CN1044595C - Leadless cadmiumless ceramic glazing pigment - Google Patents

Leadless cadmiumless ceramic glazing pigment Download PDF

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Publication number
CN1044595C
CN1044595C CN94114181A CN94114181A CN1044595C CN 1044595 C CN1044595 C CN 1044595C CN 94114181 A CN94114181 A CN 94114181A CN 94114181 A CN94114181 A CN 94114181A CN 1044595 C CN1044595 C CN 1044595C
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flux
mol
cadmiumless
sio
zrsio
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CN1128246A (en
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殷书建
张新华
张晓峰
张宇红
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Shandong Silicon Garden New Material Technology Co ltd
Zibo Fulu New Material LLC
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Shandong silicate research and design institute
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    • 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
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • 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
    • C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
    • 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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/80—Optical properties, e.g. transparency or reflexibility
    • C04B2111/82—Coloured materials

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention relates to ceramic glaze paint without lead or cadmium, which is prepared from 70 to 95 wt% of fusing agents and 5 to 30 wt% of coloring agents, wherein the fusing agents are composed of main body fusing agents, composite fluxing agents, stabilizing agents and auxiliary coloration agents, and the main body fusing agents are composed of 55.0 to 80.0 mol% of SiO2, 3.0 to 15.0 mol% of B2O3, 1.0 to 8.5 mol% of Bi2O3 and 1.0 to 9.0 mol% of Al2O3; the composite fluxing agents are composed of two kinds of alkali metal oxide and alkaline earth oxide; the stabilizing agents are composed of ZrSiO4, SnD2 and La2O3; and the auxiliary coloration agents are selected from Mgo, Cao , Zno and TiO2. The paint has the advantages of complete hue, pure and flamboyant coloration, acid resistance and alkali resistance, is suitable for screen printing, planographic printing and spraydecoration processes, and is used for decorating various ceramic glaze surfaces.

Description

Leadless cadmiumless ceramic glazing pigment and preparation method thereof
The present invention relates to a kind of leadless cadmiumless ceramic glazing pigment, belong to beramic color, it comprises toner and molten Ji.
Colour on glazed ceramics is given ceramic with beautiful outward appearance, and PbO has made outstanding contribution as the component of flux for pigment for the color generation property of the low and broad roasting burning temperature of colour on glazed ceramics, pure light; CdO is serving as important role with the gorgeous color of uniqueness again in colour on glazed ceramics.Therefore, PbO, CdO are prolonged usefulness always in the traditional ceramics pigment formula from ancient times to the present.Yet lead, cadmium and compound thereof are virulent to human beings'health, and the someone confirms: " plumbic acetate and all plumbous compounds are potential carcinogenic substances ".The health that the lead on domestic ceramics utensil, especially tableware, kitchenware surface, cadmium melt to people constitutes a threat to.Therefore the toxicity of PbO, CdO is fatal defective to its application as the colour on glazed ceramics component.For reducing and eradicate the murder by poisoning of lead, cadmium, the scientific research institution and the production department of ceramic industry are both at home and abroad doing unremitting effort always, disclose a kind of cover-coat for colour on glazed ceramics and processing and goods in Chinese patent application CN93110379.7, its purpose provides a kind of lead, the molten output of cadmium is lower than 0.3mg dm 2The cover layer, its shortcoming is complex process and does not eradicate lead poisoning.Revealed a kind of finishing material in English Patent CB2250285A, its purpose provides a kind of composition of unleaded ceramic pigment flux, and its formation is (mol%):
SiO 2 50～70
Bi 2O 3 10～40
Ai 2O 3 3～30
B 2O 3 0～15
Li 2O 0～10
Na 2O 0～10
K 2O 0～10
MgO 0～5
CaO 0～10
ZnO 0～10
ZrO 2 0～5
TiO 2 0～5
SnO 0～5
MoO 2 0～3
Rare earth 0～3
And 750～1050 ℃ of the roasting burning temperature of the flux that makes from the composition of above-mentioned formula optimization are disclosed, thermal expansivity is 7.0～12.0 * 10 -6℃ -1There is following deficiency in above-mentioned obviously flux for pigment:
A, chemical stability are relatively poor.Because Bi 2O 3Too much introducing cause the glass phase-splitting easily, be difficult for to form the uniform glass body and cause flux structure mercapto pine, it is also bad therefore to influence chemical stability acid-fast alkali-proof performance.
