CN106082682A - Glass air brushing bismuth silicon boron system's low-melting-point nano glass dust suspension and preparation method - Google Patents
Glass air brushing bismuth silicon boron system's low-melting-point nano glass dust suspension and preparation method Download PDFInfo
- Publication number
- CN106082682A CN106082682A CN201610428817.8A CN201610428817A CN106082682A CN 106082682 A CN106082682 A CN 106082682A CN 201610428817 A CN201610428817 A CN 201610428817A CN 106082682 A CN106082682 A CN 106082682A
- Authority
- CN
- China
- Prior art keywords
- glass
- low
- melting
- oxide
- glass dust
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 197
- 239000000428 dust Substances 0.000 title claims abstract description 65
- 239000000725 suspension Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- XRVSDHDAZKXFBY-UHFFFAOYSA-N [B].[Si].[Bi] Chemical compound [B].[Si].[Bi] XRVSDHDAZKXFBY-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000001680 brushing effect Effects 0.000 title claims abstract description 18
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 62
- 238000002844 melting Methods 0.000 claims abstract description 58
- 230000008018 melting Effects 0.000 claims abstract description 55
- 238000000498 ball milling Methods 0.000 claims abstract description 34
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 24
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 18
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004327 boric acid Substances 0.000 claims abstract description 9
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 7
- 238000005551 mechanical alloying Methods 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000001238 wet grinding Methods 0.000 claims abstract description 7
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- 239000006193 liquid solution Substances 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract description 17
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract description 17
- 238000005245 sintering Methods 0.000 abstract description 14
- 239000007921 spray Substances 0.000 abstract description 12
- 238000005034 decoration Methods 0.000 abstract description 5
- 239000005308 flint glass Substances 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000007639 printing Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 230000005496 eutectics Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010237 hybrid technique Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 238000003701 mechanical milling Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QDWNJWYHGDYFOG-UHFFFAOYSA-N [N+](=O)(O)[O-].[Li] Chemical compound [N+](=O)(O)[O-].[Li] QDWNJWYHGDYFOG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
Abstract
The invention belongs to glass decoration field, be particularly suited for glass air brushing field, particularly to a kind of glass air brushing bismuth silicon boron system's low-melting-point nano glass dust suspension and preparation method.It is characterized in that: solid-phase component raw material is bismuth oxide, amorphous silica, boric acid or boron oxide, lithium nitrate, aluminium oxide, zirconium oxide；First preparation method for making its preliminary mechanical alloying by carrying out high-energy ball milling after bismuth oxide, amorphous silica, aluminium oxide, zirconium oxide mix homogeneously, then the powder obtained by ball milling and boric acid or boron oxide, lithium nitrate mixing and ball milling, adds solvent wet grinding.The suspension that the present invention provides, solid phase particle diameter is at submicron or Nano grade, and the beginning temperature that glass powder with low melting point melts in a large number is 580～650 DEG C, in flint glass state after sintering on glass, high with glass adhesion, print field at glass numerial code spray drawing and be with a wide range of applications.
Description
Technical field
The invention belongs to glass decoration field, be particularly suited for glass air brushing field, use particularly to a kind of glass air brushing
Bismuth silicon boron system's low-melting-point nano glass dust suspension and preparation method.
Background technology
Raising living environment required along with development and the people of the industries such as building, automobile, decorations, furniture, people
More and more higher to the demand that glass is attractive in appearance, glass decoration is along fashion, personalization, art up, small lot, many
Pattern, the trend development of low-carbon environment-friendly.The ink of glass decoration has a variety of, is broadly divided into low-temperature quick-drying type and high temperature sintering
Type, wherein the usage of low-temperature quick-drying type glass ink be ink is coated onto on glass after, can be by through 50 DEG C～200 DEG C of bakings
Glass ink is fixedly arranged on glass, but this glass ink exists a lot of problem, such as poor adhesive force, does not bears dirty, the sourest
Caustic corrosion, fugitive color etc..The usage of high temperature sintering type ink be glass ink is coated on glass after, through 500 DEG C～700
DEG C high temperature glass ink is sintered on glass, glassy state can be presented after this ink high temperature sintering, there is adhesive force strong, resistance to
Dirty, be difficult to by advantages such as acid and alkali corrosions, not fugitive color, therefore, the market demand of this glass ink is more and more higher.
The main component of high temperature sintering glass ink is glass powder with low melting point, and the preparation of glass powder with low melting point is also that high temperature burns
The key technical problems of knot glass ink.
