CN105542512A - Preparation method of water-based zinc-titanium composite slurry - Google Patents
Preparation method of water-based zinc-titanium composite slurry Download PDFInfo
- Publication number
- CN105542512A CN105542512A CN201610077932.5A CN201610077932A CN105542512A CN 105542512 A CN105542512 A CN 105542512A CN 201610077932 A CN201610077932 A CN 201610077932A CN 105542512 A CN105542512 A CN 105542512A
- Authority
- CN
- China
- Prior art keywords
- zinc
- titanium composite
- preparation
- titanium
- water base
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
- C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/04—Compounds of zinc
- C09C1/043—Zinc oxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C1/3623—Grinding
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3669—Treatment with low-molecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3676—Treatment with macro-molecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Cosmetics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a preparation method of water-based zinc-titanium composite slurry. The preparation method has the beneficial effects that not only can the photochemical activities of zinc oxide and titanium oxide be effectively inhibited but also flocculation, agglomeration and precipitation caused due to zinc ion dissolution in the zinc-titanium composite slurry can be inhibited by carrying out silica sol coating treatment on the zinc-titanium composite slurry; the water-based zinc-titanium composite slurry prepared through coating treatment has the properties of both nano-titanium dioxide and nano-zinc oxide and has good UVA and UVB shielding properties; the application range of the water-based zinc-titanium composite slurry in the fields of industry, daily chemicals, and the like is widened.
Description
Technical field
The invention belongs to composite function nano field of material preparation, be specifically related to a kind of preparation method of water base zinc-titanium composite mortar.
Background technology
Due in solar radiation light out, have the ultraviolet (being called for short UV) of the wavelength 200 ~ 400nm of about 5%.Ultraviolet in sunlight, can be divided into by its wavelength: the long wave ultraviolet (being called for short UVA) of 320 ~ 400nm, the ultraviolet B radiation (being called for short UVB) of 280 ~ 320nm and wavelength are the short wave ultraviolet (being called for short UVC) of 200 ~ 280nm.Wherein UVC because of wavelength short, penetrance is strong, and it is absorbed by ozonosphere 98% through earth stratosphere, little to the harm of the mankind.And UVB and UVA penetrance is comparatively strong, the problems such as blackspot, erythema, chafing can be caused to the long-term irradiation of human body, time serious, even can cause skin carcinoma.
Nano zine oxide and titanium oxide are two kinds of widely used inorganic UV shield agent, but they are different to the screening ability of UVA and UVB: the effect that nano-titanium oxide intercepts UVB is very good, but not good enough to the shield effectiveness of UVA; The shield effectiveness of nano zine oxide to UVB is undesirable, but its obstruct UVA effect is better than nano titanium oxide.In order to effectively UVA and UVB can be shielded, reach the object of all wave band ultraviolet protection, usually need to add nano titanium oxide and nano zine oxide in sun care preparations and organic polymer material simultaneously.
But due to the characteristic of semiconductor of nano zine oxide and titanium dioxide, under solar light irradiation, its valence-band electrons absorbs ultraviolet and is excited and transits on conduction band, produces hole-electron pair simultaneously.Partial holes-electron pair moves to semiconductor surface, and make the water molecules of its surface hydroxyl and absorption produce hydroxyl oxyradical, hydroxyl oxyradical has extremely strong oxidation susceptibility, can make the organic matter degradation around it.Add nano particle diameter less, make hole-electron to the time shorten on migration surface, reduce the probability of electronics and hole recombine, therefore nano-oxide has very strong photochemical activity.Photochemical activity in order to inhibited oxidation zinc, titanium oxide needs to carry out surface treatment to it, in addition due to zinc oxide two property, HarveyBrown sets forth zinc oxide in its book " properties and applications of zinc oxide " (InternationalLeadZincResearchOrganization) in water, shows the activity with the multiple material of acid and sour salt and alkaline matter, causes zine ion (Zn
2+) very easily stripping, the existence of a large amount of zine ion can make the viscosity of application system increase, and even make application system flocculate, lump and precipitation, this all can cause result of use to be deteriorated and ultraviolet screener performance declines.So zine ion stripping can be reduced at its Surface coating mineral membrane, suppresses the photochemical activity site of semi-conductor.