B, Bi 2O 3Too much adding not just also can not cause the toner colour generation, especially obvious to golden red influence, to making its color development purple partially, can not present normal golden red.
C, thermal expansivity are higher, easily cause " burst porcelain " and influence product life.
D, Bi 2O 3Price higher, consumption is more, can improve the cost of product and influences the market competitiveness of commodity.
The objective of the invention is to avoid above-mentioned weak point of the prior art and provide that a kind of compact structure chemical stability is good, acid-fast alkali-proof, thermal expansivity are low, good springiness, the useless height of the pure gloss beautiful in colour of colour generation and lower-cost leadless cadmiumless ceramic glazing pigment.Thereby thoroughly eliminated the harm that plumbous cadmium causes in the waste water and gas that discharges in the plumbous cadmium stripping on ceramic utensil surface and the beramic color production environmental pollution brings to people completely.
Purpose of the present invention can reach by following measure: the invention provides a kind of leadless cadmiumless ceramic glazing pigment, be made up of the toner of the not leaded cadmium composition of the flux of the not leaded cadmium composition of 70%～95% weight and 5%～30% weight; Wherein flux constitutes (mol%) by following component:
A, main body flux comprise following component:
SiO 2 55.0～80.0
B 2O 3 3.0～15.0
Bi 2O 3 1.0～8.5
Al 2O 3 1.0～9.0
B, composite fluxing agent are at least two kinds of alkalimetal oxides choosing from following component and a kind of combination of alkaline earth metal oxide:
K 2O 0～9.0
Na 2O 0～9.0
Li 2O 0～9.0
BaO 0～4.0
SrO 0～4.0
C, stablizer comprise following component:
ZrSiO 4 1.5～12.0
SnO 2 0.3～8.5
La 2O 3 0～1.0
D, colour generation auxiliary agent, from following component, choose at least a or two more than the combination:
MgO 0～3.0
CaO 0～6.0
ZnO 0～4.0
TiO 2 0～3.0
Main body flux of the present invention has been selected the SiO of higher resultant for use 2Bi with low resultant 2O 3And an amount of Al 2O 3And B 2O 3Pure with the preparation colour generation for the glass structure that forms even compact, the pigment that chemical stability is good is laid a good foundation; The composite fluxing agent of being made up of basic metal and alkaline-earth metal when reducing the flux melt temperature, has improved the acid resistance of pigment greatly by the dry blending alkali effect, cheap ZrSiO in the stabilizer component 4Make the structure of glass tightr, for the chemical stability that improves pigment has been made outstanding contribution, face and remedied increase together because of the caused coefficient of expansion of adding of alkali metal alkaline earth metal fusing assistant in league with other components in the stablizer; The colour generation auxiliary agent is the pure important component beautiful in colour of lead-free and cadmium-free over-glaze pigment colour generation of the present invention.The prescription of the big component scientific and precise of four in the flux component makes to set up jointly between branchs and remedies mutually, additionally mutually provides ideal flux for pigment of the present invention.