Chinese patent CN104893418 discloses a kind of leadless environment-friendly glass ink and preparation method, which includes low
The preparation method of melting glass frit, this method is that through the high melt of 1100 DEG C～1500 DEG C, each raw material is prepared glass
Liquid, then through shrend, the technique such as ball milling finally prepares glass powder with low melting point.Chinese patent CN104893410, United States Patent (USP)
U.S4892847, U.S5468695, U.S4554258 and U.S4892847 etc. all disclose similar high melt method to be prepared
The method of glass powder with low melting point, this method can prepare softening temperature at 500 DEG C～the glass dust of 700 DEG C, but this
Method needs the smelting temperature of more than 1000 DEG C just can make the abundant alloying of each raw material, and energy consumption is high, and preparation cost is high.And make
The glass dust particle diameter obtained is thick, generally individually more than 2 μm, is only applicable to the traditional printings such as silk screen printing, is not suitable for glass number
Inkjet printing is this needs the ink particle diameter advanced glass printing technology below 2 μm for code, and the scope of application is narrower.
United States Patent (USP) U.S 20120138215 discloses a kind of employing sol-gel process (sol-gel) and prepares low melting point glass
The method of glass powder, this preparation method can prepare the glass dust of Nano grade, but this preparation method is in process of production
Need to use NH4The chemical reagent such as OH, it is easy to form substantial amounts of chemical spent material, to bad environmental, and this method is to production
The requirement of equipment is the highest, and production cost is of a relatively high.
Summary of the invention
Present invention aims to above-mentioned the deficiencies in the prior art, it is provided that a kind of glass air brushing bismuth silicon boron system eutectic
Point nano-glass powder suspension and preparation method.
The technical solution used in the present invention is:
Glass air brushing bismuth silicon boron system low-melting-point nano glass dust suspension, it is characterised in that its solid-phase component i.e. eutectic
The raw material of some glass dust is bismuth oxide (α-type Bi2O3), amorphous silica (SiO2), boric acid (H3BO3) or boron oxide
(B2O3), lithium nitrate (LiNO3), aluminium oxide (Al2O3), zirconium oxide (ZrO2)。
Containing boric acid (H3BO3) formula as follows: bismuth oxide (α-type Bi2O3) mass percent be 27～32%, amorphous
State silicon oxide (SiO2) mass percent be 8～11%, boric acid (H3BO3) mass percent be 21～30%, lithium nitrate
(LiNO3) mass percent be 29～33%, aluminium oxide (Al2O3) mass percent be 2～3%, zirconium oxide (ZrO2)
Mass percent is 0.5～2%, and each component sum is 100%.
Containing boron oxide (B2O3) formula as follows: bismuth oxide (α-type Bi2O3) mass percent be 34.9～
43.3%, amorphous silica (SiO2) mass percent be 12.2～14.5%, boron oxide (B2O3) mass percent be
8～13.7%, lithium nitrate (LiNO3) mass percent be 29.3～37%, aluminium oxide (Al2O3) mass percent be 2.7
～3.4%, zirconium oxide (ZrO2) mass percent be 1.2～1.5%, each component sum is 100%.
Described bismuth oxide (α-type Bi in low-melting glass powder raw material2O3), amorphous silica (SiO2), aluminium oxide
(Al2O3), zirconium oxide (ZrO2) maximum particle diameter be both needed to less than 1 μm.
Described glass numerial code spray drawing printing bismuth silicon boron system low-melting-point nano glass dust suspension, it is characterised in that it
Liquid solution is a kind of or the most several mixture in 1,2-PD dimethyl ether, ethylene glycol monoethyl ether and Ketohexamethylene.
The preparation method of described glass numerial code spray drawing printing bismuth silicon boron system low-melting-point nano glass dust suspension, it is special
Levy and be that it is broadly divided into low-melting glass powder preparation technique and solid-liquid hybrid technique.
The preparation method of described glass powder with low melting point belongs to mechanical alloying method, i.e. makes by the method for purely mechanic ball milling
Each raw material mechanical alloying, mainly includes three below step:
1) bismuth oxide (α-type Bi is weighed by certain mass percent2O3), amorphous silica (SiO2), aluminium oxide
(Al2O3) and zirconium oxide (ZrO2), and be uniformly mixed；
2) above-mentioned raw materials prepared is placed in high energy ball mill carries out high-energy ball milling by certain ball milling parameter, make above-mentioned
Preliminary mechanical alloying between four kinds of raw material each components, takes out the powder of gained after ball milling certain time, for different types of ball
Grinding machine, ball milling parameter changes accordingly.
3) by the boric acid (H of powder obtained in the previous step Yu certain mass percent3BO3) or boron oxide (B2O3), nitric acid
Lithium (LiNO3) mix homogeneously, put in high energy ball mill by certain ball milling parameter ball milling certain time, available described low
Melting glass frit.
