CN1230378C - Method for directly synthesizing nano zinc phosphate crystal by using low-heat solid phase chemical reaction - Google Patents
Method for directly synthesizing nano zinc phosphate crystal by using low-heat solid phase chemical reaction Download PDFInfo
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Abstract
The present invention relates to a synthetic method of nanometer zinc phosphate. Zinc salt powder, inorganic phosphate powder and a moulding board agent are proportionally mixed, are milled for 10 to 180 minutes under the normal pressure at 15 to 150 DEG C, and then are kept statically; thereafter, soluble inorganic salt by-products in reaction mixtures can be washed by water, are filtered, are dried, and are pulverized so that the nanometer-stage zinc phosphate crystal can be obtained. Compared with a liquid phase method, a hydrothermal method or a solvothermal method, the method has the advantages of unnecessary solvent in the reaction, mild reaction condition, easy control, simplicity, short technological route, few steps, cheap price for raw materials, wide resources, etc. The obtained nanometer phosphonic acid crystal has a medium micropore structure, can be used as novel non-poisonous antirust pigment as well as can be used as a novel medium porous material with the functions of catalysis, adsorption or separation.
Description
Technical field
The present invention relates to the zinc phosphate crystalline material, particularly nanometer zinc phosphate crystalline synthetic method.
Background technology
The zinc phosphate crystal is a kind of novel non-poisonous antirust pigment of excellent property, and consumption is huge, and purposes is very extensive, can mix mutually with various resins such as alkyd, epoxy, phenolic aldehyde, chlorinated rubber, amino, is applied to coatings industry and prepares all kinds of rust-inhibiting paints and water-borne coatings.Germany RAL7005 universal primer is exactly the rust-inhibiting paint that zinc phosphate is made rust-stabilising pigment.
On the other hand, the zinc phosphate crystal has the opening that is similar to as the zeolite and is situated between and sees microvoid structure, is a kind of type material with catalysis, absorption and separation function.
The nanometer zinc phosphate crystal both can be used as novel non-poisonous antirust pigment, and can be used as novel Jie again and see porous material with catalysis, absorption or separation function, be a kind of type material that multiple function is arranged.
Zinc phosphate crystal grain is during as the purposes of rust-stabilising pigment, and production method is a liquid phase method, mainly contains two kinds: direct method and indirect method.Indirect method is raw material synthetic obtaining in the aqueous solution with zinc salt and inorganic phosphate, and product granularity is big, and technology is complicated, and quality product is wayward.The native land is inside and outside many based on direct method production.Direct method is to be that the raw material direct reaction prepares zinc phosphate with zinc oxide and phosphoric acid.More little its dispersiveness of the granularity of zinc phosphate is good more, and the product that how to obtain small grain size is the key issue during zinc phosphate is produced.In order to obtain the product of small grain size, improve the zinc phosphate dispersing of pigments, abroad some documents disclose the method for preparing zinc phosphate, as distributing in order to obtain fine particle and uniform particle size, react under high-speed stirring or ultrasonic agitation condition; For improving dispersing of pigments and preventing precipitation, add tensio-active agent etc.Domesticly many reduce the zinc phosphate granularity improving pigment-dispersing, but still be difficult to satisfy the exported product specification of quality by pulverizing.
Just the production method of the novel non-poisonous antirust pigment zinc phosphate of understanding at present is liquid phase method, wherein is used for the many based on direct method of actual production.Its processing step is: at first, obtaining zinc phosphate with the reaction of zinc oxide slurry and dilute phosphoric acid, then, aging through being incubated, precipitate, filter, dry, grind the product zinc phosphate.The advantage of this method be raw material be easy to get, inexpensive, production cost is low, but also there are some shortcomings, show that synthetic route is long, step is many, needs with a large amount of water as solvent, produce a large amount of waste water inevitably, and how to produce and obtain fine zinc phosphate, be the still unsolved key issue of this method, also be simultaneously to be badly in need of the key issue that solves in China's exported product quality index.
Some open source literatures have been reported improved liquid phase method nanometer zinc phosphate crystal preparation method in recent years, have published " the quick Preparation by Uniform Precipitation Zn of Zhu Qiongxia poplar rich nations of Anhui Normal University as " Anhui chemical industry " 2001,27 (2) .-15-16
3(PO
4)
2Nanoparticle " adopt quick sluggish precipitation in aqueous phase system, to prepare Zn
3(PO
4)
2Nanoparticle.With H
3PO
4And Zn (NO
3)
2As the reaction starting soln, contain the cold ammoniacal liquor of surfactant polyethylene octyl phenyl ether (OF) by adding, preparing no reunion, narrow particle size distribution, particle diameter is the spherical Zn of 40-50nm
3(PO
4)
2Particulate.
