the calcite of 150 ~ 164 weight parts, the aluminium hydroxide of 20 ~ 23 weight parts, the Erbium trioxide of 0.22 ~ 0.25 weight part, the cobalt powder of 0.0006 ~ 0.0007 weight part is with the weight proportion weighing, enter mixing machine and mix, obtain admixtion.
S102, the described admixtion with 85% and 15% described glass cullet mix, and obtain mixing raw material.
Preferably, before the S102 step, also comprise:
With described glass cullet surface cleaning.
Preferably, the composition of described glass cullet is consistent with the composition of described admixtion.
S103 enters melting furnaces with described mixing raw material, in temperature is to found under the condition of 1500 ℃ ~ 1650 ℃ to obtain glass metal.
Preferably, described glass melting temperature is 1550 ℃ ~ 1560 ℃.
Following physicochemical change can occur in glass in the process of founding:
CaCO
3?+?Na
2CO
3?=?CaNa
2(CO
3)
2
β-quartz=alpha-quartz
CaNa
2(CO
3)
2?+?2SiO
2?=?Na
2SiO
3?+?CaSiO
3?+?2CO
2↑
CaNa
2(CO
3)
2?+?Na
2CO
3+3SiO
2?=2?Na
2SiO
3+?CaSiO
3?+?3CO
2↑
CaCO
3=CaO+?CO
2↑
CaNa
2(CO
3)
2=Na
2O+?CaO+?2CO
2↑
CaO+?SiO
2?=?CaSiO
3
With Er
2O
3Can form at last the high brightness glass of the doping Erbium trioxide of high brightness, high whiteness and high permeability.
S104 at 1400 ℃ ~ 1450 ℃ temperature, joins with the finings saltcake of 7 ~ 9 weight parts the glass metal that described process is founded.
Preferably, adding the temperature of finings saltcake is 1420 ℃ ~ 1430 ℃.
S105 will add the glass metal of finings saltcake to pour in forming mould, slow cooling to 1200 ℃ ~ 1250 ℃ of cooling formings, and annealing obtains high brightness glass.
This kind 40mm heavy sheet glass has visible light transmissivity at 380 ~ 780nm wavelength greater than 94.3 ~ 95.3, and whiteness is less than 0.04 ~ 0.05.
The present invention is about a kind of high brightness glass and preparation method thereof, its glass uses Erbium trioxide to substitute traditional discoloring agent selenium powder or selenide, because the Erbium trioxide thermal characteristics is stable, its consumption is not subjected to the impact of melting conditions substantially, and glassy product metachromatism can not occur because the shelf-time is long.Brightness and the whiteness of glassy product reach high requirement simultaneously, improve the quality of glassy product.
Soda-lime-silica glass production and application Erbium trioxide glass of the present invention can be coloured to rose, use selenium powder glass can be coloured to pink.Glass production can inevitably contain a certain amount of impurity iron composition because using a large amount of mineral raw materials, and its existence form has FeO and Fe
2O
3Two kinds, Fe wherein
2+Make glassy product be blue-greenish colour, Fe
3+Make glassy product be yellow-green colour, Fe
2+Tinting strength compare Fe
3+Exceed tens times.But these iron ions all can reduce brightness and the whiteness of glass.
According to the complementarity principle of color, as shown in Fig. 2 complementary colors look and wavelength corresponding diagram, redness can form complementary color with green and weaken the color keynote.Therefore, in traditional decoloring method, tend to add selenium powder or selenide to raw material, painted in pinkiness on glass, pink is yellowish green with green complementary main keynote; And the alternative selenium powder of the Erbium trioxide that the present invention uses or selenide are painted in the rose that is on glass as discoloring agent, rose and the green complementary appropriate micro-purple of the main keynote of words.The purple wavelength is near 390nm, and the yellow-green colour wavelength is near 560nm, and human eye is higher than near the susceptibility 390nm to the color of 560nm, i.e. aberration sense is stronger, human eye be can reduce to the susceptibility of color so use Erbium trioxide to substitute selenium powder, thereby brightness and the whiteness of glass promoted.And Erbium trioxide stable performance, consumption do not change with the variation of melting conditions substantially, and the glassy product that is mixed with Erbium trioxide metachromatism can not occur because the shelf-time is long.In addition, high brightness glass of the present invention is used in conjunction with the cobalt powder of reasonable amount, and the cobalt powder of reasonable amount can make glass ribbon slightly blue, and collocation can make glass colour more high-grade on the high white glass of essence.
