CN102225751A - Synthetic method of aluminium zinc phosphate nanocrystal - Google Patents
Synthetic method of aluminium zinc phosphate nanocrystal Download PDFInfo
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- CN102225751A CN102225751A CN 201110072033 CN201110072033A CN102225751A CN 102225751 A CN102225751 A CN 102225751A CN 201110072033 CN201110072033 CN 201110072033 CN 201110072033 A CN201110072033 A CN 201110072033A CN 102225751 A CN102225751 A CN 102225751A
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Abstract
A synthetic method of an aluminium zinc phosphate nanocrystal adopts a direct synthetic method of low-heating solid-state chemical reaction, uses zinc salt powder, aluminium salt powder, and phosphate powder as raw materials, and comprises the following steps: adding a template, mixing and grinding under a condition with room temperature and normal pressure, allowing the reaction mixture to stand at a temperature from room temperature to 90 DEG C, washing the reaction mixture with water to remove by products of soluble inorganic salts, filtering, drying the filter cake at 100 DEG C to obtain a product of a zinc phosphate nanocrystal with a microcrystal particle size of 35 nm. Compared with the prior art, the aluminium zinc phosphate product obtained by the method of the invention has better corrosion inhibition performance than traditional zinc phosphate or aluminium phosphate products, and is a antirust material with excellent performance. Additionally, the method has the advantages of no solvent required, mild reaction conditions, easy control, simple process, extensive raw material sources, etc.
Description
Technical field
The present invention relates to the synthetic method of phosphoric acid zinc-aluminium crystalline material, specifically is a kind of synthetic method of zinc phosphate aluminum nanocrystalline body.
Background technology
Zinc phosphate is a kind of well-known rust-stabilising pigment, and its advantage mainly contains: better performances, and nontoxic, white or light, specific refractory power is low, therefore as easy as rolling off a log toning; Can be dispersed in the various base-materials such as oleoresin type and water-based; Coating with its preparation has good construction performance, and can film with metal substrate or with finish paint and have stronger sticking power; Raw material is easy to get, moderate cost etc.Therefore it is used as a kind of selectable pigment and is promoted application.But the antirust activity deficiency of standard zinc phosphate, this mainly is because the solubleness of this pigment is low and water-disintegrable poor.Therefore, it is difficult replacing traditional poisonous rust-stabilising pigment with the standard zinc phosphate comprehensively, particularly in aqueous priming paint, does not only reach the purpose that substitutes zinc chromate with the identical PVC of zinc chromate the time, and excess adds and also is difficult to reach the alternate purpose.Another shortcoming of standard zinc phosphate is the produce effects time-delay, and the speed that promptly forms effective protective membrane is too slow, therefore can not be used for the various maintenance priming paint of provisional protective cover.Facts have proved, adopt the standard zinc phosphate separately in the aqueous priming paint of meta-alkalescence, can not overcome so-called " dodging rust " problem.Therefore, it must cooperate just with chromic salt and can be used for electrophoretic primer.
The crystal particle diameter of common zinc orthophosphate below 5 μ m, (be generally 0.5～4 μ m) [Yang Zongzhi. zinc phosphate is the development of low/non-poisonous antirust pigment. domestic and international coatings industry, 2001, (6): 38-40,46.], but because of easily assembling, the pigment particle size that really embodies is much bigger, have in addition reach 12 μ m-20 μ m or bigger, and size-grade distribution is very wide.Like this, little not good with dispersiveness because of specific surface area, antirust activity naturally just can be high.
In order to reach comprehensive purpose that tradition contains the heavy metal rust-stabilising pigment that replaces, must carry out modification to it, developing zinc phosphate of new generation is active rust-stabilising pigment.Therefore, work out that granularity is little, the modified zinc phosphate crystal of narrowly distributing is the key that improves zinc phosphate series pigments product performance and broadened application scope.
