production of nickel composite materials …the electrochemical activity of the produced sam-ples...

Journal of Chemical Technology and Metallurgy, 55, 3, 2020

608

PRODUCTION OF NICKEL COMPOSITE MATERIALS REINFORCED WITH ULTRAFINE POWDERS

Alexander N. Zadiranov, Marianna Yu. Malkova, Ramzi Abu-Nijim

ABSTRACT

The purpose of this study was to develop a composite microporous precipitation on a nickel substrate from the electrolytes suspensions with the use of powders of nanosize fraction. As a result of the research, composite materi-als on a metal substrate (MMC) from electrolytes suspensions with additives of ultrafine powders (UDP) of nano-sized fraction obtained from waste of metallurgical industry were obtained and experimentally studied. It has been established that with the use of UDP in the composition of electrolyte suspensions, MMCs are produced, reinforced with ultrafine one-dimensional elements. The effect of the concentration of additives of UDP on the porosity of the substrates and their electrochemical properties (corrosion resistance, electrochemical activity) was established. It is shown that the porosity, the corrosion resistance and the electrochemical activity of MMC are determined by the size of ultrafine elements and their concentration in the electrolyte suspension. The costs of organic additives in electrolytes providing the required surface quality of MMC were determined and optimized.

Keywords: composite materials, nickel, electrolytes suspensions, ultrafine powders, metallurgical waste.

Received 31 October 2019Accepted 16 December 2019

Journal of Chemical Technology and Metallurgy, 55, 3, 2020, 608-613

Peoples` Friendship University of Russia 117198, Miklukho-Maklaya str.6, Moscow, RussiaE-mail: [email protected]

INTRODUCTIONRecent observations of highly technological in-

dustries show that traditional composites are replaced by disperse-strengthened composites with nano-sized reinforcing materials [1 - 16]. Such composites have absolutely new exploitation properties.

Metal composite materials (MCM) are presented as microporous metal base with solid particles included in it. The major advantage of MCM is the corrosion resist-ance. In manufacturing of MCM disperse particles of oxides, carbides, nitrides, borides and other heat-resistant materials are used as strengthening phase.

MCM can be synthesized by various means, and electrochemical ones stand in a single group. The rein-forcing particles are usually about 3 - 5 microns in size, so substrate is several millimeters thick. Moreover, the more stable is the size of the fraction of reinforcing ele-ments, the higher are the physical-chemical and physical-mechanical properties of the product.

It was interesting to reduce the size of the reinforcing particles MCM to a fraction of nanometer sizes with the

aim of obtaining MCM characterized by new exploita-tion properties and economy of substrate material. In this regard, the aim of the study was to obtain compos-ite materials on a nickel substrate by electrochemical method with the use of kaolin and bentonite powders by nano-sized fraction as a dispersion-strengthening phase.

EXPERIMENTALMaterials and methods

For MCM synthesis, nickel suspended Watts-type electrolytes based on methanesulphonic acid and nickel acetate were designed. The electrolytes’ formulas and technical features are provided in Table 1.

The nickel composite sediments were synthesized via electroplating method from nickel suspended elec-trolytes. All the suspended electrolytes contain ultra-disperse powders of caolinite and bentonite fractions 100 ± 30 nm that deposited on the substrate along with nickel.

Powders with nano-sized fractions were produced from pure caolinite and bentonite via orbital-type mill [17 - 19].

Substrate was chromeplated with the use of various


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electrolytes at various conditions (Table 1). Electroplat-ing process was executed with usage of existing standard methods of cathodic sediments production.

Sediments’ structure was provided by photographs made through “MIM-8M” and “NEOFOT” microscopes at 2000x zoom. Cathodic polarization curves were built via “P-5848” potentiostat registering experiment data on “KSP-4” potentiometer tape.

Procedure b - FEM gridCathodic electroplating sediments were worked

out on “Parker”-type facility, which is schematically presented in Fig. 1[20]. Deposition was carried out on a cathode with an area of 1 cm2, from Watts-type electrolytes, methanesulphonic acid and nickel acetate (3-1 – acetate-chloride, 3-2 – sulphate-acetate-chloride).

For getting metal anode activity data anodic polariza-tion curves of nickel dissolution were built for sulphate solution that does not contain chlorine ions and has the following content (g L-1): NiSO4·7H2O – 360; H3BO3 – 40. Four nickel samples were used during the experiment: 1

Component 1 2 3-1 3-2

NiSO4·7H2O, g/l 300 - - 250 NiCl2·6H2O, g/l 60 60 14 14 Ni(CH3SO3)2, g/l - 300 - - Ni(CH3COO)2·4H2O, g/l H3BO3 , g/l

- 30

- 40

125 35

125 40

Sacharine, g/l 1 1 1 1 2-butine-1.4-diol 0.5 0.5 0.5 0.5 Bentonite, g/l Caolinite, g/l

1-1.5 1-3

1-1.5 1-3

1-1.5 1-3

1-1.5 1-3

pH Experiment time, min Temperature, оС Current density, А/dm2

4-4.1 6

45-50 1-2

4.5 8 50 3-5

4.5 6 50

15-20

4-4.1 7 50

15-20

Table 1. Chemical formulas of nickel-containing suspended electrolytes and conditions of experiments.

Fig. 1. Electroplating facility: 1- electrolyzer; 2 - electro-lyte; 3 - anode; 4 - anode bag; 5 - cathode (titanium); 6 - electric heater; 7- power supply; 8 - ammeter; 9 - voltmeter; 10 - control unit.

Nickel type Contents, %

Ni Co C Cu Zn Fe S MCM 99.67 0.03 0.005 0.005 0.001 0.1 0.002 N0 99.93 0.01 0.01 0.02 0.001 0.01 0.001 NPAN 99.37 0.03 0.005 0.005 0.001 0.03 0.01 “S”- nickel 99.92 0.05 0.004 0.003 0.0003 0.0005 0.02

Table 2. Chemical contents of various nickel types.


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is an S-type nickel manufactured by INCO Corporation, 2 – nickel of NPAN type (anodic non-passivating nickel), 3 – N0-type nickel, 4 – MCM on nickel substrate synthe-sized in this work. Chemical formulas and contents of the samples are presented in Table 2.

Corrosion tests of metallic sediments were processed by methods of cuprum-salt-vinegar spray at 50оC, 96 % moisture and pH of 3.3. Areas of corrosion were then estimated visually using special etalons. The corrosion ratio was calculated via ASTM standard.

RESULTS AND DISCUSSIONResults are presented as illustrations (Figs. 2 - 5)

and Table 3.

Microscope pictures of composite surfaces are pre-sented in Fig. 2. It is established that the character of the location of porosity classifies the received CMEs to the category of randomly reinforced ones. It is showed that metallic sediments’ porosity is estimated 4∙104 - 4∙105 pores/cm2 depending on caolinite and bentonite quantities (g L-1).

RESULTS AND DISCUSSIONQuantity and quality evaluation of synthesized

MCMs was processed during the research. The quality was estimated by means of ASTM standards. The corro-sion tests provided in Fig. 3 showed that the composite microporous sediments on nickel substrate were hit by

Parameter

Units Ratio 1 2 3-1 3-2

Contents bentonite (1) g/l 1 1 1 1 caolinite (3) g/l 3 3 3 3 caolinite+bentonite (3:1) g/l 4 4 4 4 Porosity bentonite pcs. 3.72∙104 3.91∙104 3.88∙104 4∙104 caolinite pcs. 30.6∙104 32.33∙104 32.65∙104 39.07∙104 caolinite+bentonite pcs. 39.88∙104 40.41∙104 41.11∙104 41.45∙104 ASTM ratio caolinite+bentonite (1:2) units 6 6 6 6 caolinite+bentonite (1:1) units 9 9 9 9 Change Uстан caolinite+bentonite (1:1) mV 30 28 29 30 caolinite+bentonite (1:3) mV 20 21 23 20 Icr. А/dm2 0.05 0.07 0.05 0.05 If.p. А/dm2 0.0003 0.00035 0.0003 0.0003

Table 3. Results of MCM sedimentation from nickel suspended electrolytes.

Fig. 2. Microphotographs of composite sediment on nickel substrate. Containment of nano-fraction powder mixture (g/l): а) bentonite – 2; b) caolinite – 2; c) bentonite – 1, caolinite – 3.

а) b) c)


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corrosion only after 7 testing cycles. After 10 tests the ASTM ratio fell down to 3 units. Microporous chromium electrochemical sediments synthesized on the nickel substrate from electrolyte containing 1 g L-1 of caolinite and 2 g L-1 of bentonite were affected by corrosion after 8 testing cycles. 12 testing cycles gave the result of 6 units in ASTM. The usage of composite nickel substrate manufactured from electrolyte with 3 g L-1 of caolinite nano-fraction powder and 1 g L-1 of bentonite nano-fraction powder showed no decrease in ASTM ratio even after 10 cycles of corrosion tests.

The electrochemical activity of the produced sam-ples was used as a quantity evaluation. The activity was defined by polarization curves of metal dissolution in electrolyte.

Fig. 4 illustrates that there is an increase in standard electrochemical potential of multi-layer electrochemical materials in time (salt spray method), so electrochemi-cal activity decreases, therefore, the material’s corro-sion resistance becomes higher, and the more porous (containing of nano-fraction powders in electrolyte) the material is, the more is the change.

Fig. 3. Change of corrosion ratio during the tests of electrochemical: 1 – cuprum-nickel-chrome shining; 2 – cuprum-nickel-chrome composite (1 g L-1 of caolinite + 2 g L-1 of bentonite); 3 – cuprum-nickel-chrome composite (1 g L-1 of caolinite + 3 g L-1 of bentonite).

Fig. 4. Standard potential change in time of multi-layer electrochemical materials (salt spray method): 1 – cuprum – nickel – nickel composite (1 g L-1 of caolinite + 3 g L-1 of bentonite) – chrome shining; 2 – cuprum – nickel – nickel composite (1.5 g L-1 of caolinite + 1.5 g L-1 g L-1of bentonite) – chrome shining; 3 – cuprum – nickel – chrome shining.


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Quality MCM surface esteem showed that the sus-pended electrolytes containing 1 g L-1 of caolinite and 3 g L-1 of bentonite are the most quality efficient in porosity.

The electrochemical properties of MCM were com-pared with the ones of various nickel types. The anodic polarization curves (Fig. 5) show that INCO’s nickel is the most active when dissolving in sulphate electrolyte. Critical anode current density (icr.) for this template is 22 A/dm2, and area of potentials for active dissolution is between 100 and 150 mV (a-b area). Passivation of the sediment goes at 300-1250 mV (c-d area) with the current density (if.p.) of 0.02 A/dm2. The sample dissolves at potentials of overpassivation (1250-1650 mV, d-f area) changing by area of oxygen synthesis potentials after 1700 mV (m-n area).

For NPAN-type nickel (curve 2) icr. = 4 A/dm2, and for N0-type nickel icr. = 05 A/dm2 at the potential of 150-250 mV. For this nickel type if..p. is very low and is equal to 0.001 A/dm2. At the overpassivation potentials the curve becomes more electropositive in comparison with curves 1 and 3.

The lowest critical current density (0.05 A/dm2) belongs to nickel substrate MCM. For MCM if..p is estimated to be 0.0003 А/dm2. Curve 4 is even more electropositive at overpassivation potentials compared with curves 1-3. Therefore, using polarization curves, we can state that electrochemical activity of MCM on nickel substrate (at anodic dissolution) in sulphate (non-

chlorine) electrolyte is very low.Experimentally was confirmed that caolinite and

bentonite additives in nickel electrolytes can provide manufacturing of composite materials with new exploi-tation properties.

CONCLUSIONSNew MCMs from nickel suspended electrolytes with

nano-fraction caolinite and bentonite powder additives were synthesized and experimentally researched.

Contents of nickel suspended electrolytes with nano-fraction powder additives based on Watts type electrolytes, methanesulphonic acid and nickel acetate were offered.

Dependence between concentrations of nano-frac-tion powders, porosity and electrochemical properties of sediments was established. Optimal concentrations of nano-fraction powders in suspended electrolyte guar-anteeing creation of composites with new exploitation properties were defined.

AcknowledgementsThe publication has been prepared with the support

of the «RUDN University Program 5-100».

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production of nickel composite materials …the electrochemical activity of the produced sam-ples...

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