At present, generally with silicon oxide, aluminum oxide, single-component, two-pack or the process of polycomponent coating are carried out to titanium oxide or zinc oxide.Very common to the coating process of titanium oxide, effect is all obvious, but the coating process of zinc oxide is but seemed not enough.As Chinese patent CN101024737A proposes a kind of silicon oxide that adopts, coating is carried out to zinc oxide surface, its process with silicate and sulfuric acid for raw material, but due to the strongly-acid of sulfuric acid, owing to having little time zinc oxide solution modeling zine ion when diffusion causes local acid concentration excessive in dropping process, because whole system is in alkaline environment, zine ion generation precipitin reaction generates zinc hydroxide, Zinc oxide water compound, can have a strong impact on the homogeneity of coating layer, compactness like this.Hong Ruoyu is (Chinese powder technology when studying nano zine oxide coated aluminum oxide, 4th phase in 2005) with Tai-Ace S 150 and sodium hydroxide for raw material, part of sulfuric acid aluminium is first added after getting zinc oxide fluid dispersion intensification 60 ~ 80 DEG C, then sodium hydroxide adjusts system pH=9 ~ 10, maintain 1 ~ 2 hour, then adjust system pH to neutral with Tai-Ace S 150, react 0.5 hour.Although it is not the method can not cause the precipitation of surface of nanometer zinc oxide zine ion, very good to the inhibition of the photocatalytic activity of nano zine oxide.Chinese patent CN1253513C proposes a kind of method at the coating hydrous silicon oxide of surface of nanometer zinc oxide, hydrated aluminum oxide or hydrous iron oxide, because the hydrochloric acid, sulfuric acid, acetic acid and the ammoniacal liquor that use in the coated process of the method all can cause the dissolving of nano zine oxide, zine ion stripping, causes covered effect not good enough.
Therefore, research zinc oxide and containing the process for treating surface of zinc oxide composite particles and dispersion technology significant, study the dispersion of nano combined slurries simultaneously, stability improve the precondition of material property and the basis of application further by being.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency overcome in background technology, provides a kind of stripping that effectively can suppress zine ion, can suppress again the method for coating in the photochemical activity site of semi-conductor nano particles well.
Technical scheme of the present invention is: the zinc titanium composite material prepared with method described in Chinese patent CN200810243732.8 is for raw material, and by slurrying, the techniques such as silicon sol coating have been come.
Preparation method of the present invention adopts following characteristics step:
The preparation of 1, zinc-titanium composite dispersion liquid: add 1 ~ 15% wetting dispersing agent (by powder quality) in deionized water and stir, add zinc-titanium composite granule, stir, adjust dispersion liquid pH value to be 8 ~ 10 with organic amine, then grind and obtain zinc-titanium composite dispersion liquid.
2, silicon sol preparation: deionized water is warming up to 75 ~ 95 DEG C, its pH value is regulated to be 8 ~ 10, stir while drip the sodium silicate solution of 0.1 ~ 1.5mol/L, the acidic solution simultaneously dripping 0.1 ~ 2.0mol/L is constant to maintain pH, in dropping process, solution becomes transparent light oyster white colloidal sol gradually by colourless, for subsequent use.
3, coating process: the zinc titanium composite dispersion liquid in step (1) is added under whipped state in the silicon sol that step (2) obtains, insulation 0.5 ~ 1h, then be stir the sodium silicate solution dripping 0.1 ~ 1.5mol/L 8 ~ 10 times in temperature 75 ~ 95 DEG C, pH value, the acidic solution simultaneously dripping 0.1 ~ 2.0mol/L is constant to maintain pH, after adding, insulation 0.5 ~ 1h.Then by suspension filtered and with deionized water wash to filtrate specific conductivity≤200 μ S/cm, the zinc-titanium compound filter cake of coating process is obtained.
4, the preparation of water base zinc-titanium composite mortar: the zinc titanium compound filter cake after step (3) is obtained coating process disperses again, the sanitas (by dispersion liquid quality) adding 0.5 ~ 1% stirs, then the obtained water base zinc-titanium composite mortar of grinding.
Wetting dispersing agent in described step (1) is: one or more in polycarboxylate sodium's class, special poly carboxylic acid ammonium salt class, sodium polyacrylate salt, polycarboxylic ethers;
Organic amine in described step (1) is: one or more in trolamine, α-amino isopropyl alcohol, diisopropanolamine (DIPA);
The mass concentration of the silicon sol in described step (2) is 0.1 ~ 0.5g/mL;
Acidic solution in described step (2) and step (3) is: the one in hydrochloric acid, sulfuric acid, nitric acid or its mixing solutions;
Described step (3) mesosilicic acid sodium consumption and the mass ratio of zinc-titanium composite granule are that 0.05 ~ 0.3:1 is (with the oxide S iO of water glass
2meter);
Grinding plant in described step (1) and step (4) is: the one in sand mill, ball mill, ultrasonic cell disruptor;
Sanitas in described step (4) is: the one in phenylformic acid and salt, Sorbic Acid and salt, Phenoxyethanol, sodium Diacetate, calcium propionate, Sodium.alpha.-hydroxypropionate.