Purpose of the present invention can also reach by following measure: a kind of preferred flux formula range (mol%) at first is provided:
A, main body flux comprise following component:
SiO 2 65.0～76.0
B 2O 3 5.0～12.0
Bi 2O 3 2.2～6.7
Al 2O 3 3.5～8.1
B, composite fluxing agent are at least two kinds of alkalimetal oxides choosing from following component and a kind of combination of alkaline earth metal oxide:
K 2O 0～5.7
Na 2O 0～6.8
Li 2O 0～8.2
BaO 0～3.0
SrO 0～3.2
C, stablizer comprise following component:
ZrSiO 4 2.0～7.1
SnO 2 0.5～4.2
La 2O 3 0～0.6
D, colour generation auxiliary agent, from following component, choose at least a or two more than the combination:
MgO 0～2.2
CaO 0～4.3
ZnO 0～3.0
TiO 2 0～2.0
Flux of the present invention can cooperate with multiple toner is organic, and it is lower to make the roasting temperature of burning, the glossiness height, and chemical stability is good, the leadless cadmiumless ceramic glazing pigment that color is pure, clear, bright-coloured, true to nature.The flux (mol%) composed as follows that wherein is suitable for dark green, blue green, light green, light green, Hai Lan, lake orchid, pitch black, silver grey, a white class toner:
SiO 2 55.0～70.0
Bi 2O 3 3.0～8.2
B 2O 3 3.0～15.0
Al 2O 3 3.0～7.0
Li 2O 1.0～8.0
Na 2O 1.0～9.0
K 2O 0～9.0
BaO 0.1～1.1
ZrSiO 4： 1.0～12.0
SnO 2 0.1～4.0
La 2O 3 0～1.0
MgO 0.1～3.0
CaO 0～3.0
ZnO 0.1～2.0
A kind of flux (mol%) composed as follows that is fit to do purplish red, dark red, pink, a purple blue class toner:
SiO 2 66.0～80.0
Bi 2O 3 3.0～6.0
Ai 2O 3 3.0～8.0
B 2O 3 3.0～1 2.0
Na 2O 1.0～8.0
K 2O 1.0～8.0
SrO 1.0～3.0
ZrSiO 4 2.0～9.0
SnO 2 3.0～8.5
ZnO 0.1～3.0
TiO 2 0.5～3.0
A kind of beans tea, red deeply, west red, shallow flux red, ochre one class toner (mol%) composed as follows of being suitable for:
SiO 2 65.0～70.0
Bi 2O 3 1.5～3.5
Al 2O 3 4.0～9.0
B 2O 3 3.0～12.0
Li 2O 4.0～6.0
K 2O 0.1～3.0
BaO 1.0～3.0
SrO 0～4.0
ZrSiO 4 2.0～10.0
SnO 2 1.0～3.0
La 2O 3 0.1～1.0
CaO 0.5～3.0
ZnO 0.1～3.0
A kind of flux (mol%) composed as follows that is suitable for not having golden pink class toner:
SiO 2 61.0～70.0
Bi 2O 3 2.0～3.5
Al 2O 3 2.0～7.0
B 2O 3 4.0～13.0
Li 2O 5.0～9.0
Na 2O 0.5～2.0
SrO 0.1～1.5
ZrSiO 4 2.0～4.0
SnO 2 3.0～4.1
La 2O 3 0.1～0.5
CaO 2.0～5.2
A kind of flux (mol%) composed as follows that is suitable for cobalt aluminate class toner:
SiO 2 65.0～75.0
Bi 2O 3 2.0～3.5
Al 2O 3 3.0～5.0
B 2O 3 3.0～10.0
Na 2O 2. 0～5.0
K 2O 0.5～3.0
BaO 0.1～4.0
ZrSiO 4 1.5～10.0
SnO 2 0.5～2.0
MgO 0～3.0
ZnO 1.0～4.0
A kind of flux (mol%) composed as follows of be suitable for suckling yellow peach, golden yellow class toner:
SiO 2 60.0～80.0
Bi 2O 3 2.0～3.5
Al 2O 3 1.0～6.0
B 2O 3 5.0～14.0
Li 2O 1.0～6.0
K 2O 1.0～3.5
BaO 0.1～1.5
ZrSiO 4 1.5～6.0
SnO 2 0.5～2.0
La 2O 3 0.1～0.4
TiO 2 1.0～3.0
Leadless cadmiumless ceramic glazing pigment of the present invention follows these steps to preparation:
The preparation of a, flux: mixed the fusion under 1250 ℃～1300 ℃ temperature of 60 mesh sieves after measuring respectively by the flux furnish component, molten pour into after good quench in the cold water broken;
B, mixing and ball milling: with the toner mixing and ball milling of the flux of 70%～95% kind of weight and 5%～30% weight to fineness 10um;
C, resintering, shrend, ball milling: with flux and toner through the resintering under 800～850 ℃ of temperature of the mixture behind the ball milling, after the shrend in ball milling wet-milling to fineness 5um;
D, oven dry, pulverizing, packing.
