433
A publication of
CHEMICAL ENGINEERING TRANSACTIONS
VOL. 100, 2023 The Italian Association
of Chemical Engineering
Online at www.cetjournal.it
Guest Editors: Sauro Pierucci, Flavio Manenti
Copyright © 2023, AIDIC Servizi S.r.l.
DOI: 10.3303/CET23100073
ISBN 979-12-81206-03-8; ISSN 2283-9216
The Effect of Composition and Heat Treatment on
Microhardness of Ni-P and Ni-P-nanoZrO2 Coatings
Giulia Pedrizzetti*, Laura Paglia, Virgilio Genova, Marco Conti, Lidia Baiamonte,
Francesco Marra
Dept. of Chemical Engineering Materials Environment, Sapienza University of Rome, INSTM Reference Laboratory for
Engineering of Surface Treatments, Via Eudossiana 18, Rome, Italy
[email protected]Electroless Ni-P coatings have widespread industrial usage and their composition can be tailored by the
introduction of hard ceramic nanoparticles, to create a nanocomposite coating with improved properties. In this
work, nanoZrO2 reinforced Ni-P coating with medium P content (MP, ~6 wt.%) and high P content (HP, ~11
wt.%) were produced and heat treated at 200°C, 340°C, 400°C and 600°C, to study the evolution of
microstructure and microhardness properties as a function of coating composition and annealing temperature.
Results demonstrated that introducing ZrO2 nanoparticles efficiently increases the hardness of both MP and HP
nanocomposites without altering their microstructure, either in the as-deposited state or after heat treatments.
Conversely, P content strongly affects microstructure and crystallization behavior upon heat treatments:
nanocrystalline MP coatings experience Ni3P precipitation with treatment at 340°C, with subsequent controlled
grain growth, whereas amorphous HPs undergo crystallization and Ni3P precipitation after treatment at 400°C.
Microhardness evolution according to microstructural changes was evaluated and both coatings exhibited the
highest HV50 values after treatment at 400°C, at which complete Ni 3P precipitation is achieved. Microhardness
of nanocomposite coatings is always higher than particle-free ones, demonstrating that the synergistic effect of
dispersion hardening (given by nano-ZrO2) and precipitation strengthening (given by Ni3P) can be an effective
method to improve properties and meet the demanding need of engineering applications.
1. Introduction
Electroless Nickel-Phosporus coatings have extensive applications in many industrial fields of engineering to
protect components from extreme environmental attack (Kundu et al., 2019). Thanks to their excellent properties
of corrosion and wear resistance, hardness and solderability, Ni-P coatings gained much interest as a valid
alternative to traditional commercial Cr-based electrodeposited coatings.
Finding a reasonable substitute to hard chrome plating has become an urgent need for industrial development,
since the well-established deposition baths containing Cr(VI) have been limited in the context of REACH
regulation: its hazardous nature, being carcinogenic, corrosive and strongly oxidizing, imposes health, safety
and environmental concerns (Alfort, 2017). Yet, deposition from the newly proposed Cr(III) baths from aqueous
solutions remains a challenge. Despite being a more environmentally friendly alternative, the high stability of
Cr(III) complex with water molecules and the considerable hydrogen evolution at the cathode, which in turn
results in the formation of inert compounds, considerably limits the maximum thickness of the coating, that is
generally lower than 10 µm and makes the product unsuitable for functional applications (Adachi et al., 2020;
Xu et al., 2020). Therefore, much attention is focused on finding alternatives to Cr deposition that can maintain
the excellent properties required for engineering applications. Extensive studies have shown that Ni-P coating
can offer adaptive solutions to a wide range of environmental and working conditions (Lelevic and Walsh, 2019).
In particular, Ni-P coatings have a widespread application in the energy production industry, to protect rotor and
stator components of compressors from many degradation phenomena that would invariably deteriorate their
performance, including corrosion, erosion and wear. The strategic application of Ni-P coatings can mitigate
surface degradation of materials and increase service life of components.
