CN102191396A - Preparation method of nickel-coated TiH2 foaming agent - Google Patents
Preparation method of nickel-coated TiH2 foaming agent Download PDFInfo
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- CN102191396A CN102191396A CN 201110101792 CN201110101792A CN102191396A CN 102191396 A CN102191396 A CN 102191396A CN 201110101792 CN201110101792 CN 201110101792 CN 201110101792 A CN201110101792 A CN 201110101792A CN 102191396 A CN102191396 A CN 102191396A
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Abstract
Relating to a preparation technology of foamed aluminium material through melt foaming, the invention mainly provides a method for delaying the hydrogen release of TiH2 foaming agent. The invention employs a heterogeneous nucleation technology to form a coated layer of high-melting-point metal Ni by means of chemical reduction and deposition on the surface of TiH2 particles, so that a delayed TiH2 decomposition can be realized. Specifically, the TiH2 particles are firstly subjected to pretreatments of hydrophilization, sensitization and activation, and then dispersed in an alkaline nickel solution. With sodium hypophosphate as the reducing agent, Ni ions in the solution are reduced to elemental nickel particles and are deposited on the surface of the TiH2 particles. After filtering, washing and drying, the coated particles can be used as the foaming agent for foamed aluminium production. With the foaming agent, a porous material with evenly distributed pores can be obtained without changing present production equipment and technologies of foamed aluminium. Characterized by simple coating process and mature technology, the method of the invention is suitable for large-scale industrial production. The method, based on production technology requirements of foamed aluminium, can be used to control the coating thickness so as to prepare foaming agents meeting different foaming time requirements by controlling coating conditions.
Description
Technical field
That the present invention relates to is the TiH that foam melt method prepares used parcel nickel dam in the foamed aluminium
2The preparation method of whipping agent.
Background technology
Closed pore foam aluminium has obtained widespread use owing to have good suction sound insulation, electromagnetic shielding and bumper and absorbing shock function at aspects such as aerospace, electronics, chemical industry, buildings.In its manufacture method, direct foaming of melt mass method technology is simple, production cost is low, is easy to scale operation, but owing to whipping agent TiH in the current technology
2Under 600 ℃ (blowing temperature of foamed aluminium is at 650～700 ℃), promptly begin quick decomposition, limited and impelled whipping agent equally distributed churning time in molten aluminium, make that the pore homogeneity of product is relatively poor, density and quality instability are difficult to realize to the control in aperture especially.For this reason, to existing TiH
2Carry out Passivation Treatment and develop the very big attention that substitute products have obtained industry and scientific research field, and proposed number of ways: TiH
2Surface oxidation, parcel oxide compound, the higher metal of parcel fusing point uses yellow soda ash to replace TiH
2, hydrogenation mishmetal or the like.Wherein, at TiH
2The method of surface parcel refractory metal Ni, Co must not change the production technique of existing foamed aluminium, has good operability, tool using value.For at TiH
2Particle surface superscribes high-melting-point compositions such as metal Ni, Co, patent CN1298960A has proposed methods such as High Pressure Hydrogen reduction, electrochemical plating and vacuum evaporating, and these methods need pressure vessel, equipment complexity, the production cost height, make to produce in batches to be restricted, be difficult to apply.
Summary of the invention
The object of the present invention is to provide a kind of TiH of nickel coat
2The preparation method of whipping agent, this method required equipment is simple, easy handling; And the coating that obtains is firm, and thickness is even; Can also be according to required, by method regulation and control product thickness of coating of the present invention.Method production cost of the present invention is low, constant product quality, and the hydrogen time opening of releasing of whipping agent obtains stable delaying, and the scope of application is wider, is fit to large-scale production.