The pigment that makes according to the composition and the preparation method of leadless cadmiumless ceramic glazing pigment of the present invention is 200 ℃～850 ℃ roasting burnings in ceramic surface, and it is as follows that its technical feature is made following test result:
A, glossiness: 80%～90%
Utilize the digital glossometer of GM-26D type that color technical institute produces in the Amada Co., Ltd. village, record 45 glossiness according to its technical qualification.
B, thermal expansivity: 4.0～6.5 * 10 -6C +
Utilize West Germany to produce 402E type electronic dilatometer, record according to its technical requirements.
C, chemical stability: the molten output of plumbous, cadmium is 0.00mg/dm 2Handle tone, the equal no change of color and luster through acid solution, alkali lye;
Record according to Chinese people's republicanism figure ZBY24006-89 " beramic color ".Wherein the test condition of acid-and base-resisting is: 22 ± 2 ℃ were soaked 32 hours in 4% acetum down, or 60 ± 2 ℃ of following 0.5%Na 2CO 3Soaking 40 hours after scouring airings in the solution observes.
D, electron micrograph: uniform glass body.
With Dutch PHIL IPS CM12/STEM transmission scanning electron microscope, and by its technical requirements shooting.　　　
The present invention further describes below in conjunction with embodiment:
Table I embodiment 1---7 flux prescriptions (mol%)
The component sequence number SiO 2 Bi 2O 3 Al 2O 3 B 2O 3 Li 2O Na 2O K 2O BaO SrO ZrSiO 4 SnO 2 La 2O 3 MgO CaO ZnO TiO 2 Toner
1 50.5 8.0 4.0 3.0 4.0 0.5 - 1.0 - 11.0 0.5 - 0.5 - 1.0 - The chrome green zirconium white
2 55.0 3.3 4.2 15.0 1.0 2.0 8.6 0.1 - 4.5 2.0 1.0 0.3 2.6 0.4 -
3 66.9 3.2 3.5 3.2 - 5.0 5.0 - 1.5 2.6 8.0 - - - 0.1 1.0 Golden red
4 69.0 2.5 9.0 3.7 5.0 - 0.2 1.5 4.0 2.0 2.1 0.1 - 0.7 0.2 - Iron oxide red
5 65.0 2.3 5.6 5.0 0.6 1.0 - - 0.5 2.5 4.0 0.3 - 5.2 - - Chrome alumina red
6 67.5 3.0 3.5 3.0 - 3.0 2.8 3.6 - 5.7 1.0 - 3.0 - 3.9 - Cobalt blue
7 78.0 2.6 1.2 9.0 1.0 - 2.1 0.5 - 1.5 0.9 0.2 - - - 3.0 Praseodymium yellow
The table II is executed example 1---the roasting plumbous cadmium stripping of the temperature C acid-fast alkali-proof (mg/dm that burns of 7 measurement technology index sequence numbers 2) coefficient of expansion C -1Glossiness 1 800～850 4%HAe22 ℃ 32 hours 0 6.0 * 10 -6830 ℃ (%)
0.5%Na 2CO 360 ℃ of 40 hours 87.42 800～850 equal no changes 0 6.1 * 10 -688.43 800～850 11 0 5.6 * 10 -687.14 800～850 11 0 4.9 * 1.0 -687.55 800～850 11 0 5.2 * 10 -688.26 800～850 11 0 5.0 * 10 -687.67 800～850 11 0 4.8 * 10 -687.9
The drawing of accompanying drawing is described as follows:
The electron micrograph of Fig. 1, embodiment 2 flux is a uniform glass body.
Other components in Fig. 2, embodiment 2 flux components are constant, with Bi 2O 3Content is increased to the electron micrograph of 18mol% gained flux, and wherein dark tabs is divided sign Bi 2O 3Phase-splitting, promptly rich Bi 2O 3Phase.
The present invention has following advantage compared to existing technology:
1, chemically stable is good, acid-fast alkali-proof and eradicated plumbous, cadmium poisoning;
2, colour generation is pure, and glossiness is good, pigment tone great variety of goods;
3, thermal coefficient of expansion is lower, on the base glaze that makes preparations for sowing higher adhesive force is arranged all, " burst porcelain " phenomenon can not occur;
4, processing performance is good, the processes such as applicable screen printing, offset printing, aerograph, Freehandhand-drawing, repairing;
5, the scope of application is wide, can be used for the decoration of the multiple ceramics such as hard-paste, soft-paste, Shi porcelain, fine earthenware, bone china and vitreous ceramic, is specially adapted to the decoration of unleaded glaze;
6, reduced cost.