Described solid-liquid hybrid technique is wet grinding, mainly includes two steps that next coming in order sequence is carried out:
1) being put in ball grinder by the glass powder with low melting point prepared, then pour a certain amount of liquid solution into, liquid phase is molten
The mass ratio of liquid and glass powder with low melting point is 2-4:1, with certain wet grinding parameter wet grinding certain time, obtains glass dust suspended
Liquid.
2) glass dust suspension obtained in the previous step is taken out, filter, i.e. available described low-melting-point nano glass dust
Suspension.
Step 2 in the preparation method of described glass powder with low melting point) established standards of described ball milling parameter is Ball-milling Time
Being 8～24h, ball milling parameter is usually set to: rotating speed 400～600r/min, and ratio of grinding media to material sets 6-15:1.
Step 3 in the preparation method of described glass powder with low melting point) established standards of described ball milling parameter is Ball-milling Time
Being 12～24h, ball milling parameter is usually set to: rotating speed 400～600r/min, and ratio of grinding media to material sets 6-15:1.
Step 1 in described solid-liquid hybrid technique) established standards of described wet grinding parameter be Ball-milling Time be 12～48h,
Ball milling parameter is usually set to: rotating speed 400～600r/min, ratio of grinding media to material is set as 5-10:1.
The beginning temperature that described glass powder with low melting point melts in a large number is 580～650 DEG C.
The invention has the beneficial effects as follows:
(1) the glass numerial code spray drawing that the present invention provides prints with bismuth silicon boron system low-melting-point nano glass dust suspension, this
Bright novelty devise a kind of glass powder with low melting point formula, the difference maximum with prior art is to use first bismuth oxide
(α-type Bi2O3), amorphous silica (SiO2), boric acid (H3BO3) or boron oxide (B2O3) this ternary system prepares eutectic
Point glass dust, and use lithium nitrate (LiNO first3) it is used as the flux of glass powder with low melting point, right without any lead, thallium etc.
Human harmful substance, health environment-friendly, environmental friendliness.
(2) the glass numerial code spray drawing that the present invention provides prints with bismuth silicon boron system low-melting-point nano glass dust suspension, wherein
The particle diameter of glass dust is little, and the glass dust of boric acid formula can reach Nano grade at submicron rank, the glass dust of boron oxide formula,
Glass dust suspension in the solution is good, not free settling, uses in glass inkjet printing field, can greatly reduce ink and block ink-jet
The phenomenon of head.
(3) the glass numerial code spray drawing that the present invention provides prints with bismuth silicon boron system low-melting-point nano glass dust suspension, eutectic
The beginning temperature that some glass dust melts in a large number is 580～650 DEG C, after melt temperature is low, and spray sintering is on glass, in colourless
Glassy state, high with the adhesion of glass.
(4) low in the present invention provides glass numerial code spray drawing printing bismuth silicon boron system low-melting-point nano glass dust suspension
The preparation method of melting glass frit is mechanical alloying method, overcomes prior art fusion method and the deficiency of sol-gel method, does not contains
High-temperature process, energy consumption is low, and production cost is low, and does not produce environmentally harmful waste material, environmental friendliness in production process.
Accompanying drawing explanation
Fig. 1 is the DSC figure of the glass powder with low melting point of the embodiment of the present invention one preparation.
Fig. 2 is that the glass numerial code spray drawing printing bismuth silicon boron system low-melting-point nano glass dust that the present invention implements prepared by an example hangs
The laser particle analyzer figure of turbid liquid.
Fig. 3 is the XRD figure of the glass powder with low melting point of the embodiment of the present invention one preparation.
Fig. 4 is the DSC figure of the glass powder with low melting point of the embodiment of the present invention two preparation.
Fig. 5 is that the glass numerial code spray drawing printing bismuth silicon boron system low-melting-point nano glass dust that the present invention implements prepared by two examples hangs
The laser particle analyzer figure of turbid liquid.
Fig. 6 is the XRD figure of the glass powder with low melting point of the embodiment of the present invention two preparation.
Fig. 7 is the DSC figure of the glass powder with low melting point of the embodiment of the present invention three preparation.
Fig. 8 is that the glass numerial code spray drawing printing bismuth silicon boron system low-melting-point nano glass dust that the present invention implements prepared by three examples hangs
The laser particle analyzer figure of turbid liquid.
Fig. 9 is the XRD figure of the glass powder with low melting point of the embodiment of the present invention three preparation.
Figure 10 is the DSC figure of the glass powder with low melting point of the embodiment of the present invention four preparation.
Figure 11 is the glass numerial code spray drawing printing bismuth silicon boron system low-melting-point nano glass dust that the present invention implements prepared by four examples
The laser particle analyzer figure of suspension.
Figure 12 is the XRD figure of the glass powder with low melting point of the embodiment of the present invention four preparation.