Tradition uses selenium powder decolouring glass and the present invention to use Erbium trioxide to dewater, and to carry out brightness, whiteness and transmitance simultaneous test as follows for glass:
One, prepare the simultaneous test material: the selenium powder decolouring glass of high brightness glass of the present invention and prior art
Formula according to table one composition of raw materials 1 prepares selenium powder decolouring glass;
Take 85% admixtion (according to table one composition of raw materials 2) and 15% glass cullet, and prepare with preparation method of the present invention the high brightness glass that uses the Erbium trioxide decolouring.Wherein, the composition of described glass cullet is consistent with the composition of described admixtion.That is to say the waste product glass of described glass cullet for being made by the present invention.
Table one is as follows:
Need to prove, above each raw material is the raw material consumption of the various admixtiones of ton glass metal.
Two, the method for simultaneous test and step
Be of a size of respectively the glass block of 1 * 5cm from two kinds of glassy product cuttings, measure and record the thickness of glass; Glass block with described cutting is placed on the transmitance that detects in spectrophotometer cary50 at the different wave length lower-glass respectively, is converted into the transmitance under standard thickness (40mm) and is depicted as different wave length lower-glass transmitance comparison diagram (as shown in Figure 3).Go out again brightness (Y), purity (Pe) and the predominant wavelength λ d of glass according to the CIE system-computed of international lighting, obtain table two---the optical property contrast of glass.
Three, comparative test result contrast
1, discoloring agent consumption
Selenium powder decolouring glass: selenium powder consumption 8～10g/T glass metal, cobalt powder 0.4～0.7g/T glass metal;
Erbium trioxide decolouring glass: Erbium trioxide consumption 200～250g/T glass metal, cobalt powder 0.5～0.7g/T glass metal.
2, glassy product quality of colour contrast
Use Erbium trioxide substitute selenium powder and rationally control the cobalt powder consumption, the whiteness of glassy product increases substantially, brightness also be improved significantly, see the optical property contrast of Fig. 3 glassy product color transmittance curve figure and following table two glass:
As shown in Figure 3, curve 1 is for using glass transmitance in 380nm ~ 760nm wavelength region of Erbium trioxide decolouring, and curve 2 is for using glass transmitance in 380nm ~ 760nm wavelength region of selenium powder decolouring.By curve in figure as can be known, use glass transmitance in 380nm ~ 760nm wavelength region of Erbium trioxide decolouring substantially to remain near 95%, and use the glass transmitance of selenium powder decolouring substantially to remain near 87%, therefore, both compare, transmitance of the present invention has approximately increased by 8%.Hence one can see that, uses Erbium trioxide can greatly promote the transmitance of glass as discoloring agent with respect to traditional discoloring agent.
Go out brightness (Y), purity (Pe) and the predominant wavelength λ d of glass according to the international luminouslighting council (being called for short CIE) the CIE standard chroma system-computed of setting up.Obtain following table two---the optical property contrast of glass:
| Project | Y（%） | Pe（%） | λd（nm） |
| With the selenium powder glass that decolours | 87.9 | 0.83 | 577.8 |
| With the Erbium trioxide glass that decolours | 95.3 | 0.05 | -561.4 |
Need to prove, in table 2:
1. the brightness of .Y-glass, the perviousness of the larger light of value is better, and glass is more transparent;
2. the purity of .Pe-glass colour, the whiteness of the less glass of value is higher;
3.. the keynote of λ d-glass colour, different dominant wavelength ranges glass colours are different.
As shown in Table 2, analyze Y value as can be known: the present invention uses Erbium trioxide as discoloring agent, and coordinating the brightness of the high brightness glass of cobalt powder is 95.3%, is 87.9% and use the brightness of selenium powder decolouring glass in prior art.Namely compared with prior art, the brightness of glass of the present invention has improved 7.4%, therefore, uses Erbium trioxide as discoloring agent, and coordinate cobalt powder and glass, its perviousness to light is better, glass is more transparent, can obviously improve the brightness of glass.