Chinese patent＜application number〉97101637＜denomination of invention〉liquid-preparation of zinc phosphate by liquid-liquid heterogeneous reaction＜applicant〉Kunming University of Science and Technology＜digest〉the invention discloses a kind of technology of liquid-preparation of zinc phosphate by liquid-liquid heterogeneous reaction, zinc phosphate is used for coating and tackiness agent.It selects rudimentary zinc oxide (ZnO content is 50%～95%) for use is raw material, through nitration mixture dissolving, purify, concentrate and make the solution that contains zinc 10%～18% and contain 11%～17%P
2O
5Organic phase ammonium P
2O
5React with the stoichiometric of Zn.Temperature of reaction is 70～90 ℃, and the reaction times is 40～60 minutes, and stirring velocity is 4～6 revolutions per seconds, and organic phase recycles, and solution adds alkali makes pH=3.1-4.Precipitation after filtration, washing, dry three replaces the phosphate dihydrate zinc.This method production cost is low, product yield is high, good quality of product.
Chinese patent＜application number〉96117346＜denomination of invention〉purification of wet process phosphoric acid for preparing zinc phosphate＜applicant〉Kunming University of Science and Technology＜digest〉the invention discloses a kind of zinc phosphate and make novel process, (contain butanols＞60%, TBP＜40%=extraction contains 25～40%P with mixed solvent for it
2O
5Phosphoric acid by wet process, make solvent phase and contain the aqueous suspension of ZnO＞99%.At 70～90 ℃, stirring velocity is 5～7 rev/mins, and the reaction times is to react under 30～60 minutes the condition, the precipitation of generation after filtration, washing, dry zinc phosphate.Mixed solvent is big to phosphoric acid collection output capacity, phase-splitting is functional, and proportion, viscosity are little, can reduce the bonding and phenomenon that is wrapped of zinc oxide, and reaction can be carried out fully.This method technology is simple, and product purity and yield height are with low cost.
At present, contain organic template, to have a novel zinc phosphate crystalline that be situated between to see microvoid structure synthetic by hydrothermal system, has been extended to the solvent thermal system.No matter be hydrothermal system or solvent thermal system but, all need under higher temperature and pressure insulation reaction to reach the time of several days and even tens days, synthesis cycle is long, reaction conditions harshness be these method common shortcomings.
Know that by present disclosed document the synthetic method of the synthetic method of zinc phosphate crystal during as novel non-poisonous antirust pigment when seeing porous material as being situated between is distinct.
Technology contents
In order to obtain both can be used as novel non-poisonous antirust pigment, again can be with having catalysis, the zinc phosphate crystal of absorption and separation function is situated between and sees porous material, the inventor is through testing repeatedly and exploring, to liquid phase method, hydrothermal method, quick sluggish precipitation, liquid-liquid-liquid heterogeneous reaction or solvent-thermal method contrast, and the zinc phosphate crystal all studied from both macro and micro, found a kind of existing the whole bag of tricks of being different from, technology is simple, raw material is inexpensive, pollution-free, obtain having the method for the novel zinc phosphate crystalline material one-step synthesis of multiple function, the direct synthesis of nano zinc phosphate of low-heat solid state reaction crystalline method that Here it is.
The present invention realizes its purpose as follows: with zinc salt powder, inorganic phosphate powder is basic raw material, add template, mixing the back under 15～150 ℃, non-pressurized condition grinds, then allow the reaction mixture insulation leave standstill, wash the inorganic salt by-product of solubility in the dereaction mixture then with water, filter, oven dry obtains nano level zinc phosphate crystal after the pulverizing.
Above-described synthesis of nano zinc phosphate crystalline method, its proportioning raw materials is: zinc salt: inorganic phosphate=1.0～2.5: 1.0 (mol ratios), template then account for 0.1～15% of entire reaction thing weight.
Above-described synthesis of nano zinc phosphate crystalline method, the time of grinding is 10～180 minutes.
Above-described synthesis of nano zinc phosphate crystalline method, the time that insulation is left standstill is 1～48 hour.