Figure 13 is that suspension prepared by embodiment one is coated onto un-sintered front photo on glass.
Figure 14 is the photo after suspension prepared by embodiment one is coated onto on glass sintering.
Figure 15 is that suspension prepared by embodiment four is coated onto un-sintered front photo on glass.
Figure 16 is the photo after suspension prepared by embodiment four is coated onto on glass sintering.
Detailed description of the invention
The present invention is further illustrated with embodiment below in conjunction with the accompanying drawings.
Embodiment one
Glass air brushing bismuth silicon boron system low-melting-point nano glass dust suspension, its preparation method is:
The present embodiment uses 500ml nylon ball grinder, every time mill 40g glass powder with low melting point, first according to bismuth oxide (α-type
Bi2O3) 31.4%, amorphous silica (SiO2) 10.7%, boric acid (H3BO3) 22%, lithium nitrate (LiNO3) 32.3%, oxidation
Aluminum (Al2O3) 2.5%, zirconium oxide (ZrO2) 1.1% mass percent, calculate required for ball milling 40g glass powder with low melting point
Each raw materials quality, bismuth oxide (α-type Bi2O3) 12.56 grams, amorphous silica (SiO2) 4.28 grams, boric acid (H3BO3) 8.8 grams,
Lithium nitrate (LiNO3) 12.92 grams, aluminium oxide (Al2O3) 1 gram, zirconium oxide (ZrO2) 0.44 gram then according to result of calculation weighs.
Secondly, by load weighted raw material bismuth oxide (α-type Bi2O3), amorphous silica (SiO2), aluminium oxide (Al2O3) and
Zirconium oxide (ZrO2) be placed in beaker, stirring, the ratio of grinding media to material according still further to 13:1 weighs about 237g agate ball.
Then, above-mentioned four kinds of raw materials and agate ball are poured in ball grinder together, start ball milling, in mechanical milling process,
Rotating speed 500r/min, ball milling 10h, take out the powder body obtained in ball grinder.
Then, the powder body upper step obtained and load weighted boric acid (H3BO3) and lithium nitrate (LiNO3) mix homogeneously, then
Weigh 240g agate ball according to the ratio of grinding media to material of 6:1, above-mentioned raw materials and agate ball poured in ball grinder together, start ball milling,
In mechanical milling process, rotating speed 500r/min, after ball milling 10h, stop ball milling, obtain described glass powder with low melting point；
Finally, then in the glass dust of upper step gained, add the 1,2-PD dimethyl ether of 120ml, rotating speed 500r/min,
Ball milling 48h, stops ball milling, is filtered the glass dust suspension of gained, i.e. to described bismuth silicon boron system low-melting-point nano glass
Powder suspension.
The low-melting-point nano glass dust suspension that the present embodiment obtains, color is white, and sedimentation experiment finds, this suspension
After preparing, within more than one month, just can settle, and only need agitation as appropriate after sedimentation, just can revert to suspension, therefore this product
Glass dust suspension in the solution is good, not free settling.
Fig. 1 show the DSC figure of the finished product glass powder with low melting point of the present embodiment gained, can obtain this enforcement by analysis
The beginning temperature that the glass powder with low melting point that example prepares melts in a large number is 637 DEG C.
Detect the finished product glass powder with low melting point of the present embodiment gained with laser particle analyzer, result is as in figure 2 it is shown, can from figure
To find out that the glass dust mean diameter of the present embodiment gained, at about 838nm, belongs to submicron rank.
Fig. 3 show the XRD figure spectrum of the finished product glass powder with low melting point of the present embodiment gained, by analysis, it was found that
Bi2Zr、Al1.67B22、Al2Zr、B12Zr、Si3Zr5Deng thing phase, thus can be with each raw material components of inference abundant mechanical alloy
Change.
Embodiment two
The present embodiment is similar with embodiment one experimental technique, and difference is that the mass percent shared by raw material is different.
According to bismuth oxide (α-type Bi2O3) 29.8%, amorphous silica (SiO2) 10.1%, boric acid (H3BO3) 26.2%, lithium nitrate
(LiNO3) 30.6%, aluminium oxide (Al2O3) 2.3%, zirconium oxide (ZrO2) 1% mass percent, calculate ball milling 40g eutectic
Each raw materials quality required for some glass dust, bismuth oxide (α-type Bi2O3) 11.92 grams, amorphous silica (SiO2) 4.04 grams,
Boric acid (H3BO3) 10.48 grams, lithium nitrate (LiNO3) 12.24 grams, aluminium oxide (Al2O3) 0.92 gram, zirconium oxide (ZrO2) 0.4 gram,
Then according to result of calculation weighs, below step is completely the same with embodiment 1.