Beneficial effect of the present invention is:
The present invention is with zinc titanium composite material for raw material has prepared a kind of water base zinc-titanium composite mortar by coating process, and its advantage is:
1. the reticulated structure of silicon sol is utilized to cover zinc titanium composite mortar particle surface, and then make up due to the coated uneven unsound shortcoming of silicon sol further by the acid solution of water glass, this coating process effectively inhibit the photochemical activity of zinc oxide and titanium oxide and also can also well suppress to cause due to zine ion stripping in zinc titanium composite mortar flocculation, caking and precipitation generation; 2. the water base zinc-titanium composite mortar prepared has the dual property of nano titanium oxide and nano zine oxide concurrently, all has good shield effectiveness to UVA and UVB; 3. its range of application in fields such as industry, daily use chemicals has been widened in the preparation of water base zinc-titanium composite mortar.
Embodiment
Below in conjunction with specific embodiment, illustrate the present invention further, these embodiments should be understood only be not used in for illustration of the present invention and limit the scope of the invention, after having read the present invention, the amendment of those skilled in the art to the various equivalent form of value of the present invention has all fallen within the application's claims limited range.
In the present invention, the quality of coating effect is evaluated by zinc ion concentration in filtrate before and after detection coating, and wherein in filtrate, the zinc ion concentration Vista-AX type plasma emission spectrum of Varian company of the U.S. is measured.
Embodiment 1
The preparation of 1, zinc-titanium composite dispersion liquid: the wetting dispersing agent PA25 (by powder quality) adding 0.08kg in the deionized water of 1.42kg stirs, then zinc-titanium the composite granule of 1kg is added, stir, its pH value is adjusted to be 9 with trolamine, obtain zinc-titanium compound pre-dispersed liquid, then by sand mill, zinc-titanium compound pre-dispersed liquid grinding is obtained zinc-titanium composite dispersion liquid.
2, silicon sol preparation: deionized water is warming up to 85 DEG C, its pH value is regulated to be 10 stir while drip the sodium silicate solution of 0.8mol/L, the hydrochloric acid soln simultaneously dripping 1.0mol/L is constant to maintain pH, in dropping process, solution becomes transparent light oyster white colloidal sol gradually by colourless, and obtained concentration is that 0.3g/mL silicon sol is for subsequent use.
3, coating process: get silicon sol 0.389L stirring obtained in step (2) and be warming up to 85 DEG C, then the zinc obtained in step (1)-titanium composite dispersion liquid is added in above-mentioned silicon sol under whipped state and be incubated 0.5h, then stir while drip 0.82L0.8mol/L sodium silicate solution, add 1.0mol/L hydrochloric acid soln constant to maintain pH simultaneously, after adding, insulation 0.5h.Then by suspension filtered and with deionized water wash to filtrate specific conductivity 134 μ S/cm, the zinc-titanium compound filter cake of coating process is obtained.
4, the preparation of water base zinc-titanium composite mortar: the zinc after the coating process obtained in step (3)-titanium compound filter cake is disperseed in deionized water again, the sanitas Phenoxyethanol (by dispersion liquid quality) adding 18.75g stirs, then by the obtained water base zinc-titanium composite mortar of sand mill grinding.
Embodiment 2
The preparation of 1, zinc-titanium composite dispersion liquid: the wetting dispersing agent 5040 (by powder quality) adding 0.01kg in the deionized water of 1.49kg stirs, then zinc-titanium the composite granule of 1kg is added, stir, its pH value is adjusted to be 9 with α-amino isopropyl alcohol, obtain zinc-titanium compound pre-dispersed liquid, then by ball mill, zinc-titanium compound pre-dispersed liquid grinding is obtained zinc-titanium composite dispersion liquid.
2, silicon sol preparation: deionized water is warming up to 75 DEG C, its pH value is regulated to be 9 stir while drip the sodium silicate solution of 1.5mol/L, the sulphuric acid soln simultaneously dripping 2.0mol/L is constant to maintain pH, in dropping process, solution becomes transparent light oyster white colloidal sol gradually by colourless, and obtained concentration is that 0.5g/mL silicon sol is for subsequent use.
