CN102627478B - Method for preparing yellow pigment by using commonly used color development for replacing rare-earth element praseodymium and vanadium color development - Google Patents
Method for preparing yellow pigment by using commonly used color development for replacing rare-earth element praseodymium and vanadium color development Download PDFInfo
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- CN102627478B CN102627478B CN201210129907.9A CN201210129907A CN102627478B CN 102627478 B CN102627478 B CN 102627478B CN 201210129907 A CN201210129907 A CN 201210129907A CN 102627478 B CN102627478 B CN 102627478B
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052777 Praseodymium Inorganic materials 0.000 title claims abstract description 16
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 10
- 239000001052 yellow pigment Substances 0.000 title abstract description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 26
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011737 fluorine Substances 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006229 carbon black Substances 0.000 claims abstract description 17
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 13
- 239000011592 zinc chloride Substances 0.000 claims abstract description 13
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 28
- 239000003513 alkali Substances 0.000 claims description 16
- 230000009257 reactivity Effects 0.000 claims description 16
- 235000010265 sodium sulphite Nutrition 0.000 claims description 16
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 16
- 239000007791 liquid phase Substances 0.000 claims description 11
- RFAFBXGYHBOUMV-UHFFFAOYSA-N calcium chromate Chemical compound [Ca+2].[O-][Cr]([O-])(=O)=O RFAFBXGYHBOUMV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PSUYMGPLEJLSPA-UHFFFAOYSA-N vanadium zirconium Chemical compound [V].[V].[Zr] PSUYMGPLEJLSPA-UHFFFAOYSA-N 0.000 abstract description 14
- USEGQPUGEPSVQL-UHFFFAOYSA-N [Pr].[Zr] Chemical compound [Pr].[Zr] USEGQPUGEPSVQL-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000049 pigment Substances 0.000 abstract description 8
- 239000000919 ceramic Substances 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 238000004040 coloring Methods 0.000 abstract description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- -1 iron ions Chemical class 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 abstract 1
- 229960002089 ferrous chloride Drugs 0.000 abstract 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 abstract 1
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- YLVOPDWXGHFEHW-UHFFFAOYSA-N praseodymium vanadium Chemical compound [V].[V].[V].[V].[V].[Pr] YLVOPDWXGHFEHW-UHFFFAOYSA-N 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of ceramic coloring and pigment and particularly relates to a method for preparing yellow pigment by using commonly used color development for replacing rare-earth element praseodymium and vanadium color development. The method is mainly characterized in that zirconium oxychloride, cadmium sulfate, sodium sulfide, high-activity white carbon black, fluorine-containing multi-component mineralizer, caustic soda flakes and zinc chloride or ferrous chloride are used as raw materials, a technique of doping zinc ions and iron ions in envelope cadmium sulfide pigment is adopted, a solid-liquid combination method is adopted for introducing precursors, novel mineralizer is introduced during high-temperature sintering and the yellow pigment which can replace the rare-earth element praseodymium and the vanadium color development is prepared. The resistant temperature of a product can be improved by 30-50 DEG C on the basis of the resistant temperature of the original zirconium-praseodymium yellow and vanadium-zirconium yellow, the dissolved quantity of cadmium can fully satisfy the international standard, the grain shape is more evenly and grains are spherically distributed and the color development effect is two times of the color development effect of the original product.
Description
Technical field
The invention belongs to ceramic coloring and pigment technology field, be specifically related to a kind of method of preparing yellow ultramarine to commonly use the alternative Rare Earth Elements of Praseodymium of color development and vanadium color development.
Background technology
Praseodymium, v element can be used as color development element, and as yellow in the vanadium zirconium that directly utilizes the zirconium praseodymium yellow of praseodymium color development generation and directly utilize vanadium color development to generate, it is the rare earth element of pigment industry consumption maximum.Zirconium praseodymium yellow, vanadium zirconium Huang are considered to best yellow ceramic pigment, still can keep stable up to 1250 ℃, can be used for disposable or reheating technique.Zirconium praseodymium yellow is widely used in architectural pottery and domestic ceramics is painted, also can make separately under-glaze pigment, and it colour band green light, bright in luster, is hard fire colour rare on market.And vanadium zirconium Huang is also because of the yellow of the dark phase of its distinctive band and be widely used on architectural pottery and domestic ceramics, be a kind of high temperature resistant dark yellow pigment rare on market.But since two thousand nine,, because the scarcity of Praseodymium trioxide and Vanadium Pentoxide in FLAKES and the integration of rare-earth trade have also promoted the recurrence that rare earth is worth, cause even to this day the price of praseodymium yellow and vanadium zirconium Huang to turn over octuple many.Have a strong impact on the normal production of China and the yellow material of world's pottery praseodymium vanadium, also greatly slackened China's glaze materials industry competitive power in the world.Therefore, seeking the novel yellow ultramarine that a kind of energy substitutes the common element color development of zirconium praseodymium yellow, the yellow color development of vanadium zirconium highlights important.