In order to improve the antiseptic property of zinc phosphate series pigments, it is that rust-stabilising pigment carries out the surface-coating processing and carries out the bulk doped processing that the effort that people did comprises zinc phosphate, to increase new positively charged ion or to increase new negatively charged ion or increase new positively charged ion simultaneously and new negatively charged ion, so that reach its antirust activity of raising and the purpose of broadened application scope.Wherein, mix aluminum ion and can improve its antirust activity greatly in zinc phosphate, this introducing that belongs to an amount of aluminium can be regulated the solvability of zinc phosphate and at the sticking power of metallic surface.Mix in zinc phosphate aspect aluminium synthetic, the synthetic method of at present domestic open report mainly contains:
Ding Shiwen etc. have delivered the article about " the synthetic and sign of tripolyphosphate zinc-aluminium ", this article with zinc oxide and aluminium hydroxide as zinc source and aluminium source, phosphoric acid is as the phosphorus source, at first 100-150 ℃ of dissolving down, again the viscous fluid that obtains is aggregated into the tripolyphosphate zinc-aluminium under 250～400 ℃, the rustless property of products obtained therefrom surpasses 4 times of national standard, illustrates that aluminum ions existence played collaborative rot-resistant effect (" University Of Hebei's journal (natural science edition) " 1992,12 (4): 47-50).Its shortcoming is that preparation technology is complicated, is difficult for carrying out scale operation.
Yellow wind China etc. has delivered the article about " the synthetic and sign of zinc phosphate aluminum molecular screen ZAPO-5 crystalline ", this article is a raw material to visit aluminium stone, phosphoric acid, zinc acetate, organic formwork agent, prepares phosphoric acid zinc-aluminium through 48h～96h crystallization by hydrothermal method under 160 ℃～200 ℃.When template is trolamine, synthesized P: Al: Zn=12: 11: 1 ZAPO-5 crystallite; In the fluorion system, then obtained molecular sieve ZAPO one 5 large single crystals (" synthetic chemistry " 2005,13 (3): 304-306) of length 178 μ m when being template with diethylaminoethanol.But do not see the relevant report of the phosphoric acid zinc-aluminium of forming by this as rust-stabilising pigment.
Chinese patent 200810063893.9 has been introduced " fibre reinforcing zinc aluminum phosphate based composite material and preparation method thereof ", and the preparation fibre reinforcing zinc aluminum phosphate based composite material is to be made by fiber reinforced material and zinc phosphate aluminium glue gel material; Its preparation method is as follows: under 200～600 ℃ of conditions, with fiber reinforced material thermal treatment 10min～1h; Prepare fibre reinforcing zinc aluminum phosphate based composite material according to die press technology for forming then, its processing parameter is: molding temperature is 85～300 ℃, and molding pressure is 2～15MPa, and clamp time is 6～35 hours.
In the method for the synthetic phosphoric acid zinc-aluminium of above report, as zinc source and aluminium source, phosphoric acid is higher as the liquid phase reaction method cost in phosphorus source with zinc oxide and aluminium hydroxide, and the granularity of product is easy-regulating not; Though hydrothermal synthesis method can obtain the phosphoric acid zinc-aluminium of crystallite, the processing condition harshness is difficult for realizing scale production; Sol-gel method prepares the phosphoric acid zinc-aluminium and also has the processing condition harshness, is difficult for realizing the shortcoming of scale production.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is simple to the invention provides a kind of preparation technology, is easy to suitability for industrialized production, the synthetic method of the zinc phosphate aluminum nanocrystalline body that gained zinc phosphate aluminum nanocrystalline good dispersity, corrosion inhibition are higher.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
A kind of phosphoric acid zinc-aluminium crystalline synthetic method, it adopts low-heat solid state reaction method directly synthetic, concrete technology is, with zinc salt powder, aluminium salt powder, phosphate powder is raw material, its proportioning raw materials is: zinc salt: aluminium salt: phosphatic material mass ratio is 0.05～0.95: 0.05～0.95: 2.0～3.0, add template, template accounts for 0.1～10% of entire reaction thing weight; Under room temperature, non-pressurized condition, mix the back and grind 10～120min, then allow reaction mixture under room temperature～90 ℃, leave standstill 1～5 hour, wash the inorganic salt by-product of solubility in the dereaction mixture then with water, filter, filter cake 100 ℃ of oven dry down, is obtained zinc phosphate aluminum nanocrystalline product.
Above-mentioned zinc salt is selected from a kind of or several combination under compatible situation in zinc chloride, zinc sulfate, zinc nitrate, the zinc acetate.
