Ultrathin Zirconia Passivation and Stabilization of Aluminum

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Ultrathin Zirconia Passivation and Stabilization of Aluminum Nanoparticles for Energetic Nanomaterials via Atomic Layer Deposition Rong Chen, Kai Qu, Jiawei Li, Penghui Zhu, Chenlong Duan, Jing Zhang, Xiwen Li, Xiao Liu, and Zhijian Yang ACS Appl. Nano Mater., Just Accepted Manuscript • DOI: 10.1021/acsanm.8b01005 • Publication Date (Web): 13 Sep 2018 Downloaded from http://pubs.acs.org on September 13, 2018

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ACS Applied Nano Materials

Ultrathin Zirconia Passivation and Stabilization of Aluminum Nanoparticles for Energetic Nanomaterials via Atomic Layer Deposition

Rong Chen,*,† Kai Qu,† Jiawei Li,† Penghui Zhu,† Chenlong Duan,† Jing Zhang,† Xiwen Li,† Xiao Liu,*,† and Zhijian Yang‡

†

State Key Laboratory of Digital Manufacturing Equipment and Technology, School

of Mechanical Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, People’s Republic of China. ‡

Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang,

621900, Sichuan, People’s Republic of China.

ABSTRACT:

The stability of aluminum (Al) nanoparticles is a key issue that

determines the energy performance of solid fuels, Al-based green propellants, and fuel cells.

The surface native oxide shell (Al2O3), nevertheless, cannot stabilize Al

nanoparticles under hot water conditions.

Herein, we report a passivation method

utilizing an ultrathin zirconia (ZrO2) coating via atomic layer deposition, where subnanometer coating layer could completely prevent the reactions between Al nanoparticles and hot water (80 ºC).

The weight percentage of metallic Al for

ultrathin ZrO2 coated Al nanoparticles can reach 82.2 wt%, which is close to that of original Al nanoparticles with Al2O3 native oxide (88 wt%).

The metallic Al’s

weight has been kept at 93.4 % for the ultrathin ZrO2 coated Al nanoparticles compared to the original Al nanoparticles.

As a comparison, the Al2O3 coated Al

nanoparticles results in the oxidation failure in 60 ºC water.

The proposed

passivation mechanism is attributed to ZrO2 coating’s structural stability and the enhanced hydrophobicity to water.

The ultrathin ZrO2 passivation offers a valuable

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ACS Applied Nano Materials 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

tool for enhancing the stability of Al nanoparticles, and thereby enables their potential applications in energy field. KEYWORD: Al nanoparticles, stability, ZrO2, ultrathin coating, atomic layer deposition


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1. INTRODUCTION Aluminum (Al) nanoparticles with large specific area and high energy release rate, have aroused wide attentions in the applications of solid fuels, Al-based green propellants and fuel cells.1-6 However, the major drawback for Al nanoparticles, especially when the size getting smaller and smaller, is its poor stability towards the easy oxidation under ambient conditions.7-9

The oxidation process will lead to the

decrease of the metallic core’s weight percentage and combustion efficiency of Al nanopaticles.10-12

Moreover, the stability of Al nanoparticles in hot water is of

practical engineering significance, as it is required for preparing the slurry during the Al-based green propellants fabrication.13-14

Therefore, improving the stability of Al

nanoparticles is of great significance for their practical applications in the energetic materials field. Surface passivation of Al nanoparticles is a common method to enhance the stability of Al nanoparticles.15-25

The passivation films can be classified into two

categories depending on the materials, both of which should have good oxidation resistance and thin enough to keep the weight percentage of metallic Al.15-16

The

first type is organic coating such as toluene, isopropyl alcohol, perfluorodecalin, alkyl-substituted epoxides and varieties of organic acids.16-23

These organic coatings

can effectively resist the humidity, however, they are still permeable to oxygen and water at high temperatures, which can lead to the oxidation of internal metallic Al.22 The second type involves inorganic passivation film represented by alumina (Al2O3) and silica (SiO2), which can be formed by either internal oxidation or external chemical coating.15,19,24-25

Although the Al2O3 coated Al nanoparticles exhibit good

stability at 60 ºC with the relative humidity of 90%, the thick Al2O3 coatings (≥ 5 nm) prepared by thermal oxidation process have greatly reduced the weight percentage of metallic Al.15,19

Moreover, the Al2O3 coatings has exhibited a limited resistance

under more harsh conditions, such as higher temperature and humidity, which will lead to the further loss of metallic Al.

