Final Report Summary - ADEC (Advanced Low Friction Engine Coating)
Executive Summary:
The consortium behind the AdEC project (Advanced Low Friction Engine Coatings) has developed and implemented state-of-the-art surface technologies, improved existing advanced coating processes with the aim of increased two-stroke engines performance by the incorporation of coatings on piston, piston-rings and cylinder wall.
The partner focus was along the value chain spanning the entire way from the development of novel surface functional nano diamonds (Carbodeon), electroplating (AK Chrome, IPU, Carbodeon), coating and surface treatment based on Plasma Electrolytic Oxidation - PEO (IPU) and vacuum based thin film coatings (DTI), test and validation at lab-scale (DTI) to field test involving end-users (Husqvarna and Radne).
Development of nano diamonds fully re-functionalized with hydrogen atoms has been carried out. These highly zeta positive (+68 mV) nano diamonds are aqueous soluble up to 5 wt. %. The development nano diamonds have been IPR protected in 2 granted patents and 16 patent applications.
Dispersion plating based on both the developed nano diamonds and mixtures of nano diamonds, hexa-boron nitride (BN), CaF2 and traditional Nikasil (SiC) has been developed.
A number of different plasma electrolytic conversion coatings were developed and tested on aluminium pistons, Ti rings and Ti pistons. PEO processes were developed and optimized for both Ti and Al base materials. In addition, PEO including ZrO2 doping was developed resulting in higher hardness.
Si- and W-doped DLC coatings, which can tolerate higher temperatures, have been developed. The coatings have been characterized by Raman, SEM, XRD, adhesion, nano-indentation and RBS. The coating has been tested on piston and piston rings revealing a lower friction and allowing to run the engine in a configuration where the engine would normally seizure with significant reduction of the cylinder temperature to below 270 oC. Based on dyno tests at Husqvarna the friction has been found to be ~3% better.
In house plating facilities has been built at one of the consortium SME participants (Carbodeon).
All dispersion nickel-plated solutions based on nano diamonds, CaF2 or BN coated cylinders have only revealed same performance or marginally better as compared to reference piston, piston-rings and cylinder systems.
The results have been published in one article and disseminated at a number of conferences and trade fairs. A video presentation is made it is viewable at the ADEC website (http://www.adecoating.dk/project-results.aspx).
Project Context and Objectives:
The major research objectives are organised in five areas, corresponding to the structure of the project:
1. Development of Functional Nano-particles, aiming to improve surface functionalization of nanodiamonds including their dispersion and zeta-potential to enable the development of a unique dispersion hardened coating of engine component surfaces. The work will also optimize the particle distribution and push the costs down based on intelligent compromises concerning the size distribution of the used nanodiamond particles.
2. Development of Wet Chemistry and formulation of a new electroplating bath, capable of dispersion plating a host matrix material, containing different nanoparticles. A key focus in this context is that both the embedded ceramic particles as well as the host matrix material will have to be and remain stable under combusting conditions.
Further, it is the objective to improve the performance if the particles reveal a high affinity to oil enabling lower friction properties. The materials are selected upon thermodynamically consideration to avoid thermochemical reactions with the selected ceramic particles and degradation of the host metal matrix.
3. Selection & Optimisation of material for piston has the objective to develop the optimal material combination for constructing an engine piston system having optimal efficiency. Historically, steel and aluminium have been chosen but also magnesium has been suggested for the piston rings. Due to thermal management, it is important to work with materials with small or matched thermal expansion coefficients, while the materials must have sufficient wear resistance.
Selection of titanium for the piston material makes it possible to perform Plasma Electrolytic Oxidation (PEO) of the substrate forming a thick wear resistant coating consisting of TiO2 which might also involve the integration of ZrO2 in order to obtain a harder coating. This may also be combined with a suitable surface treatment like a metal nitride or Wolfram Carbide (WC) supported Diamond-Like-Carbon (DLC) coating deposited by Physical Vapour Deposition (PVD).
Combining optimized materials and coatings in a new way will most probably enable the development of engines of the future having a much higher durability and with much lower friction properties, which will lead to engines with superior fuel efficiency.
4. Development of Diamond-Like-Carbon (DLC) for piston coating that has a tailored interaction hereunder perfect low-friction towards nanodiamond particles integrated into the dispersion plated Ni or Co/Ni matrix. A major requirement (mandatory) is that the DLC is temperature stable enough to withstand the conditions inside a combustion engine.