Paper Received: 12 January 2023; Revised: 25 April 2023; Accepted: 25 May 2023
Please cite this article as: Pedrizzetti G., Paglia L., Genova V., Conti M., Baiamonte L., Marra F., 2023, The Effect of Composition and Heat
Treatment on Microhardness of Ni-P and Ni-P-nanoZrO2 Coatings, Chemical Engineering Transactions, 100, 433-438
DOI:10.3303/CET23100073
434
The electroless plating process allows the controlled reduction of metal ions onto a catalytic substrate by the
incorporation of a reducing agent in the plating solution (Genova et al., 2019). No external current is needed
and uniform coatings can be obtained on any surface, regardless of its shape (Genova et al., 2017).
Incorporation of phosphorus in the Ni matrix affects the structure and properties of coatings: high P coatings
(HP, 10-13 wt.%) are amorphous and highly corrosion resistant, whereas medium P coatings (MP, 6-9 wt.%)
are nanocrystalline and characterized by higher hardness and wear resistance (Balaraju et al., 2006). Hardness
of Ni-P coatings can be increased by thermal treatments, which induce phase transformation and precipitation
of Ni3P hard phases. Nevertheless, crystallization may also induce the formation of micro-cracks, that negatively
affect corrosion resistance (Ahmadkhaniha et al., 2018). Another strategy to increase hardness of Ni-P deposits
without altering the microstructure consists of the introduction of nanosized hard particles, to create a
nanocomposite coating with improved properties. Among the ceramic particles proposed as the reinforcing
phase, nano-ZrO2 has gained much interest thanks to its good mechanical properties and high ζ-potential, which
guarantees low agglomeration and ease of incorporation (Chinchu et al., 2020; Shibli et al., 2019; Zielińska et
al., 2012). In this work, Ni-P and Ni-P-nanoZrO2 coatings with medium and high P content are produced with an
original lead-free solution and annealed at different temperatures, to provide a comparative study on the
combined effect of composition and microstructural evolution on microhardness properties.
2. Materials and methods
Squared specimens of ASTM 182 F22 steel with dimensions of 15 mm x 15 mm x 3 mm were selected as
substrates. All chemicals were of analytic grade and purchased by Alfa Aesar (Thermo Fisher Scientific).
2.1 Coating preparation
Samples were sandblasted with corundum (mesh 80) as abrasive material, to remove contaminants and
increase surface roughness, which promotes deposition. Just before immersion in the plating bath, acidic
pickling of substrates with 50 vol.% diluted solution of HCl 37% was performed for 1 minute at room temperature,
to remove any trace of surface oxides. Rinsing in deionized water was performed after each cleaning step.
Composition of the lead-free electroless solutions for MP and HP deposition is reported in Table 1.
Table 1: Composition of the plating solutions for deposition of MP and HP.
Compound Function Amount for MP [g/L] Amount for HP [g/L]
Sodium hypophosphite Reducing agent 70 110
Sodium acetate Buffer 15 20
Citric acid Chelating Agent 6 9
Nickel sulphate Source of Nickel 12 25
Thio-organic compound Stabilizer* 5 ppm* 8.5 ppm*
*The stabilizer was added by liquid solution (1 mol/kg) and respecting the quantity in ppm.
Commercial ZrO2 nanoparticles, with an average particle size of 50-100 nm, were purchased from Io-Li-Tec
(Ionic Liquid Technologies GmbH) and used without any further purification. Previous experimental activities
demonstrated that introduction of 13.5 g/L of nanoparticles allowed the best compromise between incorporation
in the coating and agglomeration. Weighted powders were added to aqueous solutions and sonicated with
Elmasonic S 30 (H) ultrasonic cleaning unit for at least 15 minutes, to promote dispersion, before adding them
to the plating solution. Depositions of both MP and HP particle-free and nanocomposite coatings were performed
at 90°C for 90 minutes, under continuous magnetic stirring and constant control over temperature.