3, coating process: get silicon sol 0.4L stirring obtained in step (2) and be warming up to 75 DEG C, then the zinc obtained in step (1)-titanium composite dispersion liquid is added in above-mentioned silicon sol under whipped state and be incubated 0.75h, then stir while drip 1.11L1.5mol/L sodium silicate solution, drip 2.0mol/L sulphuric acid soln to maintain pH constant simultaneously, after adding, insulation 0.75h.Then by suspension filtered and with deionized water wash to filtrate specific conductivity 167 μ S/cm, the zinc-titanium compound filter cake of coating process is obtained.
4, the preparation of water base zinc-titanium composite mortar: the zinc after the coating process obtained in step (3)-titanium compound filter cake is disperseed in deionized water again, the sanitas Sorbic Acid (by dispersion liquid quality) adding 25g stirs, and then obtains water base zinc-titanium composite mortar by ball mill grinding.
Embodiment 3
The preparation of 1, zinc-titanium composite dispersion liquid: the wetting dispersing agent 752 (by powder quality) adding 0.15kg in the deionized water of 1.35kg stirs, then zinc-titanium the composite granule of 1kg is added, stir, its pH value is adjusted to be 8 by diisopropanolamine (DIPA), obtain zinc-titanium compound pre-dispersed liquid, then by ultrasonic cell disruptor, zinc-titanium compound pre-dispersed liquid grinding is obtained zinc-titanium composite dispersion liquid.
2, silicon sol preparation: deionized water is warming up to 95 DEG C, its pH value is regulated to be 8 stir while drip the sodium silicate solution of 0.8mol/L, the salpeter solution simultaneously dripping 1.0mol/L is constant to maintain pH, in dropping process, solution becomes transparent light oyster white colloidal sol gradually by colourless, and obtained concentration is that 0.1g/mL silicon sol is for subsequent use.
3, coating process: get silicon sol 0.333L stirring obtained in step (2) and be warming up to 95 DEG C, then the zinc obtained in step (1)-titanium composite dispersion liquid is added in above-mentioned silicon sol under whipped state and be incubated 1h, then stir while drip 2.78L0.1mol/L sodium silicate solution, drip 0.1mol/L salpeter solution to maintain pH constant simultaneously, after adding, insulation 1h.Then by suspension filtered and with deionized water wash to filtrate specific conductivity 183 μ S/cm, the zinc-titanium compound filter cake of coating process is obtained.
4, the preparation of water base zinc-titanium composite mortar: the zinc after the coating process obtained in step (3)-titanium compound filter cake is disperseed in deionized water again, the sanitas Sodium.alpha.-hydroxypropionate (by dispersion liquid quality) adding 12.5g stirs, then by the obtained water base zinc-titanium composite mortar of ultrasonic cell disruptor grinding.
Embodiment 4
The preparation of 1, zinc-titanium composite dispersion liquid: the wetting dispersing agent 5060 (by powder quality) adding 0.08kg in the deionized water of 1.42kg stirs, then zinc-titanium the composite granule of 1kg is added, stir, its pH value is adjusted to be 10 with trolamine, obtain zinc-titanium compound pre-dispersed liquid, then by sand mill, zinc-titanium compound pre-dispersed liquid grinding is obtained zinc-titanium composite dispersion liquid.
2, silicon sol preparation: deionized water is warming up to 75 DEG C, its pH value is regulated to be 10 stir while drip the sodium silicate solution of 0.8mol/L, the hydrochloric acid soln simultaneously dripping 1.0mol/L is constant to maintain pH, in dropping process, solution becomes transparent light oyster white colloidal sol gradually by colourless, and obtained concentration is that 0.3g/mL silicon sol is for subsequent use.
3, coating process: get silicon sol 0.389L stirring obtained in step (2) and be warming up to 75 DEG C, then the zinc obtained in step (1)-titanium composite dispersion liquid is added in above-mentioned silicon sol under whipped state and be incubated 0.5h, then stir while drip 0.82L0.8mol/L sodium silicate solution, drip 1.0mol/L hydrochloric acid soln to maintain pH constant simultaneously, after adding, insulation 0.75h.Then by suspension filtered and with deionized water wash to filtrate specific conductivity 189 μ S/cm, the zinc-titanium compound filter cake of coating process is obtained.
4, the preparation of water base zinc-titanium composite mortar: the zinc after the coating process obtained in step (3)-titanium compound filter cake is disperseed in deionized water again, the preservative benzoic acid (by dispersion liquid quality) adding 18.75g stirs, then by the obtained water base zinc-titanium composite mortar of sand mill grinding.
