Servizio Comunitario di Informazione in materia di Ricerca e Sviluppo - CORDIS

Periodic Report Summary 1 - HARDALT (New generation of protective coatings alternative to hard chrome)

Project Context and Objectives:
The total annual estimated direct cost of corrosion, not including wear damage, in the world is estimated at about 3.1% of the world’s Gross Domestic Product (GDP). Protective coatings serve to prevent wear and corrosion and thus reduce the total loss from corrosion and wear. Hard chromium plating is one of the most widely used techniques for production of such coatings. However, hard chromium faces many problems: EU restrictions due to use hexavalent chromium, health issues for the plating industry personnel due to cancers events, functional defects of the coatings and low current efficiency. Thus, there is an urgent need to substitute chrome plating with an alternative one that could provide the same or even enhanced benefits that chrome has, without causing the above problems.
The target of the project is to eliminate the use of hard chromium plating in European electroplating industry by delivering a suitable alternative, which will be the innovative electrolytic nano-structured Ni-P and Ni-P matrix composite coatings reinforced with (nano)particles such as SiC, B4C and MWCNT. The successful outcome of the HardAlt project will lead to the restriction or even elimination of the use of hexavalent chromium in electrodeposition industry and will not be subjected in EU legislations. As HardAlt coatings will present equal or even enhanced functional properties compared to hard chrome, they will be adopted by the metal working industry in applications where wear and corrosion resistance is of crucial importance. Ni-P composite coatings with a wide range of properties can be produced by appropriate imposition of electroplating parameters and applying thermal treatment where necessary using the same infrastructure and thus meet the needs of the majority of applications where hard Cr is used.Significant benefit will be the customization of the HardAlt coatings in the need of each application using the same bath leading to raw materials saving and minimization of wastes from electroplating industry.
The key program deliverable may be defined as the integrated electroplating process of applying the HardAlt coatings that will be used as alternatives to hard chromium coating along with the training activities that will take place among the members of SME-AGs partners.

The main objectives of the project are:
Development of a 3 times faster and 70% less energy consuming pulse current electroplating technique, compared to hard chromium, for applying Ni-P coatings. This objective will be verified by measuring the electrodeposition time for specified thickness of coatings and calculating the current efficiency based on Faraday's law.
Delivery of a production line for pulse plating Ni-P deposits with hardness >700 HV and wear and corrosion resistance equal to hard chromium. At least 10 items coated with Ni-P will be provides and tested in a series of measurements such as Vickers hardness, corrosion tests, tribological tests.
Development of pulse current electroplating technique for applying Ni-P composite coatings with a high co-deposition rate of reinforcing particles and better functional properties compared to hard chromium. The codeposition rate of reinforcing particles will be determined by EDS-XRF while functional properties will be verified by hardness, wear resistance, corrosion resistance measurements.
Delivery of a production line for pulse plating Ni-P composite coatings with hardness >800 HV and enhanced wear and corrosion resistance compared to hard chromium. At least 10 items coated by Ni-P matrix composite coatings will be provided and tested in a series of measurements such as Vickers hardness, corrosion tests, tribological tests.
Development of appropriate and fast thermal treatment procedure of coatings for further enhancing of their properties (Hardness values higher than 1200 and 1600 HV for Ni-P and Ni-P composite coatings, respectively). This objective will be verified by providing at least 10 thermally treated items coated by both Ni-P and composite Ni-P deposits and testing them in a series of measurements such as Vickers hardness, corrosion tests, tribological tests.