Above-described zinc salt comprises a kind of in zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc oxalate, the zinc citrate or several combination under compatible situation;
Above-described inorganic phosphate comprises a kind of in SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, diammonium phosphate, Sodium phosphate dibasic, dipotassium hydrogen phosphate, Secondary ammonium phosphate, sodium phosphate, potassiumphosphate, the ammonium phosphate or several combination under compatible situation; Zinc salt and inorganic phosphate must a kind of crystal water that contains among both.
Above-described template can be a nonionic surface active agent, a kind of in the protonated organic amine or combination in compatible is arranged; Nonionic surface active agent in the template is a kind of in Oleum Cocois alkylamide, tween series, OP series, polyoxyethylene glycol series, polyether series, the Sorbic Acid glyceryl ester or several combination under compatible situation; Protonated organic amine be a kind of in alkane amine series, alkene amine series, the aromatic hydrocarbons amine series or under compatible situation several combinations back and mineral acid or the formed salt of organic acid.Carry out relatively fully in order to guarantee reaction, before two kinds of inorganic salt hybrid reactions, template must be pre-mixed evenly with zinc salt powder or inorganic phosphate powder, template is premixed in the zinc salt powder, perhaps template is premixed in the inorganic phosphate powder, perhaps template is sneaked in the powder of two kinds of salt respectively in advance.
Above-described synthesis of nano zinc phosphate crystalline process, the inorganic salt by-product that washes solubility in the dereaction mixture with water can reclaim to be utilized again, being about to it concentrates, can make other byproduct, as materials such as vitriolate of tartar, sodium sulfate, Repone K, sodium-acetate, saltpetre, when obtaining these byproducts, can avoid discharging environment again and pollute.
The zinc phosphate nanocrystal that obtains with above-mentioned synthetic method, productive rate is more than 95%, the median size of primary particle is less than 60nm, it is few to reunite, realized that the reaction process step is few, do not needed solvent, the productive rate height, reaction conditions gentleness, easy to control directly obtains having the purpose that Jie sees the nano level zinc phosphate crystal (comprising two hypophosphite monohydrate zinc nanocrystalline bodies and Zinc phosphate tetrahydrate nanocrystal) of microvoid structure.
The present invention mainly adopts low-heat solid state reaction synthesis method, under 15～150 ℃, non-pressurized condition, under the inducing of template, in the crystal water medium of constrained, orderly microencapsulation, carry out the double decomposition precipitation reaction by zinc salt powder and inorganic phosphate powder.Reaction generates the zinc phosphate of insoluble and the inorganic salt by-product of solubility, discharge the crystal water in the reaction raw materials simultaneously, then the inorganic salt of solubility are because of supersaturation, separate out with the crystallization of crystalline form, perhaps the zinc phosphate of Sheng Chenging generates crystal water in conjunction with free water, and these processes produce an intensive convergent force.Under induce of template, that the powerful internal pressure that above-mentioned convergent force forms is ordered about indissoluble around the inorganic salt and be difficult to the also syncrystallization of crystalline zinc phosphate as template.Because of zinc phosphate after reaction generates, be scattered in equably soluble inorganic salt around, so the particle that crystallization produces is very fine and well-balanced nanocrystal, it is all again that nanocrystalline what be subjected to is with a kind of contraction motivating force, so it is purified that reaction can obtain Chemical Composition, the zinc phosphate of single crystallographic system is nanocrystalline.In addition, owing in the raw material of reaction, contain template, after the nanocrystalline formation of zinc phosphate, the molecular layer of one deck template in the crystalline surface adsorption, help to prevent the reunionization of nanocrystal, the different temperature of control can be regulated and control the size of nanocrystal when insulation is left standstill.
Nanometer zinc phosphate crystalline low-heat solid state reaction synthetic method of the present invention is: at 15～150 ℃, under the non-pressurized condition, under agitation, in a certain amount of inorganic phosphate powder, add a certain amount of template thorough mixing (template can with the pre-mixing of inorganic phosphate powder, also can with the pre-mixing of zinc salt powder, even can be respectively and the pre-mixing of two kinds of salt powder), under agitation these inorganic phosphate powder that contain template are added in a certain amount of zinc salt powder then and (phosphate powder can be joined in the zinc salt powder, also can be conversely, the zinc salt powder is joined in the phosphate powder), add and mix back thorough mixing grinding 10～180 minutes, allow reaction mixture after insulation under 15～150 ℃ the temperature is left standstill 1～48 hour, wash the inorganic salt by-product of solubility in the dereaction mixture with water, filter, oven dry obtains nano level zinc phosphate crystal (comprising two hypophosphite monohydrate zinc nanocrystalline bodies and Zinc phosphate tetrahydrate nanocrystal) after the pulverizing.