Analyze the Pe value as can be known: the present invention uses Erbium trioxide as discoloring agent, and coordinating the purity of the high brightness glass of cobalt powder is 0.05%, is 0.83% and use the purity of selenium powder decolouring glass in prior art.Namely compared with prior art, the purity drop of glass of the present invention 0.78%.Purity is lower, and the whiteness of glass is higher.Therefore, use Erbium trioxide as discoloring agent, and coordinate cobalt powder and glass, can obviously improve the whiteness of glass.
In sum, use Erbium trioxide to substitute selenium powder as discoloring agent, and coordinate cobalt powder can obviously improve brightness, whiteness and the transmitance of glass.
Below further illustrate the present invention with specific embodiment.
Embodiment 1
The high brightness glass main raw materials in proportion is as follows:
Quartz sand 510kg, soda ash 170kg, calcite 130kg, aluminium hydroxide 18kg, Erbium trioxide 0.2kg, cobalt powder 0.0005kg.
Embodiment 2
The high brightness glass main raw materials in proportion is as follows:
Quartz sand 545kg, soda ash 185kg, calcite 130kg, aluminium hydroxide 19.3kg, Erbium trioxide 0.22kg, cobalt powder 0.0005kg.
Embodiment 3
The high brightness glass main raw materials in proportion is as follows:
Quartz sand 570kg, soda ash 185kg, calcite 148kg, aluminium hydroxide 20.5kg, Erbium trioxide 0.22kg, cobalt powder 0.0006kg.
Embodiment 4
The high brightness glass main raw materials in proportion is as follows:
Quartz sand 630kg, soda ash 208kg, calcite 164kg, aluminium hydroxide 23kg, Erbium trioxide 0.25kg, cobalt powder 0.0007kg.
Embodiment 5
The high brightness glass main raw materials in proportion is as follows:
Quartz sand 620kg, soda ash 204kg, calcite 161kg, aluminium hydroxide 22.4kg, Erbium trioxide 0.245kg, cobalt powder 0.00065kg.
Embodiment 6
The preparation method of high brightness glass is as follows:
With the quartz sand of raw material 510kg, the soda ash of 170kg, the calcite of 130kg, the aluminium hydroxide of 18kg, the Erbium trioxide of 0.2kg, the cobalt powder of 0.0005kg enter mixing machine and mix with the weight proportion weighing, obtain admixtion;
The glass cullet of the admixtion with 85% and 15% surface cleaning mix, and obtain mixing raw material;
Mixing raw material is entered melting furnaces, found under 1550 ℃ ~ 1560 ℃ and obtain glass metal;
At 1420 ℃ ~ 1430 ℃, 7kg finings saltcake is joined the glass metal that described process is founded;
The glass metal that adds finings is flow in forming mould slow cooling to 1200 ℃ ~ 1250 ℃ of cooling formings, annealing, the high brightness glass of the Erbium trioxide that obtains adulterating.
Embodiment 7
The preparation method of high brightness glass is as follows:
With the quartz sand of raw material 545kg, the soda ash of 185kg, the calcite of 130kg, the aluminium hydroxide of 19.3kg, the Erbium trioxide of 0.22kg, the cobalt powder of 0.0005kg enter mixing machine and mix with the weight proportion weighing, obtain admixtion;
The glass cullet of the admixtion with 85% and 15% surface cleaning mix, and obtain mixing raw material;
Mixing raw material is entered melting furnaces, found under 1550 ℃ ~ 1560 ℃ and obtain glass metal;
At 1420 ℃ ~ 1430 ℃, 7.3kg finings saltcake is joined the glass metal that described process is founded;
The glass metal that adds finings is flow in forming mould slow cooling to 1200 ℃ ~ 1250 ℃ of cooling formings, annealing, the high brightness glass of the Erbium trioxide that obtains adulterating.