Embodiment 5
The preparation of 1, zinc-titanium composite dispersion liquid: the wetting dispersing agent PA25 (by powder quality) adding 0.15kg in the deionized water of 1.35kg stirs, then zinc-titanium the composite granule of 1kg is added, stir, its pH value is adjusted to be 8 by diisopropanolamine (DIPA), obtain zinc-titanium compound pre-dispersed liquid, then by ultrasonic cell disruptor, zinc-titanium compound pre-dispersed liquid grinding is obtained zinc-titanium composite dispersion liquid.
2, silicon sol preparation: deionized water is warming up to 95 DEG C, its pH value is regulated to be 8 stir while drip the sodium silicate solution of 0.8mol/L, the sulphuric acid soln simultaneously dripping 1.0mol/L is constant to maintain pH, in dropping process, solution becomes transparent light oyster white colloidal sol gradually by colourless, and obtained concentration is that 0.1g/mL silicon sol is for subsequent use.
3, coating process: get silicon sol 0.333L stirring obtained in step (2) and be warming up to 95 DEG C, then the zinc obtained in step (1)-titanium composite dispersion liquid is added in above-mentioned silicon sol under whipped state and be incubated 0.75h, then stir while drip 2.78L0.1mol/L sodium silicate solution, drip 0.1mol/L sulphuric acid soln to maintain pH constant simultaneously, after adding, insulation 0.75h.Then by suspension filtered and with deionized water wash to filtrate specific conductivity 117 μ S/cm, the zinc-titanium compound filter cake of coating process is obtained.
4, the preparation of water base zinc-titanium composite mortar: the zinc after the coating process obtained in step (3)-titanium compound filter cake is disperseed in deionized water again, the sanitas Sodium.alpha.-hydroxypropionate (by dispersion liquid quality) adding 12.5g stirs, then by the obtained water base zinc-titanium composite mortar of ultrasonic cell disruptor grinding.
Comparative example 1
In comparative example, coating process in step (3) in embodiment 1 is first used silicon sol coating process with after water glass coating, other operational conditions are with embodiment 1, and concrete operations are as described below:
The preparation of 1, zinc-titanium composite dispersion liquid: the wetting dispersing agent PA25 (by powder quality) adding 0.08kg in the deionized water of 1.42kg stirs, then zinc-titanium the composite granule of 1kg is added, stir, its pH value is adjusted to be 9 with trolamine, obtain zinc-titanium compound pre-dispersed liquid, then by sand mill, zinc-titanium compound pre-dispersed liquid grinding is obtained zinc-titanium composite dispersion liquid.
2, silicon sol preparation: deionized water is warming up to 85 DEG C, its pH value is regulated to be 10 stir while drip the sodium silicate solution of 0.8mol/L, the hydrochloric acid soln simultaneously dripping 1.0mol/L is constant to maintain pH, in dropping process, solution becomes transparent light oyster white colloidal sol gradually by colourless, and obtained concentration is that 0.3g/mL silicon sol is for subsequent use.
3, coating process: the zinc in step (1)-titanium composite dispersion liquid is warming up to 85 DEG C, then stir while drip 0.82L0.8mol/L sodium silicate solution, drip 1.0mol/L hydrochloric acid soln to maintain pH constant simultaneously, after adding, insulation 0.5h, then the silicon sol obtained in step (2) is joined in above-mentioned bag silicon dispersion liquid and be incubated 0.5h, then by suspension filtered and with deionized water wash to filtrate specific conductivity 134 μ S/cm, the zinc-titanium compound filter cake of coating process is obtained.
4, the preparation of water base zinc-titanium composite mortar: the zinc after the coating process obtained in step (3)-titanium compound filter cake is disperseed in deionized water again, the sanitas Phenoxyethanol (by dispersion liquid quality) adding 18.75g stirs, then by the obtained water base zinc-titanium composite mortar of sand mill grinding.
Comparative example 2
Under the condition of identical covering amount, in comparative example, coating process in step (3) in embodiment 1 is all used silicon sol coating process, other operational conditions are with embodiment 1, and concrete operations are as described below:
The preparation of 1, zinc-titanium composite dispersion liquid: the wetting dispersing agent PA25 (by powder quality) adding 0.08kg in the deionized water of 1.42kg stirs, then zinc-titanium the composite granule of 1kg is added, stir, its pH value is adjusted to be 9 with trolamine, obtain zinc-titanium compound pre-dispersed liquid, then by sand mill, zinc-titanium compound pre-dispersed liquid grinding is obtained zinc-titanium composite dispersion liquid.