Method of the present invention is with existing liquid phase method, hydrothermal method, sluggish precipitation, liquid-liquid-liquid heterogeneous reaction or solvent-thermal method are compared fast, the substantive distinguishing features and the obvious improvement of the inventive method are: reaction does not need solvent, reaction conditions gentleness, easy to control, simple and easy, operational path is short, step is few, raw material is inexpensive, wide material sources, be easy to obtain.Both save the step of aging in the liquid phase method, precipitation, continuous crystallization, overcome the shortcoming that wastewater discharge in the liquid phase method is big, be difficult to obtain the nano level product again, also overcome many shortcomings such as long-time thermal zone pressure reaction of hydrothermal method or solvent-thermal method simultaneously.Characteristic of the present invention is that the synthetic nanometer zinc phosphate crystal that obtains both can be used as novel non-poisonous antirust pigment, can see porous material with Jie with catalysis, absorption and separation function again, i.e. the present invention has unified original two kinds of distinct methods with low-heat solid state reaction method.
Embodiment
Below be the several embodiment of low-heat solid state reaction method nanometer zinc phosphate crystalline of the present invention:
Embodiment 1:
Get zinc acetate powder 10mol (2195g), sodium phosphate powder 9mol (3421g), sodium dihydrogen phosphate powder 1mol (156g), polyoxyethylene glycol-400 (29g).In an enamelled vessel that sodium phosphate powder and sodium dihydrogen phosphate powder thorough mixing is even, it is evenly standby then to add poly-ethanol and ground and mixed, then at 45 ℃, under the normal pressure, under agitation toward in the zinc acetate powder, adding above-mentioned phosphate powder, add and mix the back and continue fully to grind to stir 100 minutes, be incubated in 130 ℃ and left standstill 5 hours, water repetitive scrubbing reaction mixture three times is to more than three times, behind the intact reactant flush away of by product sodium-acetate and unreacted, filtration under diminished pressure, with a small amount of raw spirit washing leaching cake, then filter is done as far as possible, get filter cake, smash to pieces,, pulverize in 130 ℃ of oven dry 1～2 hour, can obtain two hypophosphite monohydrate zinc nanocrystalline bodies, if 100 ℃ of following negative pressure oven dry, what then obtain is the Zinc phosphate tetrahydrate nanocrystal, yield 〉=95% (is benchmark with the zinc salt).
Embodiment 2:
Get zinc oxalate powder 13mol (2463g), sodium phosphate powder 8mol (3041g), Sodium phosphate dibasic powder 2mol (716g), OP-10 (327g).In an enamelled vessel that sodium phosphate powder and Sodium phosphate dibasic powder thorough mixing is even; Then holding at another enamel mixes zinc oxalate powder and OP-10 standby in the product; Then at 100 ℃, under the normal pressure, under agitation in the zinc oxalate powder that contains template, add above-mentioned phosphate powder, mixed the back and continued fully to grind to stir 10 minutes, 75 ℃ down insulation left standstill 24 hours, water repetitive scrubbing reaction mixture three times is to more than three times, behind the intact reactant flush away of by product sodium oxalate and unreacted, filtration under diminished pressure, with a small amount of raw spirit washing leaching cake, then filter is done as far as possible, get filter cake, smash to pieces,, pulverize in 130 ℃ of oven dry 1～2 hour, can obtain two hypophosphite monohydrate zinc nanocrystalline bodies, if 100 ℃ of following negative pressure oven dry, what then obtain is the Zinc phosphate tetrahydrate nanocrystal, yield 〉=95% (is benchmark with the zinc salt).