The low-melting-point nano glass dust suspension that the present embodiment obtains, color is white, the glass dust obtained with embodiment 1
Color class is same, and suspension is similar.
Fig. 4 show the DSC figure of the finished product glass powder with low melting point of the present embodiment gained, can obtain this enforcement by analysis
The beginning temperature that the glass powder with low melting point that example prepares melts in a large number is 608 DEG C.
Detect the finished product glass powder with low melting point of the present embodiment gained with laser particle analyzer, result is as it is shown in figure 5, can from figure
To find out that the glass dust particle diameter of the present embodiment gained, at about 465nm, belongs to submicron rank.
Fig. 6 show the XRD figure spectrum of the finished product glass powder with low melting point of the present embodiment gained, by analysis, it was found that
Bi2Zr、Al1.67B22、Al2Zr、B12Zr、Si3Zr5Deng thing phase, thus can be with each raw material components of inference abundant mechanical alloy
Change.
Embodiment three
The present embodiment is similar with embodiment one experimental technique, and difference is that the mass percent shared by raw material is different.
According to bismuth oxide (α-type Bi2O3) 28.3%, amorphous silica (SiO2) 9.6%, boric acid (H3BO3) 29.8%, lithium nitrate
(LiNO3) 29.1%, aluminium oxide (Al2O3) 2.2%, zirconium oxide (ZrO2) 1% mass percent, calculate ball milling 40g eutectic
Each raw materials quality required for some glass dust, bismuth oxide (α-type Bi2O3) 11.32 grams, amorphous silica (SiO2) 3.84 grams,
Boric acid (H3BO3) 11.92 grams, lithium nitrate (LiNO3) 11.64 grams, aluminium oxide (Al2O3) 0.88 gram, zirconium oxide (ZrO2) 0.4 gram,
Then according to result of calculation weighs, below step is completely the same with embodiment 1.
The low-melting-point nano glass dust suspension that the present embodiment obtains, color is white, and suspension is similar, with embodiment 1
The glass dust color class obtained is same.
Fig. 7 show the DSC figure of the finished product glass powder with low melting point of the present embodiment gained, can obtain this enforcement by analysis
The beginning temperature that the glass powder with low melting point that example prepares melts in a large number is 580 DEG C.
Detect the finished product glass powder with low melting point of the present embodiment gained with laser particle analyzer, result as shown in Figure 8, can from figure
To find out that the glass dust mean diameter of the present embodiment gained, at about 721nm, belongs to submicron rank.
Fig. 9 show the XRD figure spectrum of the finished product glass powder with low melting point of the present embodiment gained, by analysis, it was found that
Bi2Zr、Al1.67B22、Al2Zr、B12Zr、Si3Zr5Deng thing phase, thus can be with each raw material components of inference abundant mechanical alloy
Change.
Embodiment four
The present embodiment is similar with embodiment one preparation method, but has two differences: (1) raw material mesoboric acid (H3BO3) change
For boron oxide (B2O3)；(2) mass percent shared by each raw material is different.
According to bismuth oxide (α-type Bi2O3) 36%, amorphous silica (SiO2) 12.2%, boron oxide (B2O3) 10.7%,
Lithium nitrate (LiNO3) 37%, aluminium oxide (Al2O3) 2.8%, zirconium oxide (ZrO2) 1.3% mass percent, calculate ball milling
Each raw materials quality required for 35g glass powder with low melting point, bismuth oxide (α-type Bi2O3) 12.6 grams, amorphous silica (SiO2)
4.27 grams, boron oxide (B2O3) 3.75 grams, lithium nitrate (LiNO3) 12.95 grams, aluminium oxide (Al2O3) 0.98 gram, zirconium oxide (ZrO2)
0.45 gram, then according to result of calculation weighs, below step is completely the same with embodiment 1.
The low-melting-point nano glass dust suspension that the present embodiment obtains, color is yellow, the glass dust obtained with embodiment 1
Color is different, but suspension is similar.
Figure 10 show the DSC figure of the finished product glass powder with low melting point of the present embodiment gained, can obtain this reality by analysis
Executing the beginning temperature melted in a large number of glass powder with low melting point that example prepares is 626 DEG C.
Detect the finished product glass powder with low melting point of the present embodiment gained with laser particle analyzer, result as shown in figure 11, from figure
Can be seen that the glass dust particle diameter of the present embodiment gained, at about 67nm, belongs to Nano grade.
Figure 12 show the XRD figure spectrum of the finished product glass powder with low melting point of the present embodiment gained, by analysis, it was found that
BiZr、Al3.24B44、LiAl、B12Zr、Zr5Si4Deng thing phase, thus can be with the fully mechanical alloying of each raw material components of inference.