Above-mentioned aluminium salt comprises a kind of or several combination under compatible situation in aluminum chloride, aluminum nitrate, the Tai-Ace S 150;
Above-mentioned phosphoric acid salt is selected from a kind of or several combination under compatible situation in sodium phosphate, sodium hydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, the potassiumphosphate;
Have the two or more crystal water that contain in above-mentioned zinc salt, aluminium salt and the phosphoric acid salt at least;
It can be nonionic surface active agent that above-mentioned template is selected from above-described template, the combination under a kind of or compatible situation in the protonated organic amine; 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 fully in order to guarantee reaction, before three kinds of inorganic salt hybrid reactions, template must be pre-mixed evenly with mixture or the phosphate powder that zinc salt powder, aluminium salt powder are formed, template is premixed in the mixture that zinc salt powder, aluminium salt powder formed, perhaps template is premixed in the phosphate powder, perhaps template is sneaked in the powder of three kinds of salt respectively in advance.
The method of above-mentioned synthetic zinc phosphate aluminum nanocrystalline, before zinc salt, aluminium salt and phosphate powder hybrid reaction, template elder generation is pre-mixed evenly with the mix powder or the phosphate powder of zinc salt, aluminium salt, perhaps template is premixed in the phosphate powder, perhaps template is sneaked in the powder of three kinds of salt respectively in advance.
The process of above-described synthetic zinc phosphate aluminum nanocrystalline, the inorganic salt by-product that washes solubility in the dereaction mixture with water can reclaim and be used, being about to it concentrates, can make other byproduct, as materials such as sodium sulfate, vitriolate of tartar, ammonium sulfate, sodium-chlor, Repone K, sodium-acetate, SODIUMNITRATE, saltpetre, when obtaining these byproducts, can avoid again because of directly discharging the pollution that environment causes.
With the zinc phosphate aluminum nanocrystalline that above-mentioned synthetic method obtains, productive rate has realized that more than 95% the reaction process step is few, does not need solvent, productive rate height, reaction conditions gentleness, easy to control.Adopt product that method of the present invention obtains that the corrosion inhibition of carbon steel is better than traditional zinc phosphate or aluminum phosphate.
The present invention mainly adopts the low fever solid phase reaction synthesis method, under room temperature, non-pressurized condition, in crystal water medium, carry out the metathesis conversion reaction under the inducing of template, in constrained, orderly microencapsulation by zinc salt powder, aluminium salt powder, phosphate powder.Reaction generates the binary metal phosphoric acid salt 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 binary metal phosphoric acid salt of Sheng Chenging generates crystal water in conjunction with free-water, and these processes produce an intensive convergent force.Do in template under the inducing 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 the corresponding insoluble metal phosphoric acid salt of crystalline.Because of the difficultly-soluble phosphates of respective metal through being scattered in equably after the reaction around the inorganic salt of solubility, and do not have that the difference because of different metal indissoluble thing solubility product produces the fractional precipitation problem in the liquid phase method, so can mix equably with the yardstick of molecular level between the phosphoric acid salt of different metal, make the interionic of forming the phosphoric acid zinc-aluminium realize self-assembly, and in-situ transesterification change into zinc phosphate aluminium crystal.
Method of the present invention compared with prior art, advantage such as having reaction does not need solvent, and reaction conditions is gentle, easy to control, and technology is simple, raw material sources are wide.Both overcome when respective metal generates throw out in the liquid phase method fractional precipitation problem that the difference because of solubility product causes, overcome the big shortcoming of discharged waste water in the liquid phase method again.This law is compared with high-temperature solid phase reaction method, high-energy ball milling method, can reduce phosphoric acid zinc-aluminium crystalline formation temperature greatly.Characteristic of the present invention is to synthesize the phosphoric acid zinc-aluminium product of required component, performance on demand.
Description of drawings
Fig. 1 adopts the X-ray diffraction (XRD) of the product of the method for the invention acquisition to analyze collection of illustrative plates.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described.