The study of microstructural evolution upon exposure at high temperature was carried out performing isothermal
heat treatments at 200°C, 340°C, 400°C and 600°C for 1 hour. All treatments were performed in air in a Lenton
tube furnace (now Carbolite Gero Ltd.). The presence of through-the-thickness cracks and defects induced by
thermal exposure was investigated by the Ferroxyl reagent test (ASTM B689-97).
2.2 Coating Characterization
Surface morphology and composition of the coatings were determined with a FEG-SEM Tescan Mira3 (Tescan,
Brno, Czech Republic) equipped with Edax Octane Elect detector for energy-dispersive X-Ray spectroscopy
(EDS). X-ray diffraction analysis (XRD) was performed with a Philips X'Pert diffractometer (PANalytical BV, The
Netherlands), operating at 40 KV and 40 mA with CuKα1 radiation, with scan range of 20–80° (2θ), feed step of
0.02° and acquisition time of 2 s. The microstructural characteristics of standard and nanocomposite coatings
were investigated as a function of phosphorus content and temperature of heat treatment. The crystallite size
was calculated using Scherrer’s equation (1):
435
0.94λ
D= , (1)
𝛽 cos(𝜃)
where λ is the wavelength of the radiation used, β is the half-maximum width and θ is the position of the main
peak. No correction for instrumental broadening was made.
Microhardness of the coatings was evaluated according to ASTM E384-11 using a Leica VMHT (Leica GmbH)
with a Vickers diamond indenter, with 50 gf load condition and indentation time of 15 seconds. Distance between
two indentations was ≥50 µm, results report the average value and standard deviation of at least twenty repeated
measurements.
3. Results and discussion
Surface morphology of HP and MP coatings reinforced with nano-ZrO2 and its evolution as a function of heat
treatment temperature is reported in Figure 1. Both coatings show the typical cauliflower-like morphology of
electroless NiP layers and some ZrO2 can be observed on the Ni-P surface. As expected, deposits with high P
content exhibit smaller nodular size compared with MP ones, since the higher P content limits the lateral growth
of nodules and promotes nucleation phenomena. MP nanocomposite annealed at 340°C and 400°C for 1h have
similar morphology, with finer micronodular structure compared with those treated at 200°C. In HP
nanocomposites, a similar nodular refinement can only be observed after heat treatment at 400°C, whereas
annealing at 340°C does not induce morphological changes. After exposure at 600°C, an oxide scale is visibly
starting to grow at the surface of both types of coatings, giving a porous and sponge-like structure. Similar
results about morphology refinement after heat treatments above the crystallization temperature are described
in literature (Chinchu et al., 2020; Karthikeyan et al., 2016). Therefore, the different temperature at which smaller
spherical nodules form between MP and HP nanocomposites suggests a different crystallization behavior
depending on the P content.
Figure 1: SEM micrographs showing morphology evolution of MP and HP nanocomposite coatings according to
the different temperature of heat treatment.
To uncover this aspect, microstructural evolution was investigated via XRD analysis. Comparison of XRD
spectra of as-deposited ZrO2-reinforced MP and HP coatings is reported in Figure 1(a). EDS analysis
demonstrated that HP nanocomposites contain ~11 wt.% of P, which is sufficient to produce an amorphous Ni-
P alloy. In this case, only one broad peak of Ni (111) is detectable in the XRD spectrum. Conversely, MP
coatings, with P content ~6 wt.%, are characterized by a nanocrystalline microstructure and XRD analysis
reveals the presence of additional Ni (200) and Ni (220) peaks. ZrO2 peaks can be identified in both spectra,
confirming the presence of nanoparticles.