Embodiment 3:
Get zinc acetate powder 4mol (878g), zinc sulphate powder 12mol (3256g), sodium phosphate powder 9mol (3421g), Sodium phosphate dibasic powder 1mol (358g), tween-80 (100g), triethanolamine hydrochloride (1296g).In an enamelled vessel that sodium phosphate powder and Sodium phosphate dibasic powder thorough mixing is even, the triethanolamine hydrochloride that then adds the tween-80 of half amount and half amount mixes, standby; In another enamelled vessel that zinc acetate powder and zinc sulphate powder thorough mixing is even, the triethanolamine hydrochloride that then adds the tween-80 of half amount and half amount mixes, standby.Then at 30 ℃, under the normal pressure, the mixture that under agitation mixture of phosphate powder is added the zinc salt powder, add and mix the abundant grinding stirring of back continuation 130 minutes, insulation was left standstill 48 hours under 15 ℃, water repetitive scrubbing reaction mixture three times is to more than three times, the by product sodium-acetate, behind the zinc acetate flush away that sodium sulfate and unreacted finish, filtration under diminished pressure, with a small amount of raw spirit washing leaching cake, then filter is done as far as possible, get filter cake, smash to pieces,, pulverize in 130 ℃ of oven dry 1～2 hour, can obtain two hypophosphite monohydrate zinc nanocrystalline bodies, if 100 ℃ of following negative pressure oven dry, what then obtain is the Zinc phosphate tetrahydrate nanocrystal, yield 〉=95% (is benchmark with phosphoric acid salt).
Embodiment 4:
Zinc sulphate powder 19mol (5155g), sodium phosphate powder 8mol (3041g), Secondary ammonium phosphate powder 2mol (264.2g), OP-10 (8.5g).In an enamelled vessel that sodium phosphate powder and Sodium phosphate dibasic powder thorough mixing is even, then add OP-10 mix, standby; In another enamelled vessel that zinc acetate powder and zinc sulphate powder thorough mixing is even, standby.Then at 80 ℃, under the normal pressure, the mixture that under agitation mixture of phosphate powder is added the zinc salt powder, add and mix the back and continue fully to grind to stir 40 minutes, 150 ℃ down insulation left standstill 1 hour, water repetitive scrubbing reaction mixture three times is to more than three times, the by product sodium-acetate, behind the intact reactant flush away of sodium sulfate and unreacted, filtration under diminished pressure, with a small amount of raw spirit washing leaching cake, then filter is done as far as possible, get filter cake, smash to pieces,, pulverize in 130 ℃ of oven dry 1～2 hour, can obtain two hypophosphite monohydrate zinc nanocrystalline bodies, if 100 ℃ of following negative pressure oven dry, what then obtain is the Zinc phosphate tetrahydrate nanocrystal, yield 〉=95% (in zinc salt).
Embodiment 5:
Get zinc chloride powder 4mol (403g), zinc sulphate powder 18mol (4884g), sodium phosphate powder 8mol (3041g), Sodium phosphate dibasic powder 2mol (716g), tween-80 (91g).In an enamelled vessel that sodium phosphate powder and Sodium phosphate dibasic powder thorough mixing is even, then add tween-80 mix, standby; In another enamelled vessel that zinc acetate powder and zinc sulphate powder thorough mixing is even, standby.Then at 15 ℃, under the normal pressure, the mixture that under agitation mixture of phosphate powder is added the zinc salt powder, add and mix the abundant grinding stirring of back continuation 180 minutes, insulation was left standstill 12 hours under 100 ℃, water repetitive scrubbing reaction mixture three times is to more than three times, the by product sodium-acetate, behind the reactant flush away that sodium sulfate and unreacted finish, filtration under diminished pressure, with a small amount of raw spirit washing leaching cake, then filter is done as far as possible, get filter cake, smash to pieces,, pulverize in 130 ℃ of oven dry 1～2 hour, can obtain two hypophosphite monohydrate zinc nanocrystalline bodies, if 100 ℃ of following negative pressure oven dry, what then obtain is the Zinc phosphate tetrahydrate nanocrystal, yield 〉=95% (is benchmark with phosphoric acid salt).
Embodiment 6:
Get zinc sulphate powder 25mol (6783g), sodium phosphate powder 9mol (3421g), Secondary ammonium phosphate powder 1mol (132.1g), tween-80 (100g), ethylenediamine-hydrochloride (1060g).In an enamelled vessel that sodium phosphate powder and Sodium phosphate dibasic powder thorough mixing is even, the ethylenediamine-hydrochloride that then adds the tween-80 of half amount and half amount mixes, standby; In another enamelled vessel that zinc acetate powder and zinc sulphate powder thorough mixing is even, the ethylenediamine-hydrochloride that then adds the tween-80 of second half amount and half amount is standby.Then at 60 ℃, under the normal pressure, the mixture that under agitation mixture of phosphate powder is added the zinc salt powder, add and mix the abundant grinding stirring of back continuation 70 minutes, insulation was left standstill 36 hours under 40 ℃, water repetitive scrubbing reaction mixture three times is to more than three times, the by product sodium-acetate, behind the reactant flush away that sodium sulfate and unreacted finish, filtration under diminished pressure, with a small amount of raw spirit washing leaching cake, then filter is done as far as possible, get filter cake, smash to pieces,, pulverize in 130 ℃ of oven dry 1～2 hour, can obtain two hypophosphite monohydrate zinc nanocrystalline bodies, if 100 ℃ of following negative pressure oven dry, what then obtain is the Zinc phosphate tetrahydrate nanocrystal, yield 〉=95% (is benchmark with phosphoric acid salt).
Get above-mentioned arbitrary embodiment synthetic zinc phosphate nanocrystal, detect with XRD, crystal median size≤60nm, and also also there is the spectrum peak at 2 θ angles less than the places of 5 degree, illustrates having the sight of Jie microvoid structure.
Claims (5)
1, a kind of synthetic method of nanometer zinc phosphate, it is characterized in that: it adopts low-heat solid state reaction direct synthesis technique, concrete technology is, with the zinc salt powder, the inorganic phosphate powder is a raw material, its proportioning raw materials is: zinc salt: the mol ratio of inorganic phosphate is 1.0～2.5: 1.0, add template, template then accounts for 0.1～15% of entire reaction thing weight, at 15～150 ℃, mixing the back under the non-pressurized condition grinds, then allow the reaction mixture insulation leave standstill, wash the inorganic salt by-product of solubility in the dereaction mixture then with water, filter, oven dry obtains nano level zinc phosphate crystal after the pulverizing;
Described zinc salt is selected from a kind of in zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc oxalate, the zinc citrate or several combination under compatible situation;
Described inorganic phosphate is selected from a kind of in SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, diammonium phosphate, Sodium phosphate dibasic, dipotassium hydrogen phosphate, Secondary ammonium phosphate, sodium phosphate, potassiumphosphate, the ammonium phosphate or several combination under compatible situation;
Described zinc salt and inorganic phosphate must a kind of crystal water that contains among both;
Described template is selected from a kind of in tween series, OP series, the polyoxyethylene glycol or several combination under compatible situation; Perhaps template is the combination of ethylenediamine-hydrochloride and tween; Perhaps template is the combination of triethanolamine hydrochloride and tween.
2, the synthetic method of nanometer zinc phosphate according to claim 1 is characterized in that: the time of grinding is 10～180 minutes.
3, the synthetic method of nanometer zinc phosphate according to claim 1 is characterized in that: the time that insulation is left standstill is 1～48 hour.
4, the synthetic method of nanometer zinc phosphate according to claim 1, it is characterized in that: before zinc salt powder, the reaction of inorganic phosphate powder mixes, template is pre-mixed evenly with zinc salt powder or inorganic phosphate powder earlier, template is premixed in the zinc salt powder, perhaps template is premixed in the inorganic phosphate powder, perhaps template is sneaked in the powder of two kinds of salt respectively in advance.
5, the synthetic method of nanometer zinc phosphate according to claim 1, it is characterized in that: in the process of zinc salt powder, inorganic phosphate powder mixes and adding template, the inorganic phosphate powder is joined in the zinc salt powder, perhaps the zinc salt powder is joined in the inorganic phosphate powder.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102225751A (en) * | 2011-03-24 | 2011-10-26 | 广西冶金研究院 | Synthetic method of aluminium zinc phosphate nanocrystal |
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| CN100575454C (en) * | 2008-01-10 | 2009-12-30 | 同济大学 | Adulterated zinc ammonium phosphate orange red luminescent powder material of a kind of europium and preparation method thereof |
| CN105694570B (en) * | 2016-03-04 | 2017-07-25 | 广西民族大学 | A kind of nanometer zinc phosphate rust resisting pigment continuous producing method and process units |
| CN108569683B (en) * | 2018-04-23 | 2022-01-04 | 南京信息工程大学 | Zinc phosphate containing crystal water, preparation method thereof and application of zinc phosphate as photocatalyst |
| CN111816867B (en) * | 2020-07-01 | 2022-11-18 | 广西壮族自治区分析测试研究中心 | Sea urchin-shaped NiCo with mesoporous structure 2 O 4 Preparation method and application of three-dimensional construction graphene microsphere composite material |
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| CN102225751A (en) * | 2011-03-24 | 2011-10-26 | 广西冶金研究院 | Synthetic method of aluminium zinc phosphate nanocrystal |
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