Project Results:
During the first 18 months of the project the following work has been performed:
Within WP1 the main objectives were to generate data on the overall specifications and requirement of the HardAlt coatings and to translate these into specifications of the components and processes for the production line of the coatings. For that purpose all the partners have been actively involved and especially the SME-AGs contributed on the part of the product development by providing all the necessary data based on their experience. Partners CERTH, PoliMi, Asfimet and the SME partners that are related with the field of electroplating collaborated for generation of specification related to the electroplating equipment and all operational parameters. Further, partners CERTH, PoliMi, CETRI and SEA collaborated for generation of specification on Ni-P and Ni-P composites electroplating baths, chemicals, additives and other components that will be used during the electrodeposition process. Finally, the UoS and Falex set all the specifications requested for reliability test methods as well as the field trials.
In WP2, more specifically in Task 2.1 the specifications related to the substrate pre-treatments prior electroplating procedure were determined. Concerning the kind of substrate material it is agreed to use two types of specimens: carbon steel as basic substrate and aluminium as a hard to plate metal. Thus, appropriate substrate pre-treatment processes that will be applied prior to electrodeposition were developed. In following the optimum electrolytic parameters of direct current plating for Ni-P coatings in terms of high properties performance and low internal stresses have been defined. Both sulphate based (W-bath) and sulphamate based (S-bath) baths were developed with suitable combinations of additives, working temperature, pH and current density. Ni-P coatings with P concentrations from 3 to 18 % have been electroplated with hardness values in range 575 to 715 HV. Heat treated Ni-P coatings exhibit increases hardness to range of 955-1110 HV. The tribological study of the coatings showed comparable performance to hard chrome. The best performing Ni-P coatings that qualify for the next phase of HardAlt project have been selected and optimized DC conditions have been delivered.
The first objective of WP 3 was to select the reinforcing particles to be used for electroplating of Ni-P composite coatings. Nano-SiC, MWCNT and B4C were selected as best candidates. Following the distribution of reinforcing particles in the bath has been improved by adding suitable additives and applying ultrasounds. The effect of the electrodeposition parameters such as applied current density, working pH, addition of different additives and type and load of nanoparticles on the microstructural and mechanical properties of the composite coatings has been investigated. The optimum electrolysis conditions based on the enhanced functional characteristics of Ni-P composites has been defined. P content in composite coatings ranged from 3 to 18%. Incorporation of reinforcing particles depended on the electrolysis parameters and type of particles. The best performing Ni-P/SiC, Ni-P/CNT and Ni-P/B4C have been selected and the optimal conditions applied for their production delivered for further investigation under pulse current plating in WP5. Developed heat treatment procedure enhanced functional properties of composite coatings. Coating's hardness reached peak of 1360 HV at 400oC. In WP6 all necessary microstructural, mechanical and tribological characterization tests and measurements of the produced DC pure and composite Ni-P coatings have be performed. WP4 and WP5 are dedicated to the pulse plating of Ni-P and Ni-P composite coatings. Preliminary data show that the electrolytes developed in WP2 and WP3 can be used in pulse plating mode providing improvements in the process and layer properties. Cathodic efficiency, especially in the case of high P is benefited from pulse plating. Furthermore, an increase of reinforcing particle codeposition rate have been detected.

Potential Impact:
Europe is at the heart of a devastating economic crisis and a huge number of European SMEs struggle to overcome global competition. Innovative solutions are needed to help them produce desirable to the market products and reduce operational costs. These innovations not only shouldn’t be affiliated with cuts on security and safety of employees, but should also offer the perfect conditions to create an absolutely safe and healthy working environment. More specifically in the sector of metalworking and electroplating industry, new and effective techniques of electroplating are needed in order to comply with strict EU legislation and annihilate the occurrence of diseases caused by the use of Cr+6. The replacement of hard Cr coatings with relevant Ni-P based ones will achieve absolute compliance to the already existing and forthcoming strict EU legislations, directly saving from shutting down the companies that use HardAlt. The large SME community in Europe (22.000 electroplating companies) that needs a new and improved procedure in electroplating will manage to dramatically upgrade and optimize their products taking always into consideration environment’s protection and workers’ health and safety. SME-AGs involved in metal and metalworking, surface finishing and electroplating sectors, alongside with the European Community as a whole will be benefitted by the project’s impact in all possible aspects, offering advantages to every involving participant. HardAlt will meet the end users’ (companies in the aerospace, automotive, energy, marine, military, tools sectors etc) needs in quality, performance, and functionality while the dangers, the cost and the effort will be significantly lower to the current solutions. In conclusion, the advantages of our novel coating process and coated items are so attractive and obvious, that they will be desirable for the end users to buy them and gradually European SMEs will get established as dominant players in the global market.

The expected impacts of the project are described and justified in the process, however in bullets they are as follows:
 Clear economic benefits for the SME-AGs participating in the project, for their members involved in metal and metalworking, surface finishing and electroplating sectors and for third parties involved in exploitation.
 Solution to the problem of compliance with current and upcoming EU restrictions of Cr+6 use in electroplating, saving this way European SMEs from closing down
 Clear economic impact on EU economy from reduction of health expenditures (reduced hospital care) and increase of exports and decrease of imports
 Clear impact on workers’ health protection (significant decrease of cancer cases thanks to Cr+6 replacement)
 Better quality, cheaper and faster coatings in the aerospace, automotive, energy (oil and gas pipelines and drilling), marine, military and tools’ sectors
 Potential development of new or conformation of existing European standards and norms on electroplating and in general in health & safety metalworking protection matters
 Internationalization of SMEs through European co-operation for after project partnership
 Creation of new employment job opportunities in the EU and new start-up companies
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United Kingdom