Embodiment five
White low-melting-point nano glass dust suspension prepared by embodiment one is sintered on glass, specifically by the present embodiment
Implementing step is: white suspension embodiment one prepared is coated onto on glass uniformly, and glass uses common Gao Guang
Glass, as shown in figure 13, then dries up the white suspension on glass, puts into temperature and reached the high temperature resistance of 680 DEG C
Sintering 3～4 minutes in stove, then take out, cooling, after cooling, sintering effect is as shown in figure 14, it can be seen that low melting point after sintering
Glass dust presents flint glass state, has substantially been dissolved in glass, good with the adhesion of glass, and prepared by embodiment two and three white
Sintering effect between color low-melting-point nano glass dust suspension and glass is similar with the present embodiment.
Embodiment six
Yellow low-melting-point nano glass dust suspension prepared by embodiment four is sintered on glass, specifically by the present embodiment
Implementing step is: yellow suspension embodiment four prepared is coated onto on glass uniformly, and glass uses common Gao Guang
Glass, as shown in figure 15, then dries up the yellow suspension on glass, puts into temperature and has reached the high temperature resistance of 680 DEG C
Sintering 3～4 minutes in stove, then take out, cooling, after sintering, glass powder with low melting point presents flint glass state, is substantially dissolved into
In glass, as shown in figure 16, the best with the adhesion of glass.
Below part formulation, in actual applications, the quality of each raw material in the formula of glass powder with low melting point only it are enumerated
Percentage ratio can change within the specific limits, coordinates the variation of Ball-milling Time, can produce the low melting point with different softening temperature
Glass dust.
Part that the present invention does not relate to is the most same as the prior art maybe can use prior art to be realized.
Claims (9)
1. glass air brushing bismuth silicon boron system low-melting-point nano glass dust suspension, is mixed by glass powder with low melting point and liquid solution solid-liquid
Conjunction forms, it is characterised in that: the component of described glass powder with low melting point is: α-type Bi2O3, amorphous silica, boric acid or oxidation
Boron, lithium nitrate, aluminium oxide, zirconium oxide；
Formula containing boric acid is as follows: α-type Bi2O3Mass percent be 27～32%, the percent mass of amorphous silica
Ratio is 8～11%, and the mass percent of boric acid is 21～30%, and the mass percent of lithium nitrate is 29～33%, aluminium oxide
Mass percent is 2～3%, and zirconic mass percent is 0.5～2%, and each component sum is 100%；
Formula containing boron oxide is as follows: α-type Bi2O3Mass percent be 34.9～43.3%, the matter of amorphous silica
Amount percentage ratio is 12.2～14.5%, and the mass percent of boron oxide is 8～13.7%, and the mass percent of lithium nitrate is 29.3
～37%, the mass percent of aluminium oxide is 2.7～3.4%, and zirconic mass percent is 1.2～1.5%, each component it
With for 100%.
2. glass air brushing as claimed in claim 1 bismuth silicon boron system low-melting-point nano glass dust suspension, it is characterised in that: institute
α-type Bi in the low-melting glass powder raw material stated2O3, amorphous silica, aluminium oxide, zirconic maximum particle diameter be both needed to be less than
1μm。
3. glass air brushing as claimed in claim 1 bismuth silicon boron system low-melting-point nano glass dust suspension, it is characterised in that: institute
Stating liquid solution is a kind of or the most several mixture in 1,2-PD dimethyl ether, ethylene glycol monoethyl ether and Ketohexamethylene.
4. glass air brushing as claimed in claim 1 bismuth silicon boron system low-melting-point nano glass dust suspension, it is characterised in that: institute
Stating the beginning temperature that glass powder with low melting point melts in a large number is 580～650 DEG C.
5. glass air brushing as claimed in claim 1 bismuth silicon boron system low-melting-point nano glass dust suspension, it is characterised in that: contain
The glass dust particle diameter having boric acid formula can reach Nano grade at submicron rank, the glass dust particle diameter containing boron oxide formula,
Glass dust suspension in the solution is good, not free settling, within more than one month, just can settle, and only needs agitation as appropriate, with regard to energy after sedimentation
Revert to suspension.
6. the glass air brushing as claimed in claim 1 preparation method of bismuth silicon boron system low-melting-point nano glass dust suspension, its
It is characterised by, specifically comprises the following steps that
1) α-type Bi is weighed by mass percentage2O3, amorphous silica, aluminium oxide and zirconium oxide, and be uniformly mixed；
2) above-mentioned raw materials prepared is placed in high energy ball mill carries out high-energy ball milling, make between above-mentioned four kinds of raw material each components preliminary
Mechanical alloying, takes out the powder of gained after ball milling；
3) by step 2) powder that obtains and boric acid or boron oxide, lithium nitrate mix homogeneously, and puts into ball milling in high energy ball mill,
Obtain described glass powder with low melting point；
4) glass powder with low melting point prepared is put in ball grinder, then pour liquid solution into, liquid solution and low melting point glass
The mass ratio of glass powder is 2-4:1, and wet grinding obtains glass dust suspension；
5) by step 4) the glass dust suspension that obtains takes out, filters, and i.e. available described low-melting-point nano glass dust is suspended
Liquid.