Technical scheme of the present invention is: with the chemical reduction mode of heterogeneous nucleation at TiH
2Particle surface parcel nickel dam may further comprise the steps:
1) TiH
2Particulate pre-treatment: comprise that particulate is hydrophilic, sensitization and activation; With TiH
2Microparticulate stirs in water phase surfactant mixture, separates, washes, (10～20min is handled in sensitization in 6～20g/L), and (0.5～1.5g/L) carries out activation treatment as activator with the palladium salts solution after separating washing then in 40～50 ℃ the tin protochloride aqueous solution then; After separate, washing, dry back be standby;
2) carrying out heterogeneous nucleation deposition in alkaline nickel solution coats: with the inferior sodium phosphate is reductive agent, under the condition that includes stablizer, complexing agent, tensio-active agent and speed adjustment agent existence, the nickel ion in the solution is deposited on TiH by being reduced to nickel simple substance
2Particle surface finally can obtain having the TiH that coats nickel dam
2The whipping agent particle; Complexing agent is one or more in lactic acid, citric acid, toxilic acid or its sodium salt; Stablizer is one or both combinations in mercapto benzothiazole, thiosulphate, Potassium Iodate, the plumbic acetate.
On the basis of above technical scheme, the contriver finds also that by research the present invention is if adopt following embodiment can make the whipping agent of producing by the inventive method reach more good performance and result of use.
Described 2) concentration of the complexing agent in the step is 5～50g/L.
In the also preferred complexing agent of the present invention in employing citric acid and lactic acid, the toxilic acid one or both are used, and the shared mass percent concentration of citric acid is not less than 80%.
Described 2) concentration of the stablizer in the step is at 0.1～5mg/L.Described 2) stablizer is organic stabilizer or inorganic stabilizers in the step; The concentration of organic stabilizer is 0.1～1.5mg/L, and the concentration of inorganic stabilizers is 1～3mg/L.
Described 1) step, 2) tensio-active agent described in the step is (promptly 1) step, 2 separately independently) selected tensio-active agent of step can be identical, also can difference) be selected from a kind of the getting final product in sodium oleate, sodium lauryl sulphate, the sodium laurylsulfonate; The most suitable employing is Sodium dodecylbenzene sulfonate.
Described surfactant concentration is 20～60mg/L.
Described 1) surfactant concentration in the step is 80～120% of its micelle-forming concentration.
It is a kind of in Succinic Acid, the Sodium Fluoride that described speed is adjusted agent.It is 4～9g/L that speed is adjusted agent concentration.
The pH value of alkaline nickel solution in 8～10 scopes,, nickel ion concentration is at 0.09～0.15mol/L, and the mol ratio of hypophosphite ion is between 0.25～0.45.
The pH value of alkaline nickel solution is regulated with ammoniacal liquor.
The chemical reduction of the present invention by the heterogeneous nucleation of usefulness under a kind of normal temperature and pressure is provided is at TiH
2Particle surface parcel nickel dam replaces existing High Pressure Hydrogen reduction nickel coat technology, to prepare the whipping agent that is fit to existing flux foaming technology.TiH of the present invention
2Nickel coat technology has the integument thickness advantage of uniform that process is simple, easy handling is regulated and control, obtained, and with its foamed aluminium even air hole distribution that makes, quality product is higher.
With TiH
2Powder carries out sensitization and activation after cleaning, and puts into the groove that nickel salt, reductive agent and various additives are housed then and carries out the nickel coat processing.Solid-liquid separation goes out to be coated with the TiH of nickel dam
2Particle can obtain to be used for the whipping agent that foamed aluminium is produced after washing, the drying.
The present invention compared with prior art has the following advantages:
(1) normal temperature and pressure nickel plating, equipment is simple, easy handling;
(2) the present invention has selected combination complexing agent and stablizer especially for use, and by effectively cooperating and process optimization between each composition, can make prepared product coating firm, and thickness is even;
(3) thickness of coating can require according to foam process, and application range of products is wider, and the foamed aluminium quality that makes improves.
(4) production technique advanced person, equipment requirements is not high, and production cost is low, and constant product quality is fit to scale production.