Below be that the present invention utilizes low-heat solid state reaction method to synthesize phosphoric acid zinc-aluminium Zn
(3-1.5x)Al
x(PO
4)
2The several embodiment of (0＜x＜2) crystalline:
Embodiment 1
Preparation Zn
1.5Al
1.0(PO
4)
2
Get zinc sulfate ZnSO
47H
2O powder 15.0mol is 4313.3g, aluminum nitrate Al (NO
3)
39H
2O powder 10.0mol is 3751.3g, sodium phosphate Na
3PO
412H
2O powder 23.0mol is 8742.1g, and polyoxyethylene glycol-400 is 258g.In an enamelled vessel, add sodium phosphate powder, then add polyoxyethylene glycol-400 and mix standby, then under room temperature, normal pressure, under agitation in the sodium phosphate powder that mixes with polyoxyethylene glycol-400, add above-mentioned zinc salt powder, aluminium salt powder, add to mix in the back immigration grinding plant and fully grind 40min, at room temperature leave standstill 1.5h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution detects less than SO
4 2-Till, filtration under diminished pressure.Filter cake being dried by the fire 2～4h down at 100 ℃, dried filter cake is worn into powder, obtain zinc phosphate aluminum nanocrystalline body, is benchmark with the zinc salt, yield 〉=95%.
Embodiment 2
Preparation powder Zn
1.5Al
1.0(PO
4)
2
Get zinc sulfate ZnSO
47H
2O powder 15.0mol is 4313.3g, aluminum chloride AlCl
36H
2O powder 10.0mol is 2414.3g, sodium phosphate Na
3PO
412H
2O) powder 23.0mol is 8742.1g, and OP-10 is 338g.In an enamelled vessel, add sodium phosphate powder, it is evenly standby then to add OP-10 and ground and mixed, then under room temperature, normal pressure, under agitation to the uniform sodium phosphate powder of OP-10 ground and mixed in add above-mentioned zinc salt powder, aluminium salt powder, add to mix in the back immigration grinding plant and fully grind 50min, at room temperature leave standstill 1.5h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution detects less than SO
4 2-Till, filtration under diminished pressure.Filter cake being dried by the fire 3～4h down at 100 ℃, dried filter cake is worn into powder, obtain zinc phosphate aluminum nanocrystalline body, is benchmark with the zinc salt, yield 〉=95%.
Embodiment 3
Preparation Zn
1.5Al
1.0(PO
4)
2
Get zinc sulfate ZnSO
47H
2O powder 15.0mol is 4313.3g, aluminum nitrate Al (NO
3)
39H
2O powder 10.0mol is 3751.3g, sodium hydrogen phosphate Na
2HPO
412H
2O powder 25.0mol is 9628.5g, and tween-80 is 131g, triethanolamine hydrochloride 131g.In an enamelled vessel, add the sodium hydrogen phosphate powder, then add tween-80 of half and the triethanolamine hydrochloride of half and mix, standby.In another enamelled vessel that zinc sulphate powder, aluminum nitrate powder thorough mixing is even, then add second half tween-80 and second half triethanolamine hydrochloride and mix, standby.Then under room temperature, normal pressure, under agitation in sodium hydrogen phosphate, add above-mentioned zinc salt powder, the mixture of aluminium salt powder, add to mix in the back immigration grinding plant and fully grind 70min, at room temperature leave standstill 2h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution detects less than SO
4 2-Till, filtration under diminished pressure.Filter cake being dried by the fire 3～4h down at 100 ℃, dried filter cake is worn into powder, obtain zinc phosphate aluminum nanocrystalline body, is benchmark with the zinc salt, yield 〉=95%.
Embodiment 4
Preparation Zn
1.65Al
0.9(PO
4)
2
Get zinc nitrate Zn (NO
3)
26H
2O powder 16.5mol is 4908.4g, aluminum nitrate Al (NO
3)
39H
2O powder 9.0mol is 3376.2g, potassiumphosphate K
3PO
43H
2O powder 23.0mol is 6125.1g, and OP-10 is 223g.In an enamelled vessel, add the potassiumphosphate powder, then add OP-10 and mix, standby; In another enamelled vessel that zinc nitrate powder, aluminum nitrate powder thorough mixing is even, standby.Under room temperature, normal pressure, under agitation in the potassiumphosphate powder that mixes with OP-10, add above-mentioned zinc salt powder, the mixture of aluminium salt powder, add to mix in the back immigration grinding plant and fully grind 40min, at room temperature leave standstill 1.5h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution detects less than SO
4 2-Till, filtration under diminished pressure.Filter cake being dried by the fire 3～4h down at 100 ℃, dried filter cake is worn into powder, obtain zinc phosphate aluminum nanocrystalline body, is benchmark with the zinc salt, yield 〉=95% ().