Figures 1(b) and (c) show, respectively, the structural evolution of MP and HP nanocomposites as a function of
heat treatment temperature. The heat treatment at 200°C is necessary as dehydrogenation process: since Ni-
P deposition occurs along with H2 generation, this gas inevitably remains entrapped in the coating, causing
embrittlement and formation of porosities (Wang et al., 2011); dehydrogenation is therefore required to avoid a
dramatical reduction of mechanical properties. Since the crystallization temperature of Ni-P deposits is reported
to be around 340°C(Huang et al., 2003), aging at 200°C does not induce phase transformation and the
microstructure of both types of coatings remains similar to the as-coated condition. When the heat treatment is
performed at 340°C, a different microstructure between MP and HP deposits is observed: in MP coatings,
crystallization and precipitation of Ni3P phase occurs, whereas HP remains amorphous and no compounds other
than Ni are detected. This dissimilar behavior can be explained considering that exposure to high temperature
436
leads to two main effects: (i) grain growth of the Ni matrix and (ii) phosphorus segregation at grain boundaries
and triple junctions, with consequent formation of P-rich regions. Crystallization of the MP nanocomposite after
exposure at 340°C for 1h suggests that the initial nanocrystalline structure provides a higher number of sites for
P segregation, with a higher probability to exceed the threshold necessary for Ni 3P precipitation (reported to be
close to the eutectic concentration, ~11 wt.% of P (Farber et al., 2000)). It was proposed that the structural
changes that occur with temperature increase develop through the formation of a metastable grain boundary
phase, given by a supersaturated solid solution of phosphorus in nickel (Hentschel et al., 2000). In HP coatings,
this phase already develops in the as-deposited state due to the higher P content, giving it more thermal stability
at low temperature. Therefore, full crystallization of the amorphous HP nanocomposites is only obtained after
the treatment at 400°C. These results can also explain the differences observed in the morphological analysis.
After treatment at 600°C, the relative intensity of peaks increases and both spectra become sharper. Ni grain
growth and coalescence of Ni3P precipitates take place without the formation of other new phases, confirming
that the introduced ZrO2 nanoparticles are chemically inert and do not affect phase composition of the coatings.
The presence of nickel oxide peaks at 600°C should also be highlighted, confirming the growth of a thin oxide
scale.
Figure 2: (a) XRD spectra of HP and MP nanocomposites in the as-deposited condition; (b) XRD spectra of MP
nanocomposite coatings after 1h heat treatment at different temperature; (c) XRD spectra of HP nanocomposite
coatings after 1h heat treatment at different temperature.
Comparison of spectra at 400°C also reveals that HP coatings have sharper Ni and Ni3P peaks compared with
MP, which indicate higher grain size of Ni crystallites and precipitates. Evolution of average grain size, calculated
with Scherrer equation (eq. 1), and coarsening of Ni3P precipitates with increasing heat treatment temperature
is reported in Figure 3. Grain size of MP nanocomposite coatings is coarser than HP for heat treatment
temperature up to 340°C, where the latter still exhibit an amorphous microstructure. The trend is inverted at
400°C, where HP coatings exhibit coarser grains, indicating higher thermal stability of coatings with medium P
content when temperature is increased. This is explained considering that in MP deposits the heat treatment at
340°C temperature induces initial Ni3P precipitation: a metastable thermodynamic equilibrium is developed
between the Ni alloy and the P-enriched grain boundary phase, so that substantial grain growth is only possible
with additional formation of Ni3P, which acts a sink for P atoms (Farber et al. 2000). Moreover, increase in Ni
crystallite size is further restrained by the presence of the small precipitates themselves, due to the drag
mechanism. Conversely, in HP coatings the metastable equilibrium is already present in the as-deposited state
and, despite the higher thermal stability at low temperature, at higher temperature P segregation is more likely
to exceed the threshold for massive Ni3P precipitation, allowing major grain growth to occur (Hentschel et al.,
2000). At 600°C, precipitation is probably complete and both coatings exhibit a comparable structure.
437
Figure 3: Increase of average nickel crystallite size (a) and coarsening of Ni3P precipitates (b) with increasing
annealing temperature for MP and HP coatings reinforced with nano-ZrO2.
Both MP and HP standard and nanocomposite coatings after heat treatments are successfully tested to Ferroxyl
reagent test, indicating that neither nanoparticle introduction nor crystallization and phase change induce the
formation of through-the-thickness defects, which could prejudice mechanical properties and corrosion
resistance. Since microstructural changes induced by heat treatments are often exploited to modify coating
properties, Figure 4 shows microhardness of particle-free and nanocomposite coatings in the as-deposited
condition and after annealing at the different investigated temperatures. The synergistic effect between
nanoparticles introduction and microstructural features on coating microhardness results in higher HV50 values
for nanocomposites compared with their standard counterpart, with a progressive hardness increase up to
treatment at 400°C. Dispersion hardening effect given by hard nanoparticles introduction effectively strengthens
coatings, thanks to the simultaneous action as a barrier to dislocation motion, according to Orowan mechanism,
and the load-bearing effect (Zhang and Chen, 2008).
Both MP standard and nanocomposites have higher hardness than HP ones because deformation processes
in NiP coatings with very small grain size (between 2 nm and 15 nm) are governed by grain boundary sliding
and rotation, according to the reverse Hall-Patch effect (Apachitei et al., 2002); therefore, higher size of
crystallites, which associates with a lower amount of grain boundaries, results in enhanced microhardness.
Above 340°C, initial Ni3P precipitation in MP coatings further enhances hardness. In fact, the small and semi-
coherent precipitates are an additional barrier to dislocation motion, which have to move through the hard Ni3P
to cause deformation. Precipitation in MP coatings seems to be not yet complete after treating at 400°C, which
results in additional hardening at 400°C. Maximum hardness for HP coatings is also reached at 400°C, when,
according to XRD analysis, crystallization and precipitation occur. At 600°C, both coatings show lower hardness
due to excessive grain growth and coalescence of precipitates. These results are in agreement with those
reported by other authors in similar studies, where hardness decrease is registered after treatment at 600°C
(Amjad-Iranagh and Zarif, 2020; Jiang et al., 2016). Indeed, beyond the threshold of 15 nm, higher grain size
corresponds to lower hardness, in accordance with the Hall-Patch equation, and larger precipitates make it
easier for dislocations to loop around them, leading to a less effective Orowan strengthening.
Figure 4: Comparison of microhardness (HV) between particle-free and ZrO2-reinforced MP and HP coatings in
the as-deposited condition and after heat treatment at 200°C, 340°C, 400°C and 600°C for 1 h in air.
438
4. Conclusions
Electroless Ni-P-ZrO2 nanocomposite coatings with medium and high P content are successfully produced and
characterized. Introduction of the reinforcing phase led to a hardness increase by ~22% and ~24% for
nanocrystalline MP and amorphous HP coatings, respectively, without altering their microstructure in the as-
deposited state. A different crystallization behavior was observed for MP and HP coatings, which can be
ascribed to the different P content. ZrO2 demonstrated to be chemically inert to the Ni-P deposit and does not
alter phase composition upon heat treatments. Precipitation of the intermetallic Ni3P starts at 340°C in MP
coatings, whereas can only be observed after treatment at 400°C for HP coatings. Maximum hardness, up to
1012 HV50 for MP and 968 HV50 for HP nanocomposites, is obtained after treatment at 400°C, due to the
synergistic effect of nanoparticles dispersion hardening and Ni3P precipitation strengthening.
Reference
Adachi, K., Kitada, A., Fukami, K., Murase, K., 2020. Crystalline chromium electroplating with high current
efficiency using chloride hydrate melt-based trivalent chromium baths. Electrochim Acta 338.
Ahmadkhaniha, D., Eriksson, F., Leisner, P., Zanella, C., 2018. Effect of SiC particle size and heat-treatment
on microhardness and corrosion resistance of NiP electrodeposited coatings. J Alloys Compd 769, 1080–
1087.
Alfort, H.-J., 2017. When Does the Ban on Chromium (VI) Come into Effect? International Surface Technology
1, 48–51.
Amjad-Iranagh, S., Zarif, M., 2020. TiO2 nano-particle effect on the chemical and physical properties of Ni-P-
TiO2 nanocomposite electroless coatings. Journal of Nanostructures 10, 415–423.
Apachitei, I., Tichelaar, F.D., Duszczyk, J., Katgerman, L., 2002. The effect of heat treatment on the structure
and abrasive wear resistance of autocatalytic NiP and NiP-SiC coatings. Surf Coat Technol 149, 263-278.
Balaraju, J.N., Sankara Narayanan, T.S.N., Seshadri, S.K., 2006. Structure and phase transformation behaviour
of electroless Ni-P composite coatings. Mater Res Bull 41, 847–860.
Chinchu, K.S., Riyas, A.H., Ameen Sha, M., Geethanjali, C. v., Saji, V.S., Shibli, S.M.A., 2020. ZrO2–CeO2
assimilated electroless Ni–P anti-corrosion coatings. Surfaces and Interfaces 21.
Farber, B., Cadel, E., Menand, A., Schmitz, G., Kirchheim, R., 2000. Phosphorus segregation in nanocrystalline
Ni 3.6 at.% P investigated with the Tomographic Atomic Proble (TAP). Acta Mater 48, 789–796.
Genova, V., Marini, D., Valente, M., Marra, F., Pulci, G., 2017. Nanostructured nickel film deposition on carbon
fibers for improving reinforcement-matrix interface in metal matrix composites. Chem Eng Trans 60, 73–78.
Genova, V., Paglia, L., Marra, F., Bartuli, C., Pulci, G., 2019. Pure thick nickel coating obtained by electroless
plating: Surface characterization and wetting properties. Surf Coat Technol 357, 595–603.
Hentschel, T.H., Isheim, D., Kirchheim, R., Mu, F., Ller, È., Kreye, H., 2000. Nanocrystalline Ni 3.6 at.% and its
tranformation sequence studied by atom-probe field-ion microscopy. Acta Mater 48, 933–941.
Huang, Y.S., Zeng, X.T., Annergren, I., Liu, F.M., 2003. Development of electroless NiP-PTFE-SiC composite
coating. Surf Coat Technol 167, 207–211.
Jiang, J., Chen, H., Zhu, L., Qian, W., Han, S., Lin, H., Wu, H., 2016. Effect of heat treatment on structures and
mechanical properties of electroless Ni-P-GO composite coatings. RSC Adv 6, 109001–109008.
Karthikeyan, S., Vijayaraghavan, L., Madhavan, S., Almeida, A., 2016. Study on the Mechanical Properties of
Heat-Treated Electroless NiP Coatings Reinforced with Al2O3 Nano Particles. Metall Mater Trans A Phys
Metall Mater Sci 47, 2223–2231.
Kundu, S., Das, S.K., Sahoo, P., 2019. Friction and wear behavior of electroless Ni-P-W coating exposed to
elevated temperature. Surfaces and Interfaces 14, 192–207. https://doi.org/10.1016/j.surfin.2018.12.007
Lelevic, A., Walsh, F.C., 2019. Electrodeposition of Ni-P alloy coatings: A review. Surf Coat Technol 369, 198–
220.
Shibli, S.M.A., Chinchu, K.S., Sha, M.A., 2019. Development of Nano-tetragonal Zirconia-Incorporated Ni–P
Coatings for High Corrosion Resistance. Acta Metallurgica Sinica (English Letters) 32, 481–494.
Wang, L.L., Chen, H.J., Chen, Z.L., 2011. Study on post-treatments for electroless Ni-P coating. Surface
Engineering 27, 57–60.
Xu, L., Pi, L., Dou, Y., Cui, Y., Mao, X., Lin, A., Fernandez, C., Peng, C., 2020. Electroplating of Thick Hard
Chromium Coating from a Trivalent Chromium Bath Containing a Ternary Complexing Agent: A
Methodological and Mechanistic Study. ACS Sustain Chem Eng 8, 15540–15549.
Zhang, Z., Chen, D.L., 2008. Contribution of Orowan strengthening effect in particulate-reinforced metal matrix
nanocomposites. Materials Science and Engineering A 483–484, 148–152.
Zielińska, K., Stankiewicz, A., Szczygieł, I., 2012. Electroless deposition of Ni-P-nano-ZrO 2 composite coatings
in the presence of various types of surfactants. J Colloid Interface Sci 377, 362–367.