Summary of the invention
The object of the present invention is to provide a kind ofly from color, temperature tolerance, coloring degree, chemical stability, to reach the effect of zirconium praseodymium yellow, vanadium zirconium Huang, grain type reaches equally distributed spherical effect, even more superior to commonly use color development, substitutes the method that Rare Earth Elements of Praseodymium and vanadium color development are prepared yellow ultramarine.
The inventive method is:
(a) substitute praseodymium color development and prepare the step that yellow ultramarine comprises following order:
(1) select following raw material: basic zirconium chloride, Cadmium Sulphate, sodium sulphite, high reactivity white carbon black, fluorine-containing many group mineralizers, sheet alkali, zinc chloride;
(2) adopt liquid phase synthesizing method, basic zirconium chloride, Cadmium Sulphate, sodium sulphite, zinc chloride, sheet alkali are mixed, make zinc chloride dissolve and introduce at Cadmium Sulphate, pH value is controlled to 5.5～8.5;
(3) adopt solid-state mixing, after the material rinsing of the synthetic gained of previous step liquid phase, drying, then add fluorine-containing many group mineralizers and high reactivity white carbon black, by mixing of materials evenly and will pass through 600 order fine screen mesh;
(4) step (3) gained mixture is fired, adopted backing plate to burn colorant roller kiln equipment and fire, temperature is controlled to 1080 ℃～1120 ℃;
(5) finally material is carried out to acidifying, ball milling, acid are floated, soda boiling operation, after oven dry, obtain product;
(b) substitute vanadium color development and prepare the step that yellow ultramarine comprises following order:
(1) select following raw material: basic zirconium chloride, Cadmium Sulphate, sodium sulphite, high reactivity white carbon black, fluorine-containing many group mineralizers, sheet alkali, iron protochloride;
(2) adopt liquid phase synthesizing method, basic zirconium chloride, Cadmium Sulphate, sodium sulphite, iron protochloride, sheet alkali are mixed, iron protochloride is dissolved in Cadmium Sulphate and introduce, pH value is controlled to 7.8;
(3) adopt solid-state mixing, after the material rinsing of the synthetic gained of previous step liquid phase, drying, then add fluorine-containing many group mineralizers and high reactivity white carbon black, by mixing of materials evenly and will pass through 600 order fine screen mesh;
(4) previous step gained mixture is fired, adopted backing plate to burn colorant roller kiln equipment and fire, temperature is controlled to 1080 ℃～1120 ℃;
(5) finally material is carried out to acidifying, ball milling, acid are floated, soda boiling operation, after oven dry, obtain product.
More particularly, in the step (2) of item (a), the mass percent of component basic zirconium chloride, Cadmium Sulphate, sodium sulphite, zinc chloride, sheet alkali is respectively: 67～68%, 11.5～12%, 7～8%, 0.5～2%, 11～12%, and the concentration that adds of controlling each material is respectively: 180～200g/ml, 30～34g/ml, 20～22g/ml, 2～6g/ml, 30～36g/ml; In the step (3) of (a), the weight part of material drying, fluorine-containing many group mineralizers, high reactivity white carbon black respectively: 100,7～10,20～36.
In the step (2) of item (b), the mass percent of component basic zirconium chloride, Cadmium Sulphate, sodium sulphite, iron protochloride, sheet alkali is respectively: 66～68%, 10.5～11.5%, 7～8%, 1.5～3.5%, 11～12%, and the concentration that adds of controlling each material is respectively: 180～200g/ml, 30～34g/ml, 20～22g/ml, 3～7g/ml, 30～36g/ml; In (b) step (3), the weight part of material drying, fluorine-containing many group mineralizers, high reactivity white carbon black respectively: 100,7～10,20～36.