The failure of Al2O3 coatings is usually

attributed to the continued reaction between the metallic Al and AlOOH formed by the reaction of Al2O3 coatings and water.

Overall, developing a new method of



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uniform coating and thin passivation with high oxidation resistance opens up opportunities to enhance the stability of Al nanoparticles. Based on the self-limiting half reactions, atomic layer deposition (ALD) has been widely used to prepare uniform films on the nanoscale, which is advantageous in precisely controlling composition and thickness of films.26-27

We have successfully

utilized ALD method to passivate nanoparticles for their applications in catalysis, energy and medical fields.28-32

In this work, we report the use of ultrathin zirconia

(ZrO2) coatings prepared by ALD method to passivate Al nanoparticles.

The ZrO2

passivated Al nanoparticles exhibited higher oxidation resistance than Al nanoparticles with Al2O3 native oxide or Al2O3 coatings prepared by ALD method. Moreover, less than 1 nm of ZrO2 coatings is required for complete oxidation resistance in water at 80 ºC, which keeps the weight percentage of metallic Al compared to that of pure Al nanoparticles.

At last, the passivation mechanism of

ultrathin ZrO2 film on Al nanoparticles is investigated.

2. EXPERIMENTAL METHODS Al nanoparticles (99.5%, Aladdin) with the size of 20 ~ 200 nm were used without any pretreatment.

The untreated Al nanoparticles is labeled as Al@Al2O3,

where Al2O3 indicates the native oxide on commercial Al nanoparticles.

As shown

in Figure 1, the formed core-shell structures are named as Al@Al2O3@Al2O3-n and Al@Al2O3@ZrO2-n after the Al2O3 and ZrO2 ALD coating, where n means the ALD cycles.

All ALD processes were performed in our designed fluidized bed reactor,

which was reported in our previous study.33 In detail, the deposition of ZrO2 was performed at 150 ºC using Tetrakis(dimethylamino)zirconium (Zr(NMe2)4) and H2O as precursors.

The steel bottle contained Zr precursors were heated to 80 ºC to

ensure sufficient vapor pressure of Zr precursors.

The connecting steel pipes were

heated to 120 ºC during ZrO2 deposition to avoid precursors condensation.

The

ALD of Al2O3 was performed at 120 ºC with trimethylaluminum (TMA) and water (H2O) as precursors.

For a typical ALD process, about 200 mg Al nanoparticles are

loaded in the designed powder holder with the top and bottom being sealed by ACS Paragon Plus Environment

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stainless steel mesh.

Prior to ALD, the Al nanoparticles are fluidized by 50 mL/min

of ultrahigh purity N2 for 20 min at the reaction temperature.

One ALD cycle for

Al2O3 or ZrO2 consists of the following four steps: (1) 90 s pulse of Al or Zr precursor; (2) a purging time of 120 s; (3) 90 s pulse of H2O; (4) a purging time of 120 s.

The mass of oxide coatings with different cycles was measured by analytical

balance.

Figure 1. Scheme of Al2O3 and ZrO2 ALD coating on Al nanoparticles. The specific surface area of oxide coated samples was measured by N2 adsorption (Micromeritics ASAP 2020) after degassing treatment in a vacuum oven at 80 ºC for 5 hours.

X-ray diffraction (XRD) patterns were collected on a PANalytical

X'Pert PRO diffractometer, using Cu Kα radiation with λ = 1.5406 Å.

The

morphologies of oxide coated Al nanoparticles were characterized by scanning electron microscopy (SEM, Quanta 200) and transmission electron microscopy (TEM, Tecnai G2 F30, FEI, Inc.). using TEM.

The thickness of oxide coating layers was measured

The weight percentage of metallic Al (Al wt%) is defined as: Al wt% =

M -mAl2O3 M +moxide-ALD

where mAl2O3 is the mass of native oxide, which is calculated by the thickness measured from the TEM images. coating

and

total

mass

moxide-ALD and M are the mass gain after ALD of

Al

nanoparticles,

respectively.

Thermogravimetry/differential thermal analyzer (TG/DTA, Diamond, PerkinElmer Instruments) was used to measure the metallic Al content and exothermic ACS Paragon Plus Environment


performance of passivated Al nanoparticles.

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All TG/DTA measurements were

performed with the heating rate of 20 ºC/min in air ambient and a gas flow rate of 40 ml/min. In order to evaluate the stability of Al nanoparticles with oxide coatings, the accelerated aging test of oxide coated Al nanoparticles in hot water at different temperatures were conducted by monitoring the volume of released H2.34-35

All tests

were carried out in a round-bottom flask with its temperature controlled by water bath.