(5) whipping agent that uses the present invention to make must not change existing foamed aluminium production unit and technology, the releasing hydrogen and can obtain stable delaying of whipping agent, thus help obtaining the porous material of even air hole distribution.
To sum up, the present invention has that technology is simple, easy handling, is fit to the advantage of large-scale production; The product that obtains is released hydrogen and is lagged behind, and is fit to existing foam process, and final froth product quality can be protected.In addition, regulate reducing process parameter (time, temperature etc.), can also further facilitate the regulation and control product plating thickness and release hydrogen retardation time.
Description of drawings
Fig. 1 is TiH of the present invention
2The sem photograph of whipping agent particulate.
Fig. 2 is the whipping agent particulate scan Electronic Speculum figure that is enclosed with the metal nickel dam of the present invention.
The foamed aluminium product photo that the whipping agent that Fig. 3 adopts the present invention to make is prepared.
Embodiment
Below in conjunction with specific examples whipping agent preparation method provided by the invention is described further, but does not limit the present invention.
Embodiment 1:
Hydrophilicity-imparting treatment: take by weighing the 0.1g Sodium dodecylbenzene sulfonate and be dissolved in the 250mL deionized water, add 25gTiH
2Powder, room temperature lower magnetic force stirring reaction 5min, suction filtration separates TiH
2Powder is washed drying three times.
Sensitization is handled: weighing 1.5g tin protochloride is dissolved in the 250mL deionized water makes solution, is heated to 45 ℃, adds the TiH that hydrophilicity-imparting treatment is crossed
2Powder, stirring reaction 10min, suction filtration separates, and washes three times after drying.
Activation treatment: compound concentration is the palladium chloride solution of 0.8g/L, takes by weighing 250mL, adds the powder of sensitization, 45 ℃ of lower magnetic force stirring reaction 5min, suction filtration separate and wash three times after normal temperature dry down.
In nickel sulfate solution, add sodium lauryl sulphate (30mg/L), Trisodium Citrate (40g/L), 2-mercapto benzothiazole (0.5mg/L), Sulfothiorine (0.8mg/L) and Succinic Acid (6g/L) in turn and make plating bath, add the reductive agent inferior sodium phosphate, the pH value of regulating plating bath with ammoniacal liquor is about 9, be stirred and heated to 50 ℃ of assigned temperatures, add the TiH that had handled
2Behind the powdered reaction 12min, the suction filtration separated powder is also washed, and can obtain being enclosed with the TiH of nickel dam then at 60 ℃ of following dry 6h of loft drier
2Powder.Fig. 3 (a) is the foamed aluminium material photo that makes with this patent product.
Embodiment 2:
TiH
2Particulate pre-treating technology such as embodiment 1.
In nickel sulfate solution, add Sodium dodecylbenzene sulfonate (40mg/L), lactic acid (5g/L), citric acid (30g/L), Potassium Iodate (2mg/L) and Succinic Acid (5g/L) in turn and make plating bath, add the reductive agent inferior sodium phosphate, the pH value of regulating plating bath with ammoniacal liquor is about 9, be stirred and heated to 50 ℃ of assigned temperatures, add the TiH that had handled
2Behind the powdered reaction 15min, suction filtration separated powder and washing are then at 60 ℃ of following dry 6h of loft drier.Finally obtain the whipping agent product, its scanning electron microscope result as shown in Figure 2.
The main performance characteristics of the obtained product of the present invention is to have delayed TiH
2Decomposition, undressed TiH
2The decomposition time opening in 600 ℃ of aluminium alloy melts is about 1min, and the nickel coat TiH after the technology of the present invention is handled
2, its decomposition time opening can delay to 3～5min, makes actually operating have time enough to stir, thereby helps improving TiH
2Dispersing uniformity in molten aluminium.Integument has the thickness than homogeneous in addition, can further guarantee the quality of foamed aluminium.Fig. 3 (b) is the foamed aluminium material that makes with this patent product.
Claims (9)
1. TiH who wraps up nickel
2The preparation method of whipping agent is that chemical reduction mode with heterogeneous nucleation is at TiH
2Particle surface parcel nickel dam may further comprise the steps:
1) TiH
2Particulate pre-treatment: comprise that particulate is hydrophilic, sensitization and activation; With TiH
2Microparticulate stirs in water phase surfactant mixture, separates, washes, be that 10～20min is handled in sensitization in 6～20g/L tin protochloride aqueous solution 40～50 ℃ concentration then, separating the washing back then is that 0.5～1.5g/L palladium salts solution carries out activation treatment as activator with concentration; After separate, washing, dry back be standby;
2) carrying out heterogeneous nucleation deposition in alkaline nickel solution coats: with the inferior sodium phosphate is reductive agent, under the condition that includes stablizer, complexing agent, tensio-active agent and speed adjustment agent existence, the nickel ion in the solution is reduced to nickel simple substance is deposited on TiH
2Particle surface finally obtains having the TiH that coats nickel dam
2The whipping agent particle; Complexing agent is one or more in lactic acid, citric acid, toxilic acid or its sodium salt; Stablizer is one or both combinations in mercapto benzothiazole, thiosulphate, Potassium Iodate, the plumbic acetate.
2. method according to claim 1 is characterized in that, described 2) concentration of the complexing agent in the step is 5～50g/L.
3. method according to claim 1 and 2 is characterized in that, described 2) stablizer is organic stabilizer or inorganic stabilizers in the step; The concentration of organic stabilizer is 0.1～1.5mg/L, and the concentration of inorganic stabilizers is 1～3mg/L.
4. method according to claim 1 is characterized in that, the described 1) step, 2) tensio-active agent is independently to be selected from a kind of in sodium oleate, sodium lauryl sulphate, the Sodium dodecylbenzene sulfonate separately in the step.
5. method according to claim 4 is characterized in that 1) surfactant concentration in the step be its micelle-forming concentration 80～120%, 2) go on foot in the consumption of tensio-active agent be 20～60mg/L.
6. method according to claim 1 is characterized in that, it is a kind of in Succinic Acid, the Sodium Fluoride that described speed is adjusted agent.
7. method according to claim 6 is characterized in that, it is 4～9g/L that speed is adjusted agent concentration.
8. method according to claim 1 is characterized in that, the pH value of alkaline nickel solution is in 8～10 scopes, and nickel ion concentration is at 0.09～0.15mol/L, and the mol ratio of hypophosphite ion is between 0.25～0.45.
9. according to each described method of claim 1～8, it is characterized in that the pH value of alkaline nickel solution is regulated with ammoniacal liquor.
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| CN 201110101792 CN102191396A (en) | 2011-04-22 | 2011-04-22 | Preparation method of nickel-coated TiH2 foaming agent |
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| CN 201110101792 CN102191396A (en) | 2011-04-22 | 2011-04-22 | Preparation method of nickel-coated TiH2 foaming agent |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711446A (en) * | 2013-12-16 | 2015-06-17 | 哈尔滨顺畅工程技术咨询有限公司 | Foamed aluminum preparation technology |
| CN105316514A (en) * | 2015-10-26 | 2016-02-10 | 昆明理工大学 | Surface treatment method for titanium hydride |
| CN105821230A (en) * | 2016-03-28 | 2016-08-03 | 昆明理工大学 | Surface composite modification method for TiH2 |
| CN107225234A (en) * | 2017-04-21 | 2017-10-03 | 昆明理工大学 | A kind of Cr2The surface cladded with nickel layer method of N particles |
| CN107262718A (en) * | 2017-07-07 | 2017-10-20 | 哈尔滨工程大学 | A kind of method that utilization laser cladding forming technique prepares foamed aluminium |
| CN107398557A (en) * | 2017-06-14 | 2017-11-28 | 清华大学 | Composite foamable agent particle and preparation method thereof, and the preparation method of foamed aluminium |
| CN109837415A (en) * | 2017-11-28 | 2019-06-04 | 北京有色金属研究总院 | A kind of manufacturing method of foam aluminium alloy |
| CN110079694A (en) * | 2018-01-25 | 2019-08-02 | 清华大学 | A kind of preparation method of cladded type foaming agent and preparation method thereof and foamed aluminium |
| CN111979440A (en) * | 2020-08-20 | 2020-11-24 | 安徽工业大学 | Aluminum alloy component for preparing foamed aluminum by powder metallurgy method and foaming method |
| CN112453390A (en) * | 2020-11-06 | 2021-03-09 | 中国科学院过程工程研究所 | Sintering auxiliary agent-coated titanium powder and preparation method thereof |
| CN113290244A (en) * | 2021-06-04 | 2021-08-24 | 吉林大学 | Preparation method of impact-resistant self-recovery bionic composite material |
-
2011
- 2011-04-22 CN CN 201110101792 patent/CN102191396A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 工程科技I辑》 20100415 朱学卫 TiH2粉体表面化学镀镍工艺研究 第B015-33页 1-9 , 第4期 * |
| 《粉末冶金材料科学与工程》 20090831 朱学卫等 泡沫铝用 Ni/TiH2 包覆型发泡剂的制备工艺及性能 第270-274页 1-9 第14卷, 第4期 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711446A (en) * | 2013-12-16 | 2015-06-17 | 哈尔滨顺畅工程技术咨询有限公司 | Foamed aluminum preparation technology |
| CN105316514A (en) * | 2015-10-26 | 2016-02-10 | 昆明理工大学 | Surface treatment method for titanium hydride |
| CN105821230A (en) * | 2016-03-28 | 2016-08-03 | 昆明理工大学 | Surface composite modification method for TiH2 |
| CN107225234A (en) * | 2017-04-21 | 2017-10-03 | 昆明理工大学 | A kind of Cr2The surface cladded with nickel layer method of N particles |
| CN107225234B (en) * | 2017-04-21 | 2019-06-11 | 昆明理工大学 | A kind of Cr2The surface cladded with nickel layer method of N particle |
| CN107398557B (en) * | 2017-06-14 | 2019-07-09 | 清华大学 | The preparation method of composite foamable agent particle and preparation method thereof and foamed aluminium |
| CN107398557A (en) * | 2017-06-14 | 2017-11-28 | 清华大学 | Composite foamable agent particle and preparation method thereof, and the preparation method of foamed aluminium |
| CN107262718A (en) * | 2017-07-07 | 2017-10-20 | 哈尔滨工程大学 | A kind of method that utilization laser cladding forming technique prepares foamed aluminium |
| CN109837415A (en) * | 2017-11-28 | 2019-06-04 | 北京有色金属研究总院 | A kind of manufacturing method of foam aluminium alloy |
| CN109837415B (en) * | 2017-11-28 | 2020-10-20 | 有研工程技术研究院有限公司 | Method for manufacturing foamed aluminum alloy |
| CN110079694A (en) * | 2018-01-25 | 2019-08-02 | 清华大学 | A kind of preparation method of cladded type foaming agent and preparation method thereof and foamed aluminium |
| CN111979440A (en) * | 2020-08-20 | 2020-11-24 | 安徽工业大学 | Aluminum alloy component for preparing foamed aluminum by powder metallurgy method and foaming method |
| CN112453390A (en) * | 2020-11-06 | 2021-03-09 | 中国科学院过程工程研究所 | Sintering auxiliary agent-coated titanium powder and preparation method thereof |
| CN113290244A (en) * | 2021-06-04 | 2021-08-24 | 吉林大学 | Preparation method of impact-resistant self-recovery bionic composite material |
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Application publication date: 20110921 |