The present invention is color, temperature tolerance, coloring degree, the chemical stability that reaches zirconium praseodymium yellow, vanadium zirconium Huang, and adopt a kind of combination coating Cadmium Sulfide pigment adulterate again zine ion, iron ion technology, the introducing of precursor is adopted to solid-liquid combination, during high temperature sintering, introduce novel mineralizer.Product temperature tolerance of the present invention can improve 30～50 ℃ on the yellow basis of original zirconium praseodymium yellow, vanadium zirconium, and quantity of cadmium release can meet international standards completely, the comparatively spherical distribution of homogeneous of grain type, color development effect is existing product 2 times.
Beneficial effect of the present invention be embodied in following some:
(1) granules of pigments is shaped as 90% spherical effect, has solved in use, and bad because of grain type, glaze is difficult to fill, and part fault location has air to exist, thereby causes the phenomenon that at high temperature has pin hole.
(2), from color development angle, the color development of this product is zirconium praseodymium yellow, vanadium zirconium Huang 2-2.5 times, has fully demonstrated the requirement economizing on resources.
(3) temperature tolerance of this product improves 30～50 ℃ at zirconium praseodymium yellow, vanadium zirconium on yellow basis, also makes the product application scope of this tone further expand.
(4) fundamentally, solved the use ，Wei enterprise that reduces scarce resource praseodymium, vanadium the resource that more has ensured sustained development is provided.
Accompanying drawing explanation
Fig. 1 is production technological process of the present invention.
Embodiment
Below in conjunction with accompanying drawing and specific experiment example, the present invention is described in further detail.
One of the solution of the present invention is for substituting zirconium praseodymium yellow:
Selecting basic zirconium chloride, Cadmium Sulphate, sodium sulphite, high reactivity white carbon black, fluorine-containing many group mineralizers, sheet alkali, zinc chloride is raw material.The first step adopts liquid phase synthesizing method, utilize zinc chloride doping zine ion, the mass percent of major control component basic zirconium chloride, Cadmium Sulphate, sodium sulphite, zinc chloride, sheet alkali is respectively: 67～68%, 11.5～12%, 7～8%, 0.5～2%, 11～12%, and the concentration that adds of controlling each material is respectively: 180～200g/ml, 30～34g/ml, 20～22g/ml, 2～6g/ml, 30～36g/ml; Zinc chloride dissolves and introduces in Cadmium Sulphate, and pH value is controlled at 5.5～8.5.Second step adopts solid-state mixing, the synthetic material rinsing of liquid phase in the first step, after oven dry, add fluorine-containing many group mineralizers and high reactivity white carbon black, control material drying, fluorine-containing many group mineralizers, the weight part of high reactivity white carbon black is respectively 100, 7～10, 20～36, wherein fluorine-containing many group mineralizers play a crucial role to sintering, more sintering degree is better, but surpass certain amount, sintering procedure is difficult to control, sintered particles is increased, pellet hardness increases, in experiment embodiment of the present invention, 7～10% mass percents of total material of take are best, its component is by lithium fluoride, the combination of many groups such as lithium chloride mineralizer.Mixture is even and will pass through 600 order fine screen mesh, then enters ablating work procedure, adopts backing plate to burn colorant roller kiln (1200 ℃) equipment and fires, and controls temperature at 1080 ℃～1120 ℃; Finally enter that acidifying, ball milling, acid are floated, soda boiling operation, after oven dry, go out finished product.The mass effect of its product is: what grain type was 90% is spherical, and tinctorial yield can reach the twice of market zirconium praseodymium yellow, and temperature tolerance can improve 30～50 ℃.Synthesis process as shown in Figure 1.In experimentation, the material rate of each embodiment forms the effect of (mass percent) impact and trend as shown in Table 1:
Table one
In table, tinctorial yield, form and aspect are the result with praseodymium yellow comparison.