5. Field tests are made to evaluate and verify the developed coatings in a realistic and controlled environment. Through various tests of standard and modified engines, the achievements towards the objectives are to be compared. The primary test set-up, will be laboratorial, where electronic and calibrated equipment will be used for registration and logging of measured data. Subsequently, real time, on-road test under various conditions will be included for all engine applications.
The overall success criteria can be summarised as:
Reduce cylinder wall temperature:
Si-doped DLC coatings have been developed which can tolerate higher temperatures. The coating has been tested deposited on piston, piston rings and tested both at DTI, Husqvarna and Radne. Husqvarna reports improved friction properties, and lower temperature, whereas Radne concludes that it is only marginally better. DTI reports that it is possible to run the engine in configurations where the engine would normally seizure with significant reduction of the cylinder temperature to below 270 oC.
Lower engine weight by allowing alternative materials:
The project has developed Ti-piston, Ti piston rings and Mg-piston to test the performance of alternative materials. Ti-rings have been tested and have shown to seize. However, Si-DLC coated Ti-rings behaved surprisingly well.
The one-one copy of the aluminum piston made in Ti-piston was too heavy to be tested.
Ti-rings and Ti-piston have been PEO-treated and PEO-ZrO2-doped.
Increase in the obtainable power by op to 20 %:
All tested solutions, ND-Ni coatings, CaF2, or BN coated cylinders, DLC-coated piston and piston rings have only revealed same performance or marginally better. Based on dyno tests at Husqvarna it was found to be ~3% better. It has not been possible to obtain a power increase of 20 %.
Improved fuel economy by more than 20 %:
Lower friction will increase the fuel economy, but 20 % is beyond what is feasible.
Lowering of oil consumption:
The tests performed with improved Si-DLC have shown that it is possible to run the engine under conditions where it will otherwise seize. This might open up for running the 2-stroke engine with a lower oil content in the fuel in the future.
Improved scuff and wear resistance on cylinder bores, piston and piston rings:
- Si-DLC coated pistons show that there is no scuffing for a DLC coated piston.
- Reduced friction:
- The Si-DLC coated piston has revealed lower friction.
Lower CO2, NOx and soot/particle emission:
Lean out of the engine will give less soot/particle formation. The addition of Si-DLC to the piston, piston rings and cylinder has revealed that it is possible to run the engine at much more lean condition. This will give rise to less NOx. Hereto comes that the lower temperature caused by less friction (heat) will also give less NOx. CO2 is linked to fuel consumption, which will be lower due to less energy going to friction. However, experiments only indicated marginally improved performance.
Improve the lifetime of the engine parts:
There is no indication of significantly improved lifetime of the different engine parts tested.
Enable the use of alternative lightweight materials such as e.g. Zr-doped alumina inside the engine:
The project has successfully developed PEO and Zr-doped PEO. The PEO-treated pistons have been tested with poor performance caused by narrow prison ring grooves. Also the temperature and friction were observed to increase due to narrow tolerances. Further improvement is needed.
Project objectives for the period:
The project has worked along 9 objectives and the result of these tracks are summarized below:
Objective 1: To develop functional micro or nanoparticles based on different compositions such as BN, functionalized nanodiamonds (ND) providing non-agglomeration capabilities and a developed high affinity to lubricants by adjusting their zeta potential.
Nanodiamonds with improved dispersion have been developed creating products free of agglomerates aligned with plating-relevant chemistries. Less agglomeration and improvement is obtained in the deposited products and the developed coatings’ technical performance is better than those with previous generation nanodiamond additives, seen in the literature. Moreover, due to improved dispersion stability, the coatings’ enhanced performance is now available with a fraction of nanodiamond additive loadings into the applied nickel electrolyte. Adjustable zeta potential of the ND has been done and proven. No major improved affinity for oil could be identified/documented. This might be linked to the very low nanodiamond concentrations applied in the developed coatings.
The developed ND formulations and surface hydrogen activation have been patented and marked exploration is in progress both in the field of electroplating but also alternative applications are investigated.
Objective 2: Arrive at a minimum cost-performance ratio for the nano-particle-coating targeting to be 10-20 % cheaper than existing technologies but at the same time outperforming the existing technologies by tailoring the purity and a size distribution of the involved nanoparticles.
It is estimated that nanodiamond-containing nickel can be made comparable or even cheaper than existing Nikasil technologies. This is of course dependent on the needed content of nanodiamonds. Breakeven compared to conventional Nikasil is found for a ND content around 0.22 wt. %. The wet chemistry has been optimized and ND can be incorporated into electroplated and electroless nickel.
Objective 3: Selection of materials for piston manufacture with thermal expansion coefficients to minimal mitch match and better than currently applied materials.
Work has been made on titanium. Titania rings work surprisingly good when they are DLC-coated. A fabricated Ti-piston was PEO-treated but was found too heavy to be tested.
Normal rings coated with TiN -> gave more wear. Zr-doped PEO treated aluminium piston coated with a hereto developed Si-DLC worked, but not as good as a standard piston-cylinder configuration.
Objective 4: Development of a scalable electrochemical plating system based on dispersion plating of Co/Ni with embedded nanocrystals.
Scalable plating technology and chemistry has been developed towards incorporation of nanodiamonds (ND), CaF2 and BN. Plating of test items and cylinders has been performed.
Objective 5: Tailored DLC coating with improved adhesion through a nanodesigned WC adhesion layer. Overall with improved adhesion and temperature resistance.
New types of DLC and WC supported DLC have been developed. Increased performance and increased temperature stability have been obtained. The results are very promising and will be followed up beyond project termination.
Objective 6: Elucidation of possible improvement through plasma-electrolytic oxidation and doping with Zr.
PEO of Al, Ti and Mg has been developed, and test samples of pistons and rings have been performed. ZrO2 doping during the PEO-treatment has been developed and it is shown that the addition of ZrO2 increases the hardness even further.
Objective 7: Overall engine performance with the new coatings of 5-10% increase in the dynamic/static power.
A new DLC has been developed and tested and was found to be 3% better – based on analysis of dyno tests.
Objective 8: Carry out thermodynamic calculations for constructing of predominance diagrams, with respect for selecting best combination of metal matrix and particle combination for designing coatings for high-temperature combustion processes in engines.
Thermodynamic evaluations of the metal matrix and particle system have been performed, and a number of metal matrix and particles combinations were found to be candidates for further development. It was decided to focus on BN, CaF2 and nanodiamonds in a Ni matrix.
Objective 9: Evaluation of surface functionalization of particles by modifying surfaces on nano-by grasping with different molecules to make them active in the electric field.
Different surface-functionalized nanodiamonds have been fabricated generating different zeta potentials by changing the surface charge. This resulted in less agglomeration in the acidic electrolyte.
Objective 10: Develop dispersion models based upon Ni, Co or Co/Ni plating based on nanodiamonds and/or BN.
Different electroplating parameters were investigated for Ni hereunder the particle content and the nickel chemistry, current density and temperature. The formulation was demonstrated for BN, nanodiamonds and CaF2.
Project Results:
The focus of the AdEC project was to develop and implement state-of-the-art surface technologies and improve existing advanced coating processes focusing on Ni-Co based dispersion coatings containing a mixture of nano-diamonds and hexa-boron nitride (BN) and develop improved solutions in relation to especially two-stroke engines at Husqvarna and Radne. This development was broken down into a number of work packages:
WP2: Development of functional nano-particles
WP3: Development of wet chemistry
WP4: Selection & Optimisation of Material for Piston
WP5: Development of DLC for piston
WP6: Field Test
WP7: Dissemination and Exploitation
The overall success criteria in the DOW can be summarised as:
Reduce cylinder wall temperature:
Si-doped DLC coatings have been developed which can tolerate higher temperatures. The coating has been tested deposited on piston, piston rings and tested both at DTI, Husqvarna and Radne. Husqvarna reports improved friction properties, and lower temperature, whereas Radne concludes that it is only marginally better. DTI reports that it is possible to run the engine in configurations where the engine would normally seizure with significant reduction of the cylinder temperature to below 270 oC.
Lower engine weight by allowing alternative materials:
The project has developed Ti-piston, Ti piston rings and Mg-piston to test the performance of alternative materials. Ti-rings have been tested and have shown to seize. However, Si-DLC coated Ti-rings behaved surprisingly well.
The one-to-one copy of the aluminum piston made in Ti-piston was too heavy to be tested.
Ti-rings and Ti-piston have been PEO-treated and PEO-ZrO2-doped.
Increase in the obtainable power by op to 20 %:
All tested solutions, ND-Ni coatings, CaF2, or BN coated cylinders, DLC-coated piston and piston rings have only revealed same performance or marginally better. Based on dyno tests at Husqvarna it was found to be ~3% better. It has not been possible to obtain a power increase of 20 %.
Improved fuel economy by more than 20 %:
Lower friction will increase the fuel economy, but 20 % is beyond what is feasible.
Lowering of oil consumption:
The tests performed with improved Si-DLC have shown that it is possible to run the engine under conditions where it will otherwise seize. This might open up for running the 2-stroke engine with a lower oil content in the fuel in the future.
Improved scuff and wear resistance on cylinder bores, piston and piston rings:
Si-DLC coated pistons show that there is no scuffing for a DLC coated piston.
Reduced friction:
The Si-DLC coated piston has revealed lower friction.
Lower CO2, NOx and soot/particle emission:
Lean out of the engine will give less soot/particle formation. The addition of Si-DLC to the piston, piston rings and cylinder has revealed that it is possible to run the engine at much more lean condition. This will give rise to less NOx. Hereto comes that the lower temperature caused by less friction (heat) will also give less NOx. CO2 is linked to fuel consumption, which will be lower due to less energy going to friction. However, experiments only indicated marginally improved performance.
Improve the lifetime of the engine parts:
There is no indication of significantly improved lifetime of the different engine parts tested.
Enable the use of alternative lightweight materials such as e.g. Zr-doped alumina inside the engine:
The project has successfully developed PEO and Zr-doped PEO. The PEO-treated pistons have been tested with poor performance caused by narrow prison ring grooves. Also the temperature and friction were observed to increase due to narrow tolerances. Further improvement is needed.
Major achievements:
When asking the consortium partners, the following achievements have been highlighted:
• Development of PEO and Zr-doped PEO equipment and processes at RTO partner
• Development and patenting of new family of surface-functionalized nanodiamonds showing high zeta potential and stability in different electroplating chemistries
• Build-up of dispersion plating knowledge and capabilities at the SME
• Development of new Si-DLC and W-DLC
• Development of new test facilities at RTO partner
• Increased knowledge and network reaching beyond the project
• New business possibilities for the involved partners
• Development and test of interesting demonstrators
• Market growth possibilities of the developed nanodiamonds both in relation to electroplating as well as in other segments
• Market growth possibilities for the developed DLCs.
Exploitable results:
The involved partners have identified the following exploitable results:
• Electroless dispersion plating of nickel-containing nanodiamonds (ND) at the in-house facilities at Adec SME partner Carbodeon – focus on customer-paid development and new R&D projects
• Electroplating of nickel and chrome coatings containing nanodiamonds at the in-house facilities at Carbodeon – focus on customer-paid development and new R&D projects
• Worldwide market exploitation. Continue market push of different surface functionalized nanodiamonds for various applications. Hereunder especially the single-digit ND with D90 = 4.9 nm revealing Zeta potentials up to +68 mV developed under the AdEC project
• Industrial implementation of Si-doped DLC coatings
• Industrial implementation of W doped DLC coatings
• Product-near application-oriented projects in connection with further optimization of Si- and W-doped DLC coatings
• New R&D projects in connection with PEO treatment and commercial product near PEO treatments
• Product-near dispersion plating on commercial level
• More experiments concerning the Si-doped DLC-coated cylinder and piston capable at running at low O2/Fuel ratio without ceasing
• Commercial test facilities have been built up at AdEC RTD-partner Danish Technological Institute
The objective and the S/T results achieved in the different WPs has been summarized below.
WP2: Development of functional nano-particles
Progress summary towards objective:
The objective of WP2 was to improve the surface functionalization of nanodiamonds hereunder their dispersion and zeta potential to enable the development of a unique dispersion-hardened coating. The work also involved the optimization of the particle distribution, and pushes the costs down based on intelligent compromises concerning the size distribution of the used nanodiamond particles.
Results:
The first objective of WP2 was to optimize the surface functionalization of the nanodiamonds hereunder their dispersion and zeta-potential to result in a functionalized nanodiamond prototype. The purpose of producing the prototype is to enable the development of a unique dispersion-hardened coating. The development of the functionalized nanodiamond prototype has been carried out using two different kinds of Carbodeon’s proprietary technologies, namely surface re-functionalization and dispersion manufacturing technologies. The developed functionalized nanodiamond prototype is a highly zeta positive (up to +68 mV), essentially re-functionalized with hydrogen atoms only being fully aqueous soluble up to 5 wt.% nanodiamond. The developed nanodiamond material has been patented.
Plating tests have been conducted with the different types of nanodiamonds. The tested nanodiamond materials included a nanodiamond suspension uDiamond Vivace (nanodiamonds are in agglomerated form) and uDiamond Andante (the first generation nanodiamond dispersion, dispersion stable within pH range 3 to 6) and the highly zeta positive fully hydrogenated single digit nanodiamonds.
The second objective was an optimization of the price/value with respect to the performance of the dispersion-plated coating. It has been shown that the developed nanodiamond prototype can be applied in the nickel electrolytes without the need for ultrasonic treatments. The developed hydrogenated nanodiamond is thus much more stable and will not agglomerate improving the overall stability and economics of the process. A business plan has been developed and it is estimated that, with respect to Nikasil, the nanodiamond process will have equivalent costs at a nanodiamond content of 0.22 wt.%.
It was found that addition of nanodiamonds directly into the electrolyte provides an efficient method for making up industrially stable composite electrolytes. Furthermore, the hydrogenated nanodiamonds are highly dispersed and there is no need for ultrasonic agitation, which again makes it easier to implement on an industrial scale.
2 patents have been granted and 16 patent applications has been filed.
Task 2.1: Developing surface functionalization of nanodiamonds
Different surface functionalization chemistries will be elucidated to improve the dispersion of Carbodeon’s nanodiamonds. This task will be highly intertwined with WP3 enabling plating of second-to-none dispersion platings based on the developed surface functionalities.
Three types of nanodiamonds have been tested hereunder a developed nanodiamond type being fully terminated by hydrogen zeta positive (up to +68 mV), essentially re-functionalized with hydrogen atoms being fully aqueous soluble up to 5 wt. % nanodiamond content. The developed nanodiamond material has been patented.
Task 2.2: Price/value optimization with respect to the performance of the dispersion-plated coating
The particle distribution should be optimized in order to achieve the optimal dispersion plating with respect to the price. It is evident that the more narrow the size distribution and the more pure the nanodiamond suspension, the more expensive the product will be.
Based on the result obtained it will be possible to add the developed fully hydrogenated nanodiamonds directly into conventional electroplating formulations without changing the chemistry and without adding expensive ultrasound agitation equipment in order to prevent agglomeration. The developed hydrogenated surface formulation has been patented.
Deliverables:
D2.1) Preliminary results for nanodiamonds: Preliminary test results, indicating the possibility of finding the right surface functionalization of nanodiamonds [month 9, DONE on time, improved and re-submitted].
D2.2) Functionalised nanodiamonds: Optimal surface functionalization of nanodiamonds suitable for WP3
[month 12, DONE on time, improved and re-submitted with more results included].
D2.3) Results summary: Summary of results suitable for inclusion on organization website, press releases etc. excluding any results not yet protected [month 13, DONE on time].
WP3: Development of wet chemistry
Progress summary towards objective:
The objective of the work package on Wet Chemistry is to develop the chemistry and formulation of a new electroplating bath capable of dispersion plating a host matrix material containing different micro/nanoparticles. Evidently, both the co-deposited ceramic particles as well as the host matrix material will have to be stable under combusting conditions and the particles preferentially must reveal a high affinity to oil enabling lower friction properties. The selected particles to be embedded were guided by thermodynamic calculations.
Results:
A first generation of particles/matrix chemistry suitable for coating cylinder sleevings has been developed based on a scalable electrochemical dispersion plating system. To this chemistry various types of micro- and/or nanoparticles can be and have been added. Additionally, a first generation of an electroless dispersion plating system has been developed and tested with nanodiamonds as particle material.
The first generation of particles/matrix chemistry developed in the present project is based on a Ni sulphate electrolyte with the following composition: 500 g/L Scanimet Nickel Salt, 40 g/L boric acid, 40 g/L Scanimet SiC and 16.5 mL/L Scanimet TA. Based upon thermodynamic considerations and literature studies it was chosen to focus the experimental work with co-deposition of the following particles: Various types of nanodiamonds, SiC, Si3N4, B4C, BN, Ca2F and CeO2. These powders showed an acceptable affinity to oil (SiC and B4C) or offers good dry lubrication properties (CaF2 and BN). Prototypes of coated cylinders prepared with this first generation of particle/matrix chemistry have been produced. CaF2 and nanodiamonds (ND) are promising particles to provide better performance in wear resistance compared to conventional Ni-SiC-based coatings. A new type of hydrogenated diamond, which enables easier formation of a stable electrolyte, was tested. The performance of the resulting coating was comparable to the coatings obtained from an electrolyte containing the conventional nanodiamond dispersion named Andante. From an economical point of view, the amount of nanodiamond used must be optimised in order to limit the consumption and keeping the cost/benefit as high as possible. Results from engine tests show that the adhesion of the dispersion-plated Ni is critical. Two tests at Husqvarna revealed delamination and a third passed at Radne with similar performance as a standard engine. The ND test at DTI revealed good adhesion but increased wear. Additionally, a setup for deposition of a top layer of electroless plated Ni-diamond on a Nikasil coated Husqvarna cylinder was successfully developed. This new type of layer will be subjected to future engine field tests.
To the best of the knowledge of the consortium, the developed chemistry is beyond state-of-the-art in the following formulations:
• It is the first time that Carbodeon’s new type of nanodiamonds (Andante or hydrogenated nanodiamonds) has been incorporated into a nickel plating suitable for cylinders.
• It is the first time that BN and CaF2 have been incorporated into a nickel plating simultaneously being suitable for cylinder plating.
• A setup and chemistry for performing electroless plating of Ni-diamond on a Nikasil-coated Husqvarna cylinder were successfully developed.
• Temperature stability, friction coefficient, wear resistance, oil affinity of the developed platings have been elucidated.
• It is the first time engine cylinders have been plated at IPU.
• Plating knowledge and capabilities have been transferred to Carbodeon building up inhouse plating facilities.
Task 3.1: Selection of particle type and size with high-stability affinity to oil for cylinder wall
The task involves thermodynamic calculation of stability diagram for different nanoparticles. Among the considered parties were: SiC, Si3N4, B4C, BN, CaF2, CeO2 and nanodiamonds. Test platings were fabricated and the affinity to oil was characterized by wetting angle measurements. Hardness was measured both before and after heating. Friction properties were studied by pin-on-disk measurements.
Task 3.2: Selection of metal matrix for coating at cylinder wall or cylinder sleeving
This task deals with the selection of a suitable host material. The stability of the Ni-P-O and the Co-Ni-O systems was compared. Co3O4 can appear at the surface of a NiCo alloy coating. The Co3O4 is a unique compound, which has a spinel structure with a mixture of Co2+ and Co3+. The matrices of NiP and NiCo are therefore candidates to replace the Ni-matrix if a Ni-based coating does not offer better performance as compared to the current Nikasil coating.
Task 3.3: Developing of process technology for the plating engine cylinders
This task deals with the development of a dispersion plating process for both electrolytic and
electroless processes. The outcome of the word was electroless and electroplating processes including CaF2, BN, ND and SiC particles.
Deliverables:
D3.1) Preliminary chemistry: Preliminary configuration of the expected particle / matric chemistry [month 9, DONE on time, improved and re-submitted with more results included]
D3.2) Particle / matrix chemistry: Development of first generation of particle/matrix chemistry to use [month 12 DONE on time, improved and re-submitted with more results included]
WP4: Selection & Optimisation of Material for Piston
Progress summary towards objective:
The objective of WP4 was to find the optimal material combination for constructing an engine piston system with optimal efficiency improving the engine performance going beyond steel and aluminum. The use of e.g. Ti titanium for the piston material makes it possible to perform plasma electrolytic oxidation (PEO) of the substrate forming a thick wear-resistant coating consisting of TiO2 which might also involve the integration of ZrO2 in order to obtain a harder coating. This may also be combined with a suitable surface treatment like a metal nitride or wolfram carbide (WC) supported DLC coating deposited by PVD (WP5)
Results:
From an analysis of temperature stability, mechanical properties, availability and applicability of the materials to the PEO and PVD processes, it was together with the involved engine companies (Husqvarna and Radne) concluded to employ the aluminium alloys (M145 and M138) used by Husqvarna and Radne for the piston and cylinder, respectively, supplied by Mahle. For the piston rings it was suggested to use grey cast iron. However, unlike the pistons employed at Husqvarna and Radne, no Sn coating should be applied to the pistons prior to coating and the piston rings should not be phosphatised. These obstacles were solved.
Task 4.1: Selections of material for the piston ring
Aluminium alloy M145 and M138 was selected for the piston and cylinder and grey cast iron for the piston rings. Later a parallel tract was initiated working with titanium piston and piston rings.
Task 4.2: Selection and development of coatings for piston rings
A number of different coatings were developed and tested on aluminium pistons, grey cast piston rings, Ti rings and Ti pistons. PEO processes were developed and optimized for both Ti and Al base materials. In addition, PEO including ZrO2 doping was developed and demonstrated. New DLC coatings were developed for piston and piston rings and even used on the interior of the cylinder.