7. the glass air brushing as claimed in claim 6 preparation method of bismuth silicon boron system low-melting-point nano glass dust suspension, its
It is characterised by: step 2) in, Ball-milling Time is 8～24h, rotating speed 400～600r/min, and ratio of grinding media to material sets 6-15:1.
8. the glass air brushing as claimed in claim 6 preparation method of bismuth silicon boron system low-melting-point nano glass dust suspension, its
It is characterised by: step 3) in, Ball-milling Time is 12～24h, rotating speed 400～600r/min, and ratio of grinding media to material sets 6-15:1.
9. the glass air brushing as claimed in claim 6 preparation method of bismuth silicon boron system low-melting-point nano glass dust suspension, its
It is characterised by: step 4) in, the Ball-milling Time of wet grinding is 12～48h, rotating speed 400～600r/min, and ratio of grinding media to material is set as 5-10:
1。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610428817.8A CN106082682A (en) | 2016-06-16 | 2016-06-16 | Glass air brushing bismuth silicon boron system's low-melting-point nano glass dust suspension and preparation method |
| PCT/CN2016/094098 WO2017215099A1 (en) | 2016-06-16 | 2016-08-09 | Bismuth-silicon-boron-based low-melting-point nano glass powder suspension for glass jet drawing and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610428817.8A CN106082682A (en) | 2016-06-16 | 2016-06-16 | Glass air brushing bismuth silicon boron system's low-melting-point nano glass dust suspension and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106082682A true CN106082682A (en) | 2016-11-09 |
Family
ID=57235305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610428817.8A Pending CN106082682A (en) | 2016-06-16 | 2016-06-16 | Glass air brushing bismuth silicon boron system's low-melting-point nano glass dust suspension and preparation method |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN106082682A (en) |
| WO (1) | WO2017215099A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107352806A (en) * | 2017-08-14 | 2017-11-17 | 广东工业大学 | Print glass ink coloured glass powder and its preparation method and application |
| CN111187006A (en) * | 2020-02-22 | 2020-05-22 | 刘世伟 | Low-melting-point powder special for high-temperature sintering printing ink and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080210122A1 (en) * | 2003-08-25 | 2008-09-04 | Dip Tech. Ltd. | Ink for Ceramic Surfaces |
| US20140243185A1 (en) * | 2011-10-20 | 2014-08-28 | Inha-Industry Partnership Institute | Method and apparatus for manufacturing a low melting point nano glass powder |
| CN105062199A (en) * | 2015-09-02 | 2015-11-18 | 江苏繁华玻璃股份有限公司 | Bismuth-oxide-base ink for glass digital inkjet printing and preparation method thereof |
| CN105086623A (en) * | 2015-09-02 | 2015-11-25 | 江苏繁华玻璃股份有限公司 | Bismuth oxide-based white pigment for digital glass ink-jet printing and preparation method of pigment |
| CN105111822A (en) * | 2015-09-02 | 2015-12-02 | 江苏繁华玻璃股份有限公司 | Solvent of bismuth-oxide-base ink for glass digital inkjet printing |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE59802213D1 (en) * | 1997-08-08 | 2002-01-10 | Dmc2 Degussa Metals Catalysts | Lead-free glass compositions with a low melting point |
| CN105062198A (en) * | 2015-09-02 | 2015-11-18 | 江苏大学 | Bismuth-oxide-based black pigment used for glass digital inkjet printing and preparation method of bismuth-oxide-based black pigment |
| CN105086622A (en) * | 2015-09-02 | 2015-11-25 | 江苏大学 | Bismuth oxide-based yellow pigment for digital glass ink-jet printing and preparation method of pigment |
| CN105062215A (en) * | 2015-09-02 | 2015-11-18 | 江苏大学 | Bismuth-oxide-base red pigment for glass digital inkjet printing and preparation method thereof |
| CN105084375A (en) * | 2015-09-02 | 2015-11-25 | 江苏大学 | Submicron bismuth silicate powder for glass printing ink and preparation method |
| CN105131714A (en) * | 2015-09-02 | 2015-12-09 | 江苏大学 | Bismuth oxide based green pigment for glass digital jet printing and preparation method thereof |
| CN105062216A (en) * | 2015-09-02 | 2015-11-18 | 江苏大学 | Bismuth oxide-based blue pigment for digital air-brush and printing of glass and preparation method thereof |
| CN106085006A (en) * | 2016-06-16 | 2016-11-09 | 江苏大学 | Glass surface inkjet printing bismuth silicon boron system low melting point ink and preparation method thereof |
-
2016
- 2016-06-16 CN CN201610428817.8A patent/CN106082682A/en active Pending