For each test, 100 mg Al nanoparticles and 4 mL deionized water were added

into the round-bottom flask.

The volume of released H2 gas was measured by a

graduated cylinder using the dehydration method.

The conversion yield (%) was

defined as the volume ratio of released H2 gas (V) and the theoretical volume after 100 mg pure Al nanoparticles being oxidized completely (V0).34-35

3. RESULT AND DISCUSSION 3.1 ALD growth of ZrO2 and Al2O3 The mass gains of oxides coated Al nanoparticles (Al@Al2O3@ZrO2 and Al@Al2O3@Al2O3) are shown in Figure 2(a), which exhibit linear increase with respect to ALD cycles of ZrO2 and Al2O3.

The mass gain rates of ZrO2 and Al2O3

coatings are about 1.76 mg/cycle and 1.10 mg/cycle, respectively.

According to the

specific surface area of Al nanoparticles (16.26 m2/g) and the densities of passivation films, the growth rates of ZrO2 and Al2O3 on Al nanoparticles can be estimated to be 0.93 ± 0.02 Å/cycle and 1.2 ± 0.05 Å/cycle, which are similar to that on planar substrates (Figure S1 in supporting information (SI)).36-38

The XRD patterns of Al

nanoparticles, as well as 50 cycles of ZrO2 and Al2O3 coated Al nanoparticles (Al@Al2O3@ZrO2-50 and Al@Al2O3@Al2O3-50) are shown in Figure 2(b).

All the

diffraction patterns can be well assigned to the characteristic reflection planes of standard Al metal phase (JCPDS No. 89-2837).

There are no typical crystalline

peaks of ZrO2 and Al2O3 observed in the XRD patterns of oxide coated Al nanoparticles, indicating the amorphous nature of coating layers.

The amorphous

coating, similar to corrosion resistance films, is of importance to avoid the grain ACS Paragon Plus Environment

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boundary defects.

The calculated average crystallite sizes of Al@Al2O3,

Al@Al2O3@Al2O3-50 and Al@Al2O3@ZrO2-50 from the XRD profile using the Scherrer equation are 32.6 nm, 35.2 nm and 35.7 nm, indicating that the ALD process has not altered the crystal structures of the metallic Al cores.

The weaker diffraction

peaks of Al@Al2O3@Al2O3-50 and Al@Al2O3@ZrO2-50 than that of pristine Al nanoparticles may be due to the mass ratio’s decrease of Al nanoparticles as shown in Figure 2(a).

Figure 2. (a) The mass gains and Al nanoparticles’ mass ratios of Al@Al2O3@Al2O3 and Al@Al2O3@ZrO2 as the function of ALD cycles, (b) XRD patterns of Al nanoparticles, Al@Al2O3@Al2O3-50 and Al@Al2O3@ZrO2-50.

The TEM images in Figure 3(a) show that Al nanoparticles are spherical in shape with a size of 20 ~ 200 nm.

Clearly, Al nanoparticles exhibit a core-shell structure

with the native oxide of amorphous Al2O3 as shown in Figure 3(b).

The measured d

spacing of 0.23 nm is assigned to the (111) surface of metallic Al. thickness of Al2O3 shell is about 5.7 ± 0.7 nm.

The average

According to the density of Al2O3,

the calculated weight percentage of metallic Al for Al nanoparticles without pretreatment is about 88%, which is close to that in previous studies.22,39

The TEM

images of Al@Al2O3@ZrO2-50 in Figure 3(c) and (d) exhibit two shells on the metallic Al cores, which are the Al2O3 native oxide and grown ZrO2.

Figure 3(e) and

(f) also exhibit the double shell structure for Al@Al2O3@Al2O3-50.

The XPS results

in Figure S2 show that the organic residues are limited in the coated oxide layer.



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Moreover, both Al2O3 and ZrO2 shells are amorphous phase, which agrees well with the XRD patterns.

The measured thicknesses of ZrO2 and Al2O3 shells are about 4.5

nm and 6.1 nm, respectively, which agree well with their linear growth rates estimated by the mass gains.

Figure 3. (a)(b) TEM images of Al nanoparticles, (c)(d) TEM images of Al@Al2O3@ZrO2-50, and (e)(f) TEM images of Al@Al2O3@Al2O3-50.

3.2 Stability tests of Al@Al2O3@ZrO2 and Al@Al2O3@Al2O3 The effectiveness of coated oxides passivation has been evaluated by performing the accelerated aging test in hot water at different temperatures, in which the yields of hydrogen gas are monitored.

As shown in Figure 4(a), no hydrogen gas is detected

when Al nanoparticles stay in water at 40 ºC, which is due to the resistance of Al2O3 native oxide.

When the temperature increases to 60 ºC, the Al nanoparticles start to

react with water after a stabilization period of 17.6 min.

The Al nanoparticles can be

completely oxidized at 60 ºC with the max hydrogen gas yield of 88.6%, which is consistent with the calculated weight percentage of metallic Al after considering the mass of Al2O3 native oxide.

Moreover, when the temperature increases to 80 ºC, the

reaction between Al nanoparticles and water is more rapid and violent with the ACS Paragon Plus Environment

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stabilization period of 3.8 min and completed reaction time of 4.2 min. Figure 4(b) shows the hydrogen gas yields for different ALD cycles of Al@Al2O3@Al2O3 samples at 60 ºC.

Although the stabilization periods are

lengthened with increasing of ALD cycles, the metallic Al can still be completely oxidized by water within 30 min for Al@Al2O3@Al2O3-100, indicating that both Al2O3 native oxide and coated oxide cannot resist the oxidation.

For the

Al@Al2O3@ZrO2 samples under the same tests at 60 ºC, it is interesting that the oxidation rate can be greatly decreased after only 1 cycle coating of ZrO2 as shown in Figure 4(c).

Moreover, 5 cycles of ZrO2 can completely resist the oxidation of

metallic Al by water at 60 ºC, which can be related to the formation of continuous film on Al nanoparticles.

When the temperature increases to 80 ºC, the oxidation

reaction can also be completely resisted by just increasing several ALD cycles of ZrO2 as shown in Figure 4(d).

Figure 4. The yields of hydrogen gas as the function of time for (a) Al nanoparticles in water at 40 ºC, 60 ºC and 80 ºC, (b) Al@Al2O3@Al2O3 in water at 60 ºC, (c) Al@Al2O3@ZrO2 in water at 60 ºC and (d) Al@Al2O3@ZrO2 in water at 80 ºC.



The

TG/DTA

analysis

of

Al

nanoparticles,

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Al@Al2O3@ZrO2-8

Al@Al2O3@Al2O3-50 has been performed as shown in Figure 5.

and

The mass gain of

Al nanoparticles at about 550 ºC is assigned to the oxidation of metallic Al cores.40 The oxidation temperatures of Al nanoparticles after ZrO2 and Al2O3 coating will be increased due to the enhancement of their stability.

The mass gains of Al

nanoparticles, Al@Al2O3@ZrO2-8 and Al@Al2O3@Al2O3-50 are 78.3%, 72.5%, and 60.8%, respectively.

The mass gains due to the oxidation of metallic Al cores are

consistent with the calculated weight percentages of metallic Al after considering the mass of Al2O3 native oxide and coated oxides.

The DTA profiles exhibit the

exothermic process of Al@Al2O3, Al@Al2O3@ZrO2-8 and Al@Al2O3@Al2O3-50 at 544.2 ºC, 549.5 ºC and 588.7 ºC.

The released heat of Al@Al2O3@ZrO2-8

determined by measuring the area of the DTA peaks is slightly less than Al nanoparticles.

However, the released heat of Al@Al2O3@Al2O3-50 is greatly

decreased compared to Al nanoparticles.

The results indicate that the oxidation of Al

nanoparticles just has slightly been retarded after the ultrathin ZrO2 coating, which is important for the applications in solid fuels and Al-based green propellants.

The

similar areas of the exothermic peaks of Al@Al2O3 and Al@Al2O3@ZrO2-8 also agree well with the mostly remained weight percentage of metallic Al for Al@Al2O3@ZrO2-8 (82.2 wt%) compared to that of Al@Al2O3 (88 wt%).


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Figure 5. TG/DTA analysis of Al nanoparticles, Al@Al2O3@ZrO2-8 and Al@Al2O3@Al2O3-50.

3.3 Morphologies of oxide coated Al nanoparticles after stability tests Figure 6(a) and (b) show the morphologies of Al@Al2O3@ZrO2-8 before and after stability tests at 80 ºC. Clearly, the samples can keep the spherical shape well, which is consistent with the test of hydrogen gas yield in Figure 4(d).

TEM image in

Figure 6(c) shows the ZrO2 coatings on the surface of Al@Al2O3@ZrO2-8, in accordance with the element line scanning result in Figure 6(d).

The thickness of

ZrO2 is about 0.6 nm, agreeing well with the growth rate of ZrO2 as the previous discussion of Figure 2(a).

As a comparison, the SEM image of Al@Al2O3@ZrO2-6

after stability test presents the porous surface as shown in Figure S3, which indicates the water have broken the ZrO2 coatings and reacted with the metallic Al cores.

The

morphologies of Al@Al2O3@Al2O3-50 before and after stability test are also presented in Figure 6(e) and (f).

The particles with irregular morphology in Figure

6(f) can be attributed to the Al2O3 products after stability test, indicating the complete oxidation as the hydrogen gas yield in Figure 4(b).

Figure 6. SEM images of Al@Al2O3@ZrO2-8 (a) before and (b) after stability test at ACS Paragon Plus Environment


80 ºC.

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(c) TEM image and (d) element line scanning of Al@Al2O3@ZrO2-8 after

stability test.

SEM images of Al@Al2O3@Al2O3-50 (e) before and (f) after stability

test at 60 ºC.

3.5 Proposed passivation mechanism The passivation mechanism of ZrO2 and Al2O3 coated Al nanoparticles has been discussed.

When the Al@Al2O3@Al2O3 samples stay into water at 60 ºC, the Al2O3

coatings on the surface can react with water and generate hydration products (AlOOH), which is reactive to the metallic Al core by forming hydrogen gas.41-42

As

shown in Figure 7(a), the generated hydrogen gas can break the Al2O3 coatings and escape from the surface, which results in the failure of Al2O3 passivation film. Therefore, Al2O3 coating could not completely block the reaction between Al2O3 and water no matter of its thickness.

On the other hand, the ultrathin ZrO2 coating can

greatly enhance the hydrophobicity of Al2O3 film as shown in Figure S4.

The

previous studies have also reported that the Al2O3/ZrO2 laminated film can exhibit high permeation barrier to water, which is due to the formation of ZrAlxOy phase at the interface between Al2O3 and ZrO2 films.43-44

Therefore, the continuously

ultrathin ZrO2 coatings on Al nanoparticles could completely resist the oxidation reaction as shown in Figure 7(b).

The ZrO2 coating should be thick enough to avoid

the formation of cracks due to the existence of tensile stress in the ZrO2 coating for Al@Al2O3@ZrO2, whose thermal expansion coefficient is smaller than that of Al nanoparticles.45-46


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Figure 7. The schematic diagram of passivation mechanism for (a) Al@Al2O3@Al2O3 and (b) Al@Al2O3@ZrO2.

4. CONCLUSION In this paper, ultrathin ZrO2 has been coated on Al nanoparticles to enhance the stability using ALD method.

The Al@Al2O3@ZrO2-8 exhibits excellent stability in

water at 80 ºC, with 82.2 wt% of metallic Al, maintaining about 93.4% of pure Al nanoparticles.

In comparison, the Al@Al2O3@Al2O3 cannot resist the oxidation by

water at 60 ºC due to the reactivity between Al2O3 and water.

The passivation

mechanism of ZrO2 coatings can be attributed to their structural stability and enhanced hydrophobicity to water.

Our work on the enhanced stability of Al

nanoparticles in hot water can enable their safe applications in energy field.

■ ASSOCIATED CONTENT Supporting Information Growth rates of ZrO2 and Al2O3 on planar substrate; XPS characterizations of Al nanoparticles, Al@Al2O3@Al2O3-50 and Al@Al2O3@ZrO2-8; SEM images of Al@Al2O3@ZrO2-6 before and after stability test at 80 ºC. Water contact angle characterizations of Al2O3 film and Al2O3/ZrO2 laminate film. This material is available free of charge via the Internet at http://pubs.acs.org.



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■ AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] (R. C.). *E-mail: [email protected] (X. L.).

Notes The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (51575217) and the China Postdoctoral Science Foundation (2018M630856).

X. L.

gratefully acknowledges the support of Postdoctoral Innovation Talents Support Program (BX20180104).

We would also like to acknowledge the technology

supports from the Analytic Testing Center and Flexible Electronics Research Center of HUST.

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Figure1 215x126mm (300 x 300 DPI)


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Figure2 215x84mm (300 x 300 DPI)



Figure3 215x143mm (300 x 300 DPI)


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Figure4 195x171mm (300 x 300 DPI)



Figure5 273x213mm (300 x 300 DPI)


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Figure6 215x141mm (300 x 300 DPI)



Figure7 215x124mm (300 x 300 DPI)


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TOC 1054x546mm (150 x 150 DPI)


Ultrathin Zirconia Passivation and Stabilization of Aluminum

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