Embodiment 5
Preparation Zn
1.65Al
0.9(PO
4)
2
Get zinc chloride ZnCl
2Powder 16.5mol is 2248.8g, aluminum chloride AlCl
36H
2O powder 9.0mol is 2172.9g, ammonium phosphate (NH
4)
3PO
43H
2O powder 23.0mol is 4672.0g, and tween-80 is 133g.In an enamelled vessel, add the ammonium phosphate powder, then add tween-80 and mix, standby; In another enamelled vessel that zinc chloride powder, aluminum chloride powder thorough mixing is even, standby.Under room temperature, normal pressure, under agitation to the uniform ammonium phosphate powder of tween-80 ground and mixed in add above-mentioned zinc salt powder, the mixture of aluminium salt powder, add to mix in the back immigration grinding plant and fully grind 60min, at room temperature leave standstill 2h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution detects less than SO
4 2-Till, filtration under diminished pressure.Filter cake being dried by the fire 3～4h down at 100 ℃, dried filter cake is worn into powder, obtain zinc phosphate aluminum nanocrystalline body, is benchmark with the zinc salt, yield 〉=95%.
Embodiment 6
Preparation Zn
1.65Al
0.9(PO
4)
2
Get zinc acetate Zn (CH
3COO)
22H
2O powder 16.5mol is 4908.4g, aluminum chloride AlCl
36H
2O powder 9.0mol is 2172.9g, sodium phosphate Na
3PO
412H
2O powder 23.0mol is 8742.8g, and tween-80 is 113g, ethylenediamine-hydrochloride 113g.In an enamelled vessel, add sodium phosphate powder, then add tween-80 of half and the ethylenediamine-hydrochloride of half and mix, standby.In another enamelled vessel that zinc acetate powder, aluminum chloride powder thorough mixing is even, then add second half tween-80 and second half ethylenediamine-hydrochloride and mix, standby.Under room temperature, normal pressure, under agitation in the sodium phosphate powder that tween-80 and ethylenediamine-hydrochloride mix, add above-mentioned zinc salt powder, the mixture of aluminium salt powder, add to mix in the back immigration grinding plant and fully grind 60min, at room temperature leave standstill 2h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution detects less than SO
4 2-Till, filtration under diminished pressure.Filter cake being dried by the fire 3～4h down at 100 ℃, dried filter cake is worn into powder, obtain zinc phosphate aluminum nanocrystalline body, is benchmark with the zinc salt, yield 〉=95%.
Get above-mentioned arbitrary embodiment synthetic phosphoric acid zinc-aluminium crystal, carry out XRD analysis, according to the Scherrer formula, the particle diameter that calculates zinc phosphate aluminium powder form crystallite is about 35nm.As scheme shown in the l, from the XRD analysis collection of illustrative plates as can be seen, adopting the method for the invention synthetic phosphoric acid zinc-aluminium product is a kind of crystalline compounds.
Claims (3)
1. the synthetic method of a zinc phosphate aluminum nanocrystalline body, it is characterized in that: it adopts low-heat solid state reaction method directly synthetic, concrete technology is, with zinc salt powder, aluminium salt powder, phosphate powder is raw material, its proportioning raw materials is: zinc salt: aluminium salt: phosphatic material mass ratio is 0.05～0.95: 0.05～0.95: 2.0～3.0, add template, template accounts for 0.1～10% of entire reaction thing weight; Under room temperature, non-pressurized condition, mix the back and grind 10～120min, then allow reaction mixture under room temperature～90 ℃, leave standstill 1～5 hour, wash the inorganic salt by-product of solubility in the dereaction mixture then with water, filter, filter cake is dried down at 100 ℃, obtain zinc phosphate aluminum nanocrystalline body product, its crystallite particle diameter is about 35nm
Above-mentioned zinc salt is selected from a kind of or several combination under compatible situation in zinc chloride, zinc sulfate, zinc nitrate, the zinc acetate;
Above-mentioned aluminium salt comprises a kind of or several combination under compatible situation in aluminum chloride, aluminum nitrate, the Tai-Ace S 150;
Above-mentioned phosphoric acid salt is selected from a kind of or several combination under compatible situation in sodium phosphate, sodium hydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, the potassiumphosphate;
Have the two or more crystal water that contain in above-mentioned zinc salt, aluminium salt and the phosphoric acid salt at least;
Above-mentioned template comprises a kind of in tween series, 0P 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 zinc phosphate aluminum nanocrystalline body according to claim 1, it is characterized in that: before zinc salt, aluminium salt and phosphate powder hybrid reaction, earlier mix powder or the phosphate powder with template and zinc salt, aluminium salt is pre-mixed evenly, perhaps template is premixed in the phosphate powder, perhaps template is sneaked in the powder of three kinds of salt respectively in advance.