- 2016-08-09 WO PCT/CN2016/094098 patent/WO2017215099A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080210122A1 (en) * | 2003-08-25 | 2008-09-04 | Dip Tech. Ltd. | Ink for Ceramic Surfaces |
| US20140243185A1 (en) * | 2011-10-20 | 2014-08-28 | Inha-Industry Partnership Institute | Method and apparatus for manufacturing a low melting point nano glass powder |
| CN105062199A (en) * | 2015-09-02 | 2015-11-18 | 江苏繁华玻璃股份有限公司 | Bismuth-oxide-base ink for glass digital inkjet printing and preparation method thereof |
| CN105086623A (en) * | 2015-09-02 | 2015-11-25 | 江苏繁华玻璃股份有限公司 | Bismuth oxide-based white pigment for digital glass ink-jet printing and preparation method of pigment |
| CN105111822A (en) * | 2015-09-02 | 2015-12-02 | 江苏繁华玻璃股份有限公司 | Solvent of bismuth-oxide-base ink for glass digital inkjet printing |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107352806A (en) * | 2017-08-14 | 2017-11-17 | 广东工业大学 | Print glass ink coloured glass powder and its preparation method and application |
| CN107352806B (en) * | 2017-08-14 | 2020-12-15 | 广东工业大学 | Colored glass powder for printing glass ink and preparation method and application thereof |
| CN111187006A (en) * | 2020-02-22 | 2020-05-22 | 刘世伟 | Low-melting-point powder special for high-temperature sintering printing ink and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017215099A1 (en) | 2017-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2017215111A1 (en) | Bismuth-silicon-boron type low-melting-point ink for glass surface spray painting and printing and preparation method therefor | |
| CN104860720B (en) | Ceramic decoration high temperature scarlet color ink-jet ink and preparation method and applications | |
| CN103177791B (en) | A kind of aluminum conductive electric slurry used for solar batteries and preparation method thereof | |
| CN107141888B (en) | A kind of inorganic frit of tempered glass ink-jet printing ink and its tempered glass of automobile ink-jet printing ink being formulated | |
| CN103295659B (en) | Conductive paste for solar cell and preparation method thereof | |
| CN106082682A (en) | Glass air brushing bismuth silicon boron system's low-melting-point nano glass dust suspension and preparation method | |
| CN103295662A (en) | Electrocondution slurry for solar cell and manufacturing method thereof | |
| CN105086623A (en) | Bismuth oxide-based white pigment for digital glass ink-jet printing and preparation method of pigment | |
| CN103183474B (en) | A kind of unorganic glass powder and preparation method thereof, a kind of electrocondution slurry and preparation method thereof | |
| CN108384312A (en) | A kind of high temperature cut resistant black ink and preparation method thereof | |
| CN105062198A (en) | Bismuth-oxide-based black pigment used for glass digital inkjet printing and preparation method of bismuth-oxide-based black pigment | |
| CN103204632B (en) | Conductive glass powder and preparation method thereof, crystal silicon solar energy battery aluminum conductive electric slurry and preparation method | |
| CN105968889A (en) | Low temperature lead-free green glass paste | |
| CN108752051A (en) | A kind of preparation method of thermostabilization high tenacity ceramic glaze | |
| CN104496546A (en) | Vanadium zirconium blue ceramic pigment | |
| CN103093862B (en) | A kind of conductive silver slurry used for solar batteries | |
| CN101984493B (en) | Lead-free environment-friendly electronic aluminum paste and preparation method thereof | |
| CN100455529C (en) | Production of optical glass and colour glass under low-temperature | |
| CN110669385A (en) | High-acid-alkali-resistance white environment-friendly slurry and preparation method thereof | |
| CN103426496A (en) | Aluminum back field slurry applied to solar battery, preparation method thereof, preparation method of solar battery piece and solar battery piece | |
| CN111333335B (en) | High-acid-resistance automobile glass printing ink and preparation method thereof | |
| CN104449045B (en) | A kind of preparation method of colored glazed glass jet ink | |
| CN104529541A (en) | Preparation method for modified fused zirconia and praseodymium yellow pigment | |
| CN104318979A (en) | Composite-material-based thick-film circuit rare earth electrode slurry and preparation process thereof | |
| CN105062215A (en) | Bismuth-oxide-base red pigment for glass digital inkjet printing and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161109 |