Claims (9)

1, a kind of leadless cadmiumless ceramic glazing pigment is made up of the flux of 70%～95% weight and the toner of 5%～30% weight, it is characterized in that flux constitutes (mol%) by following component:
A, main body flux comprise following component:
SiO 2 55.0～80.0
B 2O 3 3.0～15.0
Bi 2O 3 1.0～8.5
Al 2O 3 1.0～9.0
B, composite fluxing agent are at least two kinds of alkalimetal oxides choosing from following component and a kind of combination of alkaline earth metal oxide:
K 2O 0～9.0
Na 2O 0～9.0
Li 2O 0～9.0
BaO 0～4.0
SrO 0～4.0
C, stablizer comprise following component:
ZrSiO 4 1.5～12.0
SnO 2 0.3～8.5
La 2O 3 0～1.0
D, colour generation auxiliary agent, from following component, choose at least a or two more than the combination:
MgO 0～3.0
CaO 0～6.0
ZnO 0～4.0
TiO 2 0～3.0
2,, it is characterized in that it is (mol%) that preferred flux is formed according to the described leadless cadmiumless ceramic glazing pigment of claim 1:
A, main body flux comprise following component:
SiO 2 65.0～76.0
B 2O 3 5.0～12.0
Bi 2O 3 2.2～6.7
Al 2O 3 3.5～8.1
B, composite fluxing agent are at least two kinds of alkalimetal oxides choosing from following component and a kind of combination of alkaline earth metal oxide:
K 2O 00～5.7
Na 2O 0～6.8
Li 2O 0～8.2
BaO 0～3.0
SrO 0～3.2
C, stablizer comprise following component:
ZrSiO 4 2.0～7.1
SnO 2 0.5～4.2
La 2O 3 0～0.6
D, colour generation auxiliary agent, from following component, choose at least a or two more than the combination:
MgO 0～2.2
CaO 0～4.3
ZnO 0～3.0
TiO 2 0～2.0
3,, it is characterized in that a kind of dark green, blue green, light green, light green, Hai Lan, lake orchid, flux pitch black, silver grey, the white group toner (mol%) composed as follows of being suitable for according to the described leadless cadmiumless ceramic glazing pigment of claim 1:
SiO 2 55.0～70.0
Bi 2O 3 3.0～8.2
B 2O 3 3.0～15.0
Al 2O 3 3.0～7.0
Li 2O 1.0～8.0
Na 2O 1.0～9.0
K 2O 0～9.0
BaO 0.1～1.1
ZrSiO 4 1.0～12.0
SnO 2 0.1～4.0
La 2O 3 0～1.0
MgO 0.1～3.0
CaO 0～3.0
ZnO 0.1～2.0
4,, it is characterized in that a kind of flux (mol%) composed as follows that is suitable for purplish red, dark red, pink, a purple blue class toner according to the described leadless cadmiumless ceramic glazing pigment of claim 1:
SiO 2 66.0～80.0
Bi 2O 3 3.0～6.0
Al 2O 3 3.0～8.0
B 2O 3 3.0～12.0
Na 2O 1.0～8.0
K 2O 1.0～8.0
SrO 1.0～3.0
ZrSiO 4 2.0～9.0
SnO 2 3.0～8.5
ZnO 0.1～3.0
TiO 2 0.5～3.0
5,, it is characterized in that a kind of beans tea, red deeply, west red, shallow flux red, ochre one class toner (mol%) composed as follows of being suitable for according to the described leadless cadmiumless ceramic glazing pigment of claim 1:
SiO 2 65.0～70.0
Bi 2O 3 1.5～3.5
Al 2O 3 4.0～9.0
B 2O 3 3.0～12.0
Li 2O 4.0～6.0
K 2O 0.1～3.0
BaO 1.0～3.0
SrO 0～4.0
ZrSiO 4 2.0～10.0
SnO 2 1.0～3.0
La 2O 3 0.1～1.0
CaO 0.5～3.0
ZnO 0.1～3.0
6,, it is characterized in that a kind of flux (mol%) composed as follows that is suitable for not having golden pink class toner according to the described leadless cadmiumless ceramic glazing pigment of claim 1:
SiO 2 61.0～70.0
Bi 2O 3 2.0～3.5
Al 2O 3 2.0～7.0
B 2O 3 4.0～13.0
Li 2O 5.0～9.0
Na 2O 0.5～2.0
SrO 0.1～1.5
ZrSiO 4 2.0～4.0
SnO 2 3.0～4.1
La 2O 3 0.1～0.5
CaO 2.0～5.2
7,, it is characterized in that a kind of flux (mol%) composed as follows that is suitable for cobalt aluminate class toner according to the described leadless cadmiumless ceramic glazing pigment of claim 1:
SiO 2 65.0～75.0
Bi 2O 3 2.0～3.5
Al 2O 3 3.0～5.0
B 2O 3 3.0～10.0
Na 2O 2.0～5.0
K 2O 0.5～3.0
BaO 0.1～4.0
ZrSiO 4 1.5～10.0
SnO 2 0.5～2.0
MgO 0～3.0
ZnO 1.0～4.0
8,, it is characterized in that a kind of flux (mol%) composed as follows yellow, golden yellow class toner that is suitable for suckling according to the described leadless cadmiumless ceramic glazing pigment of claim 1:
SiO 2 60.0～80.0
Bi 2O 3 2.0～3.5
Al 2O 3 1.0～6.0
B 2O 3 5.0～14.0
Li 2O 1.0～6.0
K 2O 1.0～3.5
BaO 0.1～1.5
ZrSiO 4 1.5～6.0
SnO 2 0.5～2.0
La 2O 3 0.1～0.4
TiO 2 1.0～3.0
9,, it is characterized in that its preparation method comprises the steps: according to the preparation method of the described leadless cadmiumless ceramic glazing pigment of claim 1
A, flux preparation: by prescription metering batch mixing, 1250 ℃～1300 ℃ following fusions of temperature, cold water is quenched broken;
B, mixing ball mushroom: flux and toner mixing and ball milling are to fineness 10um;
C, resintering shrend, ball milling: resintering under 800 ℃～850 ℃ temperature, after the shrend in ball milling wet-milling to fineness 5um;
D, oven dry, pulverizing, packing.
CN94114181A 1994-11-17 1994-11-17 Leadless cadmiumless ceramic glazing pigment Expired - Lifetime CN1044595C (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4282035A (en) * 1980-02-15 1981-08-04 Corning Glass Works Lead-free and cadmium-free frits
US4282731A (en) * 1979-06-04 1981-08-11 Taksony Joseph G Pin-tumbler-type lock having antipick security action
US4590171A (en) * 1985-05-29 1986-05-20 Corning Glass Works Low temperature lead and cadmium-free frits
US4892847A (en) * 1988-06-13 1990-01-09 Ciba-Geigy Corporation Lead-free glass frit compositions
CN1042698A (en) * 1989-10-25 1990-06-06 山东省硅酸盐研究设计院 Low-temp ceramics over-glaze pigment and preparation method thereof
US5304516A (en) * 1991-04-17 1994-04-19 Cookson Group Plc Glaze compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4282731A (en) * 1979-06-04 1981-08-11 Taksony Joseph G Pin-tumbler-type lock having antipick security action
US4282035A (en) * 1980-02-15 1981-08-04 Corning Glass Works Lead-free and cadmium-free frits
US4590171A (en) * 1985-05-29 1986-05-20 Corning Glass Works Low temperature lead and cadmium-free frits
US4892847A (en) * 1988-06-13 1990-01-09 Ciba-Geigy Corporation Lead-free glass frit compositions
CN1042698A (en) * 1989-10-25 1990-06-06 山东省硅酸盐研究设计院 Low-temp ceramics over-glaze pigment and preparation method thereof
US5304516A (en) * 1991-04-17 1994-04-19 Cookson Group Plc Glaze compositions

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