Two of the solution of the present invention is alternative vanadium zirconium Huang:
Selecting basic zirconium chloride, Cadmium Sulphate, sodium sulphite, high reactivity white carbon black, fluorine-containing many group mineralizers, sheet alkali, iron protochloride is raw material.The first step adopts liquid phase synthesizing method, the mass percent of major control component basic zirconium chloride, Cadmium Sulphate, sodium sulphite, iron protochloride, sheet alkali is respectively: 66～68%, 10.5～11.5%, 7～8%, 1.5～3.5%, 11～12%, and the concentration that adds of controlling each material is respectively: 180～200g/ml, 30～34g/ml, 20～22g/ml, 3～7g/ml, 30～36g/ml; Iron protochloride dissolves and introduces in Cadmium Sulphate, and pH value is controlled at 7.8.Other production process is identical with alternative zirconium praseodymium yellow technique.The mass effect of its product is: what grain type was 90% is spherical, and more than tinctorial yield can reach the twice of market vanadium zirconium Huang, temperature tolerance can improve 30～50 ℃.Synthesis process as shown in Figure 1.In experimentation, the material rate of each embodiment forms the effect of (mass percent) impact and trend as shown in Table 2:
Table two
In table, tinctorial yield, form and aspect are and the yellow result relatively of vanadium zirconium.
Claims (1)
1. to commonly use the alternative Rare Earth Elements of Praseodymium of color development and vanadium color development, prepare a method for yellow ultramarine, it is characterized in that:
(a) substitute praseodymium color development and prepare the step that yellow ultramarine comprises following order:
(1) select following raw material: basic zirconium chloride, Cadmium Sulphate, sodium sulphite, high reactivity white carbon black, fluorine-containing many group mineralizers, sheet alkali, zinc chloride;
(2) adopt liquid phase synthesizing method, basic zirconium chloride, Cadmium Sulphate, sodium sulphite, zinc chloride, sheet alkali are mixed, make zinc chloride dissolve and introduce at Cadmium Sulphate, pH value is controlled to 5.5～8.5;
(3) adopt solid-state mixing, after the material rinsing of the synthetic gained of previous step liquid phase, drying, then add fluorine-containing many group mineralizers and high reactivity white carbon black, by mixing of materials evenly and will pass through 600 order fine screen mesh;
(4) step (3) gained mixture is fired, adopted backing plate to burn colorant roller kiln equipment and fire, temperature is controlled to 1080 ℃～1120 ℃;
(5) finally material is carried out to acidifying, ball milling, acid are floated, soda boiling operation, after oven dry, obtain product;
(b) substitute vanadium color development and prepare the step that yellow ultramarine comprises following order:
(1) select following raw material: basic zirconium chloride, Cadmium Sulphate, sodium sulphite, high reactivity white carbon black, fluorine-containing many group mineralizers, sheet alkali, iron protochloride;
(2) adopt liquid phase synthesizing method, basic zirconium chloride, Cadmium Sulphate, sodium sulphite, iron protochloride, sheet alkali are mixed, iron protochloride is dissolved in Cadmium Sulphate and introduce, pH value is controlled to 7.8;
(3) adopt solid-state mixing, after the material rinsing of the synthetic gained of previous step liquid phase, drying, then add fluorine-containing many group mineralizers and high reactivity white carbon black, by mixing of materials evenly and will pass through 600 order fine screen mesh;
(4) previous step gained mixture is fired, adopted backing plate to burn colorant roller kiln equipment and fire, temperature is controlled to 1080 ℃～1120 ℃;
(5) finally material is carried out to acidifying, ball milling, acid are floated, soda boiling operation, after oven dry, obtain product;
In the step (2) of item (a), the mass percent of component basic zirconium chloride, Cadmium Sulphate, sodium sulphite, zinc chloride, sheet alkali is respectively: 67～68%, 11.5～12%, 7～8%, 0.5～2%, 11～12%, and the concentration that adds of controlling each material is respectively: 180～200g/ml, 30～34g/ml, 20～22g/ml, 2～6g/ml, 30～36g/ml; In the step (3) of (a), the weight part of material drying, fluorine-containing many group mineralizers, high reactivity white carbon black respectively: 100,7～10,20～36;
In the step (2) of item (b), the mass percent of component basic zirconium chloride, Cadmium Sulphate, sodium sulphite, iron protochloride, sheet alkali is respectively: 66～68%, 10.5～11.5%, 7～8%, 1.5～3.5%, 11～12%, and the concentration that adds of controlling each material is respectively: 180～200g/ml, 30～34g/ml, 20～22g/ml, 3～7g/ml, 30～36g/ml; In (b) step (3), the weight part of material drying, fluorine-containing many group mineralizers, high reactivity white carbon black respectively: 100,7～10,20～36.
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