Embodiment 8
The preparation method of high brightness glass is as follows:
With the quartz sand of raw material 570kg, the soda ash of 185kg, the calcite of 148kg, the aluminium hydroxide of 20.5kg, the Erbium trioxide of 0.22kg, the cobalt powder of 0.0006kg enter mixing machine and mix with the weight proportion weighing, obtain admixtion;
The glass cullet of the admixtion with 85% and 15% surface cleaning mix, and obtain mixing raw material;
Mixing raw material is entered melting furnaces, found under 1550 ℃ ~ 1560 ℃ and obtain glass metal;
At 1420 ℃ ~ 1430 ℃, 8kg finings saltcake is joined the glass metal that described process is founded;
The glass metal that adds finings is flow in forming mould slow cooling to 1200 ℃ ~ 1250 ℃ of cooling formings, annealing, the high brightness glass of the Erbium trioxide that obtains adulterating.
Embodiment 9
The preparation method of high brightness glass is as follows:
With the quartz sand of raw material 630kg, the soda ash of 208kg, the calcite of 164kg, the aluminium hydroxide of 23kg, the Erbium trioxide of 0.25kg, the cobalt powder of 0.0007kg enter mixing machine and mix with the weight proportion weighing, obtain admixtion;
The glass cullet of the admixtion with 85% and 15% surface cleaning mix, and obtain mixing raw material;
Mixing raw material is entered melting furnaces, found under 1550 ℃ ~ 1560 ℃ and obtain glass metal;
At 1420 ℃ ~ 1430 ℃, 8.6kg finings saltcake is joined the glass metal that described process is founded;
The glass metal that adds finings is flow in forming mould slow cooling to 1200 ℃ ~ 1250 ℃ of cooling formings, annealing, the high brightness glass of the Erbium trioxide that obtains adulterating.
Embodiment 10
The preparation method of high brightness glass is as follows:
With the quartz sand of raw material 620kg, the soda ash of 204kg, the calcite of 161kg, the aluminium hydroxide of 22.4kg, the Erbium trioxide of 0.245kg, the cobalt powder of 0.0005kg enter mixing machine and mix with the weight proportion weighing, obtain admixtion;
The glass cullet of the admixtion with 85% and 15% surface cleaning mix, and obtain mixing raw material;
Mixing raw material is entered melting furnaces, found under 1550 ℃ ~ 1560 ℃ and obtain glass metal;
At 1420 ℃ ~ 1430 ℃, 9kg finings saltcake is joined the glass metal that described process is founded;
The glass metal that adds finings is flow in forming mould slow cooling to 1200 ℃ ~ 1250 ℃ of cooling formings, annealing, the high brightness glass of the Erbium trioxide that obtains adulterating.
Need to prove, the preparation method of the corresponding embodiment 6 of the formula of above-described embodiment 1, the preparation method of the corresponding embodiment 7 of the formula of embodiment 2, the preparation method of the corresponding embodiment 8 of the formula of embodiment 3, the preparation method of the corresponding embodiment 9 of the formula of embodiment 4, the preparation method of the corresponding embodiment 10 of the formula of embodiment 5.
Above-described embodiment 6 to 10 is gone out brightness (Y), purity (Pe) and the predominant wavelength λ d of glass according to the international luminouslighting council (being called for short CIE) the CIE standard chroma system-computed of setting up.Obtain following table three---the optical property contrast of glass:
| Project | Y（%） | Pe（%） | λd（nm） |
| Embodiment 1 | 94.3 | 0.040 | -561.4 |
| Embodiment 2 | 94.8 | 0.042 | -561.4 |
| Embodiment 3 | 95.1 | 0.048 | -561.4 |
| Embodiment 4 | 95.3 | 0.050 | -561.4 |
| Embodiment 5 | 95.2 | 0.046 | -561.4 |
Above disclosed is only a kind of preferred embodiment of the present invention, certainly can not limit with this interest field of the present invention, and the equivalent variations of therefore doing according to claim of the present invention still belongs to the scope that the present invention is contained.
Claims (10)
1. a high brightness glass, is characterized in that, the total raw material formula of described production high brightness glass comprises admixtion, and described admixtion is as follows in the main raw material formula of weight part:
Quartz sand 510 ~ 630
Soda ash 170 ~ 208
Calcite 130 ~ 164
Aluminium hydroxide 18 ~ 23
Erbium trioxide 0.2 ~ 0.25
Cobalt powder 0.0005 ~ 0.0007.
2. high brightness glass according to claim 1, is characterized in that, the total raw material formula of described production high brightness glass comprises admixtion, and described admixtion is as follows in the main raw material formula of weight part:
Quartz sand 610 ~ 630
Soda ash 190 ~ 208
Calcite 150 ~ 164
Aluminium hydroxide 20 ~ 23
Erbium trioxide 0.22 ~ 0.25
Cobalt powder 0.0006 ~ 0.0007.