2, silicon sol preparation: deionized water is warming up to 85 DEG C, its pH value is regulated to be 10 stir while drip the sodium silicate solution of 0.8mol/L, the hydrochloric acid soln simultaneously dripping 1.0mol/L is constant to maintain pH, in dropping process, solution becomes transparent light oyster white colloidal sol gradually by colourless, and obtained concentration is that 0.3g/mL silicon sol is for subsequent use.
3, coating process: get 0.3g/mL silicon sol 0.584L stirring obtained in step (2) and be warming up to 85 DEG C, then the zinc obtained in step (1)-titanium composite dispersion liquid is added in above-mentioned silicon sol under whipped state and be incubated 0.5h, then by suspension filtered and with deionized water wash to filtrate specific conductivity 134 μ S/cm, the zinc-titanium compound filter cake of coating process is obtained.
4, the preparation of water base zinc-titanium composite mortar: the zinc after the coating process obtained in step (3)-titanium compound filter cake is disperseed in deionized water again, the sanitas Phenoxyethanol (by dispersion liquid quality) adding 18.75g stirs, then by the obtained water base zinc-titanium composite mortar of sand mill grinding.
Comparative example 3
Under the condition of identical covering amount, in comparative example, coating process in step (3) in embodiment 1 is all used water glass coating process, other operational conditions are with embodiment 1, and concrete operations are as described below:
The preparation of 1, zinc-titanium composite dispersion liquid: the wetting dispersing agent PA25 (by powder quality) adding 0.08kg in the deionized water of 1.42kg stirs, then zinc-titanium the composite granule of 1kg is added, stir, its pH value is adjusted to be 9 with trolamine, obtain zinc-titanium compound pre-dispersed liquid, then by sand mill, zinc-titanium compound pre-dispersed liquid grinding is obtained zinc-titanium composite dispersion liquid.
2, coating process: the zinc obtained in step (1)-titanium composite dispersion liquid is stirred and is warming up to 85 DEG C, then stir while drip 2.46L0.8mol/L sodium silicate solution, drip 1.0mol/L hydrochloric acid soln to maintain pH constant simultaneously, after adding, and insulation 0.5h.Then by suspension filtered and with deionized water wash to filtrate specific conductivity 134 μ S/cm, the zinc-titanium compound filter cake of coating process is obtained.
3, the preparation of water base zinc-titanium composite mortar: the zinc after the coating process obtained in step (2)-titanium compound filter cake is disperseed in deionized water again, the sanitas Phenoxyethanol (by dispersion liquid quality) adding 18.75g stirs, then by the obtained water base zinc-titanium composite mortar of sand mill grinding.
Table 1 is the stripping test of zine ion in zinc-titanium composite mortar
In the present invention, the quality of coating effect is evaluated by zinc ion concentration in filtrate before and after detection coating, and experimental result as shown in Table 1.Significantly can reduce zine ion stripping phenomenon in zinc-titanium composite mortar by present invention process as seen by table 1, and then more stable zinc-titanium composite mortar can be prepared widen its Application Areas.
Claims (8)
1. a preparation method for water base zinc-titanium composite mortar, is characterized in that: described preparation method's processing step is as follows:
(1) preparation of, zinc-titanium composite dispersion liquid: the wetting dispersing agent adding powder total mass 1 ~ 15% in deionized water stirs, add zinc-titanium composite granule, stir, regulate dispersion liquid pH value to be 8 ~ 10 with organic amine, then grind and obtain zinc-titanium composite dispersion liquid;
(2), silicon sol preparation: deionized water is warming up to 75 ~ 95 DEG C, its pH value is regulated to be 8 ~ 10, stir while drip the sodium silicate solution of 0.1 ~ 1.5mol/L, the acidic solution simultaneously dripping 0.1 ~ 2.0mol/L is constant to maintain pH, in dropping process, solution becomes transparent light oyster white colloidal sol gradually by colourless, for subsequent use;
(3), coating process: the zinc titanium composite dispersion liquid in step (1) is added under whipped state in the silicon sol that step (2) obtains, insulation 0.5 ~ 1h, then be stir the sodium silicate solution dripping 0.1 ~ 1.5mol/L 8 ~ 10 times in temperature 75 ~ 95 DEG C, pH value, the acidic solution simultaneously dripping 0.1 ~ 2.0mol/L is constant to maintain pH, after adding, insulation 0.5 ~ 1h; Then by suspension filtered and with deionized water wash to filtrate specific conductivity≤200 μ S/cm, the zinc-titanium compound filter cake of coating process is obtained;
(4), the preparation of water base zinc-titanium composite mortar: the zinc titanium compound filter cake after obtaining coating process in step (3) is disperseed again, the sanitas adding dispersion liquid quality 0.5 ~ 1% stirs, then the obtained water base zinc-titanium composite mortar of grinding.
2. the preparation method of water base zinc-titanium composite mortar as claimed in claim 1, is characterized in that: the wetting dispersing agent in described step (1) is: one or more in polycarboxylate sodium's class, special poly carboxylic acid ammonium salt class, sodium polyacrylate salt, polycarboxylic ethers.
3. the preparation method of water base zinc-titanium composite mortar as claimed in claim 1, is characterized in that: the organic amine in described step (1) is: one or more in trolamine, α-amino isopropyl alcohol, diisopropanolamine (DIPA).
4. the preparation method of water base zinc-titanium composite mortar as claimed in claim 1, is characterized in that: the mass concentration of the silicon sol in described step (2) is 0.1 ~ 0.5g/mL.
5. the preparation method of water base zinc-titanium composite mortar as claimed in claim 1, is characterized in that: the acidic solution in described step (2) and step (3) is: the one in hydrochloric acid, sulfuric acid, nitric acid or its mixing solutions.
6. the preparation method of water base zinc-titanium composite mortar as claimed in claim 1, it is characterized in that: the mass ratio of described step (3) mesosilicic acid sodium and zinc-titanium composite granule is 0.05 ~ 0.3:1, and the mass ratio of described amount of sodium silicate and zinc-titanium composite granule is with the oxide S iO of water glass
2meter.
7. the preparation method of water base zinc-titanium composite mortar as claimed in claim 1, is characterized in that: the grinding plant in described step (1) and step (4) is: the one in sand mill, ball mill, ultrasonic cell disruptor.
8. the preparation method of water base zinc-titanium composite mortar as claimed in claim 1, is characterized in that: the sanitas in described step (4) is: the one in phenylformic acid and salt, Sorbic Acid and salt, Phenoxyethanol, sodium Diacetate, calcium propionate, Sodium.alpha.-hydroxypropionate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610077932.5A CN105542512B (en) | 2016-02-03 | 2016-02-03 | A kind of preparation method of water base zinc titanium composite mortar |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610077932.5A CN105542512B (en) | 2016-02-03 | 2016-02-03 | A kind of preparation method of water base zinc titanium composite mortar |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105542512A true CN105542512A (en) | 2016-05-04 |
| CN105542512B CN105542512B (en) | 2018-01-02 |
Family
ID=55822092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610077932.5A Active CN105542512B (en) | 2016-02-03 | 2016-02-03 | A kind of preparation method of water base zinc titanium composite mortar |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105542512B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004528A (en) * | 2019-10-29 | 2020-04-14 | 龙蟒佰利联集团股份有限公司 | Coating-grade titanium white and titanium dioxide with high storage stability and preparation method thereof |
| CN115818708A (en) * | 2022-12-15 | 2023-03-21 | 常州纳欧新材料科技有限公司 | Preparation method of titanium-containing flaky zinc oxide composite physical sun-screening agent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1511889A (en) * | 2002-12-27 | 2004-07-14 | 北京服装学院 | Surface modified nano zinc oxide water dispersion and its preparing method and use |
| CN1785817A (en) * | 2005-12-21 | 2006-06-14 | 四川大学 | Preparation of shielding ultra violest ray nano-ZnO/TiO2 composite powder |
| CN101024737A (en) * | 2007-03-29 | 2007-08-29 | 上海大学 | Method for preparing anti-ultraviolet nano zinc oxide composite powder |
| CN101428845A (en) * | 2008-12-12 | 2009-05-13 | 江苏河海纳米科技股份有限公司 | Inorganic surface treating method for nano-zinc oxide |
| CN103232733A (en) * | 2013-04-10 | 2013-08-07 | 雅安百图高新材料有限公司 | Nano-scale silica-coated titanium dioxide powder |
-
2016
- 2016-02-03 CN CN201610077932.5A patent/CN105542512B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1511889A (en) * | 2002-12-27 | 2004-07-14 | 北京服装学院 | Surface modified nano zinc oxide water dispersion and its preparing method and use |
| CN1785817A (en) * | 2005-12-21 | 2006-06-14 | 四川大学 | Preparation of shielding ultra violest ray nano-ZnO/TiO2 composite powder |
| CN101024737A (en) * | 2007-03-29 | 2007-08-29 | 上海大学 | Method for preparing anti-ultraviolet nano zinc oxide composite powder |