3. the synthetic method of zinc phosphate aluminum nanocrystalline body according to claim 1, it is characterized in that: mix and add in the process of template in zinc salt powder, aluminium salt powder, phosphate powder, the mixture that zinc salt powder, aluminium salt powder are formed joins in the phosphate powder, perhaps phosphate powder is added in the mixture that zinc salt powder and aluminium salt powder formed.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881711A (en) * | 2014-03-24 | 2014-06-25 | 广西大学 | Method for preparing manganese doped lithium zinc phosphate yellow green fluorescent powder by adopting low heat solid-phase reaction |
| CN105206832A (en) * | 2015-08-27 | 2015-12-30 | 张家港智电芳华蓄电研究所有限公司 | Sintering preparation method for zinc anode material |
| CN105694570A (en) * | 2016-03-04 | 2016-06-22 | 广西民族大学 | Nanometer zinc phosphate antirust pigment continuous production method and device |
| CN106634373A (en) * | 2015-11-03 | 2017-05-10 | 无锡市太湖防腐材料有限公司 | Waterborne zinc aluminum phosphate anti-rusting primer and preparation method thereof |
| CN110697672A (en) * | 2019-11-22 | 2020-01-17 | 浙江大学台州研究院 | Preparation method of zinc phosphate for water-based anticorrosive paint |
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| CN1230378C (en) * | 2003-04-09 | 2005-12-07 | 广西大学 | Method for directly synthesizing nano zinc phosphate crystal by using low-heat solid phase chemical reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1230378C (en) * | 2003-04-09 | 2005-12-07 | 广西大学 | Method for directly synthesizing nano zinc phosphate crystal by using low-heat solid phase chemical reaction |
Non-Patent Citations (1)
| Title |
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| 《化工技术与开发》 20041231 骆明 新一代磷酸锌系防锈颜料--磷酸铝锌的合成和应用 第8页第1-2段 1-3 第33卷, 第6期 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881711A (en) * | 2014-03-24 | 2014-06-25 | 广西大学 | Method for preparing manganese doped lithium zinc phosphate yellow green fluorescent powder by adopting low heat solid-phase reaction |
| CN103881711B (en) * | 2014-03-24 | 2017-01-11 | 广西大学 | Method for preparing manganese doped lithium zinc phosphate yellow green fluorescent powder by adopting low heat solid-phase reaction |
| CN105206832A (en) * | 2015-08-27 | 2015-12-30 | 张家港智电芳华蓄电研究所有限公司 | Sintering preparation method for zinc anode material |
| CN105206832B (en) * | 2015-08-27 | 2019-02-22 | 张家港智电芳华蓄电研究所有限公司 | A kind of sintering preparation method of zinc load material |
| CN106634373A (en) * | 2015-11-03 | 2017-05-10 | 无锡市太湖防腐材料有限公司 | Waterborne zinc aluminum phosphate anti-rusting primer and preparation method thereof |
| CN105694570A (en) * | 2016-03-04 | 2016-06-22 | 广西民族大学 | Nanometer zinc phosphate antirust pigment continuous production method and device |
| CN110697672A (en) * | 2019-11-22 | 2020-01-17 | 浙江大学台州研究院 | Preparation method of zinc phosphate for water-based anticorrosive paint |
| CN110697672B (en) * | 2019-11-22 | 2021-05-11 | 浙江大学台州研究院 | Preparation method of zinc phosphate for water-based anticorrosive paint |
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