3. the described high brightness glass of any one according to claim 1 and 2, is characterized in that, described admixtion also comprises in the main raw material formula of weight part:
Finings saltcake 7 ~ 9.
4. high brightness glass according to claim 3, is characterized in that, the total raw material formula of described production high brightness glass also comprises glass cullet, and the composition of described glass cullet is consistent with the composition of described admixtion;
Described admixtion accounts for 85% of total raw material, and described glass cullet account for 15% of total raw material.
5. high brightness glass according to claim 4, is characterized in that, this kind 40mm heavy sheet glass has visible light transmissivity at 380 ~ 780nm wavelength greater than 94.3 ~ 95.3, and whiteness is less than 0.04 ~ 0.05.
6. the preparation method of a high brightness glass, is characterized in that, comprises the following steps successively:
With the quartz sand of 510 ~ 630 weight parts, the soda ash of 170 ~ 208 weight parts, the calcite of 130 ~ 164 weight parts, the aluminium hydroxide of 18 ~ 23 weight parts, the Erbium trioxide of 0.2 ~ 0.25 weight part, the cobalt powder of 0.0005 ~ 0.0007 weight part is with the weight proportion weighing, enter mixing machine and mix, obtain admixtion;
Described admixtion with 85% and 15% described glass cullet mix, and obtain mixing raw material;
Described mixing raw material is entered melting furnaces, is to found under the condition of 1500 ℃ ~ 1650 ℃ to obtain glass metal in temperature;
At 1400 ℃ ~ 1450 ℃ temperature, the finings saltcake of 7 ~ 9 weight parts is joined the glass metal that described process is founded;
To add the glass metal of finings saltcake to pour in forming mould, slow cooling to 1200 ℃ ~ 1250 ℃ of cooling formings, annealing obtains high brightness glass.
7. the preparation method of high brightness glass glass according to claim 6, is characterized in that, described preparation method comprises the following steps successively:
Quartz sand with 610 ~ 630 weight parts, the soda ash of 190 ~ 208 weight parts, the calcite of 150 ~ 164 weight parts, the aluminium hydroxide of 20 ~ 23 weight parts, 0.22 the Erbium trioxide of ~ 0.25 weight part, mix 0.0006 the cobalt powder of ~ 0.0007 weight part with the weight proportion weighing, enters mixing machine, obtain admixtion;
Described admixtion with 85% and 15% described glass cullet mix, and obtain mixing raw material;
Described mixing raw material is entered melting furnaces, is to found under the condition of 1550 ℃ ~ 1560 ℃ to obtain glass metal in temperature;
At 1420 ℃ ~ 1430 ℃ temperature, the finings saltcake of 7 ~ 9 weight parts is joined the glass metal that described process is founded;
To add the glass metal of finings saltcake to pour in forming mould, slow cooling to 1200 ℃ ~ 1250 ℃ of cooling formings, annealing obtains high brightness glass.
8. the preparation method of the according to claim 6 or 7 described high brightness glass glass of any one, is characterized in that, the described admixtion with 85% and 15% described glass cullet mix, and before obtaining the step of mixing raw material, also comprise:
With described glass cullet surface cleaning.
9. the preparation method of high brightness glass according to claim 8, is characterized in that, the composition of described glass cullet is consistent with the composition of described admixtion.
10. high brightness glass according to claim 9, is characterized in that, this kind 40mm heavy sheet glass has visible light transmissivity at 380 ~ 780nm wavelength greater than 94.3 ~ 95.3, and whiteness is less than 0.04 ~ 0.05.
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| CN106242278A (en) * | 2016-08-29 | 2016-12-21 | 浙江伟兴水晶有限公司 | A kind of white colour crystal bead blank and preparation method thereof |
| CN113307492A (en) * | 2021-04-26 | 2021-08-27 | 侯硕 | Production process of high-transparency glass bottle |
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| CN102219375A (en) * | 2010-04-16 | 2011-10-19 | 信义光伏产业(安徽)控股有限公司 | Solar super-white rolling glass and preparation method thereof |
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