| CN101428845A (en) * | 2008-12-12 | 2009-05-13 | 江苏河海纳米科技股份有限公司 | Inorganic surface treating method for nano-zinc oxide |
| CN103232733A (en) * | 2013-04-10 | 2013-08-07 | 雅安百图高新材料有限公司 | Nano-scale silica-coated titanium dioxide powder |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004528A (en) * | 2019-10-29 | 2020-04-14 | 龙蟒佰利联集团股份有限公司 | Coating-grade titanium white and titanium dioxide with high storage stability and preparation method thereof |
| CN111004528B (en) * | 2019-10-29 | 2021-09-17 | 龙蟒佰利联集团股份有限公司 | Coating-grade titanium white and titanium dioxide with high storage stability and preparation method thereof |
| CN115818708A (en) * | 2022-12-15 | 2023-03-21 | 常州纳欧新材料科技有限公司 | Preparation method of titanium-containing flaky zinc oxide composite physical sun-screening agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105542512B (en) | 2018-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107604644B (en) | Preparation method of TiO 2/illite inorganic ultraviolet screening agent | |
| Wang et al. | Remarkable changes in the optical properties of CeO2 nanocrystals induced by lanthanide ions doping | |
| Yan et al. | Preparation and properties of ce-doped TiO2 photocatalyst | |
| Satar et al. | Facile green synthesis of ytrium-doped BiFeO3 with highly efficient photocatalytic degradation towards methylene blue | |
| Xue et al. | An interesting Eu, F-codoped BiVO4 microsphere with enhanced photocatalytic performance | |
| Liu et al. | (Sulfur, Nitrogen)‐Codoped Rutile‐Titanium Dioxide as a Visible‐Light‐Activated Photocatalyst | |
| Manimegalai et al. | Magneto-optical and photocatalytic properties of magnetically recyclable Mn x Zn 1− x S (x= 0.0, 0.3, and 0.5) nanocatalysts | |
| CN101429348B (en) | Process for producing nano-titanium dioxide-zinc oxide composite powder | |
| CN104945957A (en) | Graphene-base all-band ultraviolet shielding material and preparation method thereof | |
| CN111084727B (en) | Method for preparing nano zinc oxide surface modification and reverse phase dispersion slurry | |
| CN104844829A (en) | Preparation method of ultraviolet rejection attapulgite material | |
| Zhu et al. | One-pot hydrothermal synthesis of BiVO 4 microspheres with mixed crystal phase and Sm 3+-doped BiVO 4 for enhanced photocatalytic activity | |
| Chen et al. | Effects of citric acid and urea on the structural and morphological characteristics of BiVO 4 synthesized by the sol–gel combustion method | |
| Wang et al. | Enhanced photo-degradation methyl orange by N–F co-doped BiVO4 synthesized by sol–gel method | |
| CN108502922B (en) | Anatase titanium dioxide microsphere and preparation method thereof | |
| Zhao et al. | Fabrication, characterization and photocatalytic activity of Gd3+-doped titania nanoparticles with mesostructure | |
| CN105542512A (en) | Preparation method of water-based zinc-titanium composite slurry | |
| Yadav et al. | Quercetin-sensitized BiOF nanostructures: An investigation on photoinduced charge transfer and regeneration process for degradation of organic pollutants | |
| CN101948127B (en) | Industrial preparation method of non-oxidative cerium oxide nanoparticles | |
| CN105233821A (en) | Strontium-doped and silver-doped nanometer titanium dioxide visible light catalyst | |
| CN108485599B (en) | Preparation method of attapulgite-based broad-spectrum ultraviolet shielding material | |
| Mkhalid et al. | Photocatalytic visible-light-driven removal of the herbicide imazapyer using nanocomposites based on mesoporous TiO 2 modified with Gd 2 O 3 | |
| CN107297205A (en) | The method of hexagonal phase content in a kind of modulation monoclinic phase/hexagonal phase out-phase knot tungsten trioxide photocatalyst | |
| CN104607218A (en) | Composite silver bromide-bismuth phosphate heterojunction photocatalytic material and preparation method thereof | |
| Wu et al. | Simple Fabrication of Visible Light-Responsive Bi-BiOBr/BiPO4 Heterostructure with Enhanced Photocatalytic Activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220819 Address after: Room 410, Building 2, No. 261, Xiongzhou East Road, Xiongzhou Street, Liuhe District, Nanjing City, Jiangsu Province, 210000 Patentee after: Jiangsu Kona New Materials Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |