CN103613958A - Environment-friendly titanium pigment prepared by using complexation-precipitation process - Google Patents
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Abstract
The invention discloses environment-friendly titanium pigment prepared by using a complexation-precipitation process. The process comprises the following steps: quantitatively weighing titanium dioxide or titanium dioxide and antimonous oxide to be added into a solution into which a surfactant is dissolved, and dispersing uniformly; adding a mixture solution of coloring ions R<+1> and a complexing agent, controlling the contents of the complexing agent and the coloring ions so as to establish a stable system of the coloring irons and the complexing agent, adjusting the pH value of the system and enabling the system to be in a stable state; performing precipitation reaction on the coloring ions and an dropped alkali solution; aging and subsequently washing and filtering the reaction system so as to remove impurity ions; performing spraying drying treatment; adding a mineralizer into the dry powder, uniformly mixing, subsequently calcining in air atmosphere in a muffle furnace, and controlling the temperature and the temperature preserving time so as to obtain expected powder. The pigment overcomes the defects that in the conventional titanium yellow preparation, the particle size of the pigment is large, the distribution interval is wide, the color is not bright, agglomeration happens, the coloring capability is poor, and the like, and the cost of the titanium pigment is greatly lower than that of a developed product in market.
Description
Technical field
The present invention relates to field of powder metallurgy preparation, especially relate to environmental protection titanium pigment prepared by employing complexing-depositing technology.
Background technology
Problem of environmental pollution is more and more subject to the extensive concern of international community, promotes Green Product, strengthens energy-saving and emission-reduction and be environment that reply goes from bad to worse and the important means of shortage of resources.The mineral dye that contains plumbous and cadmium is because color and luster is vivid, and price is lower, occupies market greatly, yet, for to policy and the consideration to environment protection health aspect, seek safety, the nontoxic environmental-friendly pigment of human body has been become to a kind of common recognition of people.
Along with mineral dye Application Areas is constantly expanded, the characteristic of pigment itself is also had higher requirement, especially in photostabilization, weathering resistance and chemical stability aspect.Inorganic titanium series pigments has excellent performance, safety and environmental protection, and cost performance is high, has market very widely.
Comparatively ripe product adopts solid phase method technique more in the market, and reason is that the method technique is simple to operation, and cost is relatively low, and product is comparatively stable.Shortcoming, because the method is to realize batch mixing by techniques such as high speed ball millings between oxide compound, cannot reach the even mixing of the such molecular level level of liquid phase method.The problems such as therefore, product performance exist tinting strength poor, and color and luster is vivid not, do not reach the technical indicator of high-end product.
Along with improving constantly of nano material technology of preparing, the application of liquid phase method synthesis technique in environmental-friendly pigment is more and more wider, and owing to being that the powder fineness obtaining is good at other even batch mixing of molecular level, calcining temperature is low, and product quality is also in continuous improve.Yet it is easily to bring agglomeration traits in the process of preparation that liquid phase method exists general deficiency, affects color development, because technique is comparatively complicated, product stability is wayward simultaneously, and yield is lower, and cost is relatively high.Therefore, seek a kind of can improving product quality, the technique that can significantly reduce costs again becomes the emphasis of scientific research personnel's research.
Summary of the invention
The object of the invention is to the titanium yellow pigment quality defect existing for prior art, provide a kind of product quality excellent, and cost is significantly lower than market-ripe product, is easy to suitability for industrialized production, the environmental protection titanium pigment that adopts complexing-depositing technology to prepare.
Environmental protection titanium pigment prepared by employing complexing-depositing technology provided by the invention comprises the steps:
1) take the titanium dioxide of certain part by weight, or the antimonous oxide that takes the titanium dioxide of certain part by weight and account for titanium dioxide weight 10-15% joins in the aqueous solution that is dissolved with tensio-active agent, be uniformly dispersed, the weight of wherein said tensio-active agent is the 0.2-0.5% of titanium dioxide weight;
2) add coloring ion R
+with the mixing solutions of complexing agent, control the content of described complexing agent and described coloring ion, make coloring ion R
+and between complexing agent, form stable system, the pH value of regulation system, makes system in steady state;
3) drip slowly 0.5mol l alkaline solution to step 2) in, make coloring ion and the alkaline solution generation precipitin reaction that splashes into;
4) after alkaline solution titration finishes, ageing 2h, carries out rinsing to reaction system, filters, and removes foreign ion;
5) slurry after rinsing is carried out to spray drying treatment;
6) at dried powder, add mineralizer, carry out air atmosphere calcining after mixing in retort furnace, temperature is controlled at 900-1200 ℃, and insulation 1-2h, obtains required powder.
In above-mentioned steps:
Particularly, described tensio-active agent is Sodium hexametaphosphate 99.
Particularly, described step 2) in, described coloring ion R
+for Ni
2+, Cr
3+, Co
2+, Zn
2+.
Further, contain described coloring ion R
+compound be one or more in nickelous nitrate, chromium nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or zinc nitrate, account for the 20-50% of described titanium dioxide weight.
Particularly, described complexing agent is triethylene tetramine or/and citric acid, accounts for the 0.2%-1% of described titanium dioxide weight.
Particularly, described step 2) in, the mol ratio of coloring ion and complexing agent is controlled between 0.5-2, the PH that measures system with test paper is between 6-8, temperature of reaction is elevated to 50-70 ℃, control stir speed (S.S.) 400-600r min, the treatment time is 0.5h-4h.
Particularly, in described step 3), the speed of response that alkaline solution clear liquor drips is controlled in 10-15ml/min, and control pH value is 8-12.
Further, described alkaline solution is sodium hydroxide solution and/or potassium hydroxide solution.
Particularly, described step 5) drying treatment parameter: charging total amount 10-12kg h, negative pressure is 400-600Kpa in tower, inlet temperature 150-165 ℃, temperature of outgoing air 60-65 ℃.
Particularly, the described mineralizer adding in described step 6) is one or more in borax and silicon-dioxide, zinc oxide, wherein said borax is the 0.1-10%g of titanium dioxide weight, and silicon-dioxide is the 0.4-6% of titanium dioxide weight, and zinc oxide is the 0.1-5% of titanium dioxide weight.
The titanium yellow pigment that the present invention adopts complexing-depositing technology to prepare, has overcome the defects such as the pigment particle size of current titanium yellow pigment existence is large, and distributed area is wide, and color is not vivid, and existence is reunited, and tinting strength is poor.Than solid phase method technique, the powder color and luster that the present invention obtains is vivid, and size distribution interval is narrow, strong coloring force; Than liquid phase method technique, after powder calcination of the present invention, present bulk Powdered, do not need ball milling can reach fineness requirement, only need simple pigment aftertreatment technology just can reach application requiring, simplified to a certain extent production technique, reduced production cost.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Environmental protection titanium pigment prepared by employing complexing-depositing technology provided by the invention, comprises the steps:
1) take a certain amount of titanium dioxide, or the antimonous oxide that takes a certain amount of titanium dioxide and account for titanium dioxide weight 10-15% joins in the aqueous solution that is dissolved with tensio-active agent, be uniformly dispersed.
In this step, add antimonous oxide in follow-up pigment preparation process in temperature rising, under the atmosphere that antimonous oxide exists at oxygen, to change into antimony peroxide, provide electric charge to supplement, avoid occurring lattice imperfection.
The weight of tensio-active agent is between the 0.2-0.5% of titanium dioxide weight.Described tensio-active agent is Sodium hexametaphosphate 99, can be used as dispersion agent, and the surface tension of titanium dioxide raw material is reduced, and can make titanium dioxide be dispersed in solution uniformly, and makes the particulate after dispersion keep stable state.
2) add coloring ion R
+mixing solutions with complexing agent, control the mol ratio of described complexing agent and described coloring ion between 0.5-2, the PH that measures system with test paper is between 6-8, temperature of reaction is elevated to 50-70 ℃, control stir speed (S.S.) 400-600r min, treatment time is 0.5h-4h, makes to form between coloring ion and complexing agent stable system;
In this step, described coloring ion R
+for Ni
2+, Cr
3+, Co
2+, Zn
2+.
Contain coloring ion R
+compound can preferably nitrate, can select one or more in nickelous nitrate, chromium nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or zinc nitrate, account for the 20-50% of described titanium dioxide weight.Selecting nitrate is when being to form precipitation with alkali lye, and monovalent salt more easily forms the little and precipitation uniformly of particle diameter.
Described complexing agent is triethylene tetramine or/and citric acid, accounts for the 0.2%-1% of described titanium dioxide weight
Adding of complexing agent can form meta structure with nitrate, reduced the degree of supersaturation of system, along with constantly adding of alkaline solution, the pH value of system increases, formed meta structure starts slowly to discharge nitrate ion, and sluggish is carried out uniformly, reduces the agglomeration traits of bringing.
3) drip slowly 0.5mol l alkaline solution to step 2) in, the speed of response control dripping, in 10-15ml/min, to control the nucleation and growth speed of nano material, is controlled pH value 8-12 simultaneously.Along with the pH value of system constantly raises, complex system plays pendulum, and coloring ion R+ is released gradually, with the alkaline solution generation precipitin reaction splashing into; Due to coloring ion R
+slowly be released, the precipitation of formation is not almost reunited.When reaching titration end point, stop splashing into alkali lye.
In this step, alkaline solution can be selected sodium hydroxide solution and/or potassium hydroxide solution.When selecting the mixing solutions of sodium hydroxide and potassium hydroxide, its solution is sodium hydroxide by weight: potassium hydroxide=1:2 carries out proportioning.
The dropping of alkali lye has activated the surface tissue of titanium dioxide on the one hand, has changed the acid-basicity of system, makes its surface form great amount of hydroxy group chemical bond, when it splashes into the coloring ion R of nitrate
+(Ni
2+, Cr
3+, Co
2+, Zn
2+) time, coloring ion R
+can form fine and close coating film uniformly at titanium dioxide surface deposition, form Ti-O-R simultaneously
+chemical bond, in later stage high-temperature calcination, coloring ion can enter in titanium dioxide lattice uniformly, forms substitutional solid solution, reduces calcining temperature, save energy; And can when process on titanium dioxide surface, make the titanium dioxide surface after processing form the weak sodium titanate of alkalescence, be conducive to reduce speed of response, control nano material fineness.
4), after alkaline solution titration finishes, ageing 2h, carries out rinsing, filtration to reaction system, removes unnecessary foreign ion.Treat that foreign matter content is lower than 20ppm, during the nearly neutrality of solution pH value, rinsing is complete;
5) slurry after rinsing is carried out to spray drying treatment.Drying temperature is unsuitable too high, the agglomeration traits of bringing in drying process to reduce powder.Spray-dired parameter is: charging total amount 10-12kg h, negative pressure is 400-600Kpa in tower, inlet temperature 150-165 ℃, temperature of outgoing air 60-65 ℃.
6) at dried powder, add mineralizer, carry out air atmosphere calcining after mixing in retort furnace, reach after certain temperature, temperature is controlled at 900-1200 ℃, and insulation 1-2h, obtains required powder.
In this step, the mineralizer adding is at least one the mixture in borax and silicon-dioxide, zinc oxide, wherein said borax is the 0.1-10%g of titanium dioxide weight, and silicon-dioxide is the 0.4-6% of titanium dioxide weight, and zinc oxide is the 0.1-5% of titanium dioxide weight.
Adding first of mineralizer can form fine and close carbon coating film in xeraphium surface, suppressed the reunion of nano material, finally can obtain particle diameter little, the powder of good dispersity; Secondly, adding of the zwitterion mineralizer of small radii, in powder high-temperature calcination, can promote the conversion of rutile-type, is conducive to form substitutional solid solution, significantly reduces calcining temperature; The 3rd, there is the adding of mineralizer of oxidisability, in high-temperature calcination, can release portion oxygen, make the atmosphere of calcining system in oxygen enrichment, crystal formation is fully transformed, the temperature while reducing calcining, reduces calcination time.
Wherein, adding of borax can promote lattice to transform, and reduces the calcining temperature in preparation process, reduces production costs; Zinc oxide adds, and adjustable reaction system promotes the carrying out of reaction, can promote dispersed in solution of raw material simultaneously.Silicon-dioxide, can make calcining in oxygen enrichment atmosphere, impels crystal formation fully to transform, and avoids producing lattice imperfection.
In above-mentioned preparation method, when titanium dioxide disperses in earlier stage, by adding a certain amount of tensio-active agent, can make titanium dioxide in high dispersing state, add coloring ion R simultaneously
+(Ni
2+, Cr
3+, Co
2+, Zn
2+) and complexing agent, now complexing agent can form rock steady structure with coloring ion, when reducing reaction system degree of supersaturation, makes system in metastable state, can, because local concentration is excessive when adding alkaline solution, not produce comparatively serious agglomeration traits, simultaneously, when alkaline solution slowly drips, because the pH value of system starts to raise, destroy the steady state of original system, the complexing agent forming starts slow release coloring ion, coloring ion and then be slowly precipitated out with alkali lye, because the continuous low price of coloring ion along with alkali lye slowly releases, can form uniformly precipitation, can be because local degree of supersaturation is bigger than normal, produce local agglomeration, the powder of preparation is almost without reuniting, good dispersity, the work in-process that obtain after later stage calcining are also loose powdered shapes, do not need just can reach good fineness through art breading such as ball millings.Complexing-depositing technology that preparation method of the present invention adopts is that application in environmental-friendly pigment does not also have relevant report so far both at home and abroad at the synthetic titanium of liquid phase method
Compare to existing solid phase method technique, the powder color and luster that titanium pigment prepared by the present invention obtains is vivid, and size distribution interval is narrow, strong coloring force; Than liquid phase method technique, after powder calcination, present bulk Powdered, do not need ball milling can reach fineness requirement, only need simple pigment aftertreatment technology just can reach application requiring, like this, simplify to a certain extent production technique, reduced production cost.
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment 1:
1) respectively 82g titanium dioxide and 15g antimonous oxide are joined in 970ml water, 16g nickelous nitrate joins in 160ml water, standby after nickel nitrate solution clarification;
2) join in the mixed solution of titanium dioxide after taking the sodium hexametaphosphate solution of 0.3g, it is disperseed to 0.5h;
3) in step 2) in add the nickel nitrate solution having dissolved, stir 10-30min;
4) by 0.2g complexing agent---triethylene tetramine joins in the nickel nitrate solution having dissolved, the mol ratio of nickelous nitrate and triethylene tetramine is controlled between 0.5-2, the pH value of system is controlled between 6-8, temperature of reaction system is elevated to 50-70 ℃, control stir speed (S.S.) 400-600r min, the treatment time is 0.5h-4h;
5) by the concentration preparing, be 0.5-2mol the sodium hydroxide clear liquor of L be slowly added drop-wise in step 4) nickel nitrate solution, control rate of addition is 10ml/min, after all dropping finishes, regulate reacting system PH value in 10 left and right, ageing 2h, the nano-sized nickel hydroxide pattern forming on titanium dioxide surface is subsphaeroidal, and size distribution is even, and size is in 30nm left and right;
6) slurry is carried out to vacuum filtration, repetitive scrubbing three times, detect solution pH value to neutral, carry out spray drying treatment, control drying parameter: charging total amount 10kg h, in drying tower, negative pressure is 500Kpa, 165 ℃ of inlet temperature, 65 ℃ of temperature of outgoing airs, obtain fineness at the subsphaeroidal powder granule of 1um left and right;
7) powder of oven dry is added to the mineralizer preparing, wherein borax is 8g, silicon-dioxide 5g, zinc oxide 2g, batch mixing evenly after, calcine, heat-up rate be 5 ℃ min, be warming up to 950 ℃, insulation 1.5h, obtains required powder pigment.
Embodiment 2:
1) respectively 75g titanium dioxide and 10g antimonous oxide are joined in 850ml water, 15g chromium nitrate joins in 150ml water, standby after chromium nitrate solution clarification;
2) join in the mixed solution of titanium dioxide after taking the sodium hexametaphosphate solution of titanium dioxide weight 0.25g, it is disperseed to 0.5h;
3) in step 2) in add the chromium nitrate solution having dissolved, stir 10-30min;
4) get the complexing agent of 0.4g---citric acid joins in the chromium nitrate solution having dissolved, the mol ratio of chromium nitrate and citric acid is controlled between 0.5-2, the pH value of system is controlled between 6-8, temperature of reaction system is elevated to 50-70 ℃, control stir speed (S.S.) 400-600r min, the treatment time is 0.5h-4h;
5) by the concentration preparing, be 0.5-2mol the potassium hydroxide clear liquor of L be added drop-wise to slowly in step 4) chromium nitrate solution, control rate of addition is 10ml/min, after all dripping and finishing, regulates reacting system PH value in 8 left and right, ageing 2h.The nanometer chromium hydroxide pattern forming on titanium dioxide surface is subsphaeroidal, and size distribution is even, and size is in 40nm left and right;
6) solution of being prepared by step 5) carries out vacuum filtration, repetitive scrubbing three times, detect solution pH value to neutral, carry out spray drying treatment, control drying parameter: charging total amount 11kg h, in drying tower, negative pressure is 500Kpa, 165 ℃ of inlet temperature, 65 ℃ of temperature of outgoing airs, obtain fineness at the subsphaeroidal powder granule of 1um left and right;
7) powder of oven dry is added to the mineralizer preparing, wherein borax is 2g, silicon-dioxide 4g, zinc oxide 1g, batch mixing evenly after, calcine, heat-up rate be 5 ℃ min, be warming up to 1000 ℃, insulation 2h, obtains required powder pigment.
Embodiment 3:
1) 70g titanium dioxide is joined in 700ml water, 10g nickelous nitrate, 15g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 5g zinc nitrate join in 300ml water, standby after nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, zinc nitrate solution clarification;
2) join in the mixed solution of titanium dioxide after taking the sodium hexametaphosphate solution of titanium dioxide weight 0.35g, it is disperseed to 0.5h;
3) in step 2) in add the nickelous nitrate having dissolved, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and zinc nitrate solution, stir 10-30min;
4) by the complexing agent of 0.7g---triethylene tetramine and citric acid (ratio 1:1) join the nickelous nitrate having dissolved, in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and zinc nitrate solution, nickelous nitrate, the mol ratio of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and zinc nitrate and triethylene tetramine and citric acid is controlled between 0.5-2, the pH value of system is controlled between 6-8, temperature of reaction system is elevated to 50-70 ℃, control stir speed (S.S.) 400-600r min, the treatment time is 0.5h-4h;
5) by the concentration preparing, be 0.5-2mol sodium hydroxide, the potassium hydroxide clear liquor of L be slowly added drop-wise in step 4) nickel nitrate solution, control rate of addition is 15ml/min, after all dropping finishes, regulate reacting system PH value in 9 left and right, ageing 2h, the nano-sized nickel hydroxide pattern forming on titanium dioxide surface is subsphaeroidal, and size distribution is even, and size is in 35nm left and right; 6) slurry is carried out to vacuum filtration, repetitive scrubbing three times, detect solution pH value to neutral, carry out spray drying treatment, control drying parameter: charging total amount 12kg h, in drying tower, negative pressure is 500Kpa, 160 ℃ of inlet temperature, 60 ℃ of temperature of outgoing airs, obtain fineness at the subsphaeroidal powder granule of 1um left and right;
7) powder of oven dry is added to the mineralizer preparing, wherein borax is 0.5g, silicon-dioxide 0.5g, zinc oxide 1.5g, batch mixing evenly after, calcine, heat-up rate be 5 ℃ min, be warming up to 900 ℃, insulation 1h, obtains required powder pigment.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the environmental protection titanium pigment that prepared by complexing-depositing technology, is characterized in that, comprises the steps:
1) take the titanium dioxide of certain part by weight, or the antimonous oxide that takes the titanium dioxide of certain part by weight and account for titanium dioxide weight 10-15%, join in the aqueous solution that is dissolved with tensio-active agent, be uniformly dispersed, the weight of wherein said tensio-active agent is the 0.2-0.5% of titanium dioxide weight;
2) add coloring ion R
+with the mixing solutions of complexing agent, control the content of described complexing agent and described coloring ion, make to form stable system between coloring ion and complexing agent, the pH value of regulation system, makes system in steady state;
3) drip slowly 0.5mol l alkaline solution to step 2) in, make coloring ion and the alkaline solution generation precipitin reaction that splashes into;
4) after alkaline solution titration finishes, ageing 2h, carries out rinsing to reaction system, filters, and removes foreign ion;
5) slurry after rinsing is carried out to spray drying treatment;
6) at dried powder, add mineralizer, carry out air atmosphere calcining after mixing in retort furnace, temperature is controlled at 900-1200 ℃, and insulation 1-2h, obtains required powder.
2. the environmental protection titanium pigment that prepared by a kind of complexing-depositing technology according to claim 1, is characterized in that, described tensio-active agent is Sodium hexametaphosphate 99.
3. the environmental protection titanium pigment that prepared by a kind of complexing-depositing technology according to claim 1, is characterized in that, described step 2) in, described coloring ion R
+for Ni
2+, Cr
3+, Co
2+, Zn
2+.
4. the environmental protection titanium pigment that prepared by a kind of complexing-depositing technology as claimed in claim 3, is characterized in that, contains described coloring ion R
+compound be one or more in nickelous nitrate, chromium nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or zinc nitrate, account for the 20-50% of described titanium dioxide weight.
5. the MMO environmental protection titanium pigment as described in claim 3 or 4, is characterized in that: described complexing agent is triethylene tetramine or/and citric acid, accounts for the 0.2%-1% of described titanium dioxide weight.
6. the environmental protection titanium pigment that prepared by a kind of complexing-depositing technology as described in claim 1-4 any one, it is characterized in that, described step 2) in, the mol ratio of coloring ion and complexing agent is controlled between 0.5-2, the PH that measures system with test paper is between 6-8, temperature of reaction is elevated to 50-70 ℃, control stir speed (S.S.) 400-600r min, the treatment time is 0.5h-4h.
7. the environmental protection titanium pigment that prepared by a kind of complexing-depositing technology as claimed in claim 1, is characterized in that: in described step 3), the speed of response that alkaline solution clear liquor drips is controlled in 10-15ml/min, and control pH value is 8-12.
8. the environmental protection titanium pigment that prepared by a kind of complexing-depositing technology as described in claim 1 or 7, is characterized in that: described alkaline solution is sodium hydroxide solution and/or potassium hydroxide solution.
9. the environmental protection titanium pigment that prepared by a kind of complexing-depositing technology as claimed in claim 1, it is characterized in that: described step 5) drying treatment parameter: charging total amount 10-12kg h, in tower, negative pressure is 400-600Kpa, inlet temperature 150-165 ℃, temperature of outgoing air 60-65 ℃.
10. the environmental protection titanium pigment that prepared by a kind of complexing-depositing technology as claimed in claim 1, it is characterized in that, the described mineralizer adding in described step 6) is one or more in borax and silicon-dioxide, zinc oxide, wherein said borax is the 0.1-10%g of titanium dioxide weight, silicon-dioxide is the 0.4-6% of titanium dioxide weight, and zinc oxide is the 0.1-5% of titanium dioxide weight.
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| CN107325586A (en) * | 2017-06-16 | 2017-11-07 | 华南理工大学 | A kind of method of soft mechanical force and chemical assisted Solid-state method titania type titanium yellow ceramic pigment |
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| CN108165052A (en) * | 2017-12-14 | 2018-06-15 | 华南理工大学 | A kind of ceramic pigment with near-infrared reflection and preparation method thereof |
| CN117488431A (en) * | 2023-11-07 | 2024-02-02 | 广州傲群刷业科技有限公司 | Yellow flame-retardant nylon yarn and preparation method and application thereof |
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| CN107325586A (en) * | 2017-06-16 | 2017-11-07 | 华南理工大学 | A kind of method of soft mechanical force and chemical assisted Solid-state method titania type titanium yellow ceramic pigment |
| CN108165052A (en) * | 2017-12-14 | 2018-06-15 | 华南理工大学 | A kind of ceramic pigment with near-infrared reflection and preparation method thereof |
| CN108165052B (en) * | 2017-12-14 | 2020-11-24 | 华南理工大学 | Ceramic pigment with near-infrared reflection function and preparation method thereof |
| CN108084768A (en) * | 2017-12-19 | 2018-05-29 | 江南大学 | A kind of preparation method of the near-infrared reflection insulating color pigment with nucleocapsid |
| CN117488431A (en) * | 2023-11-07 | 2024-02-02 | 广州傲群刷业科技有限公司 | Yellow flame-retardant nylon yarn and preparation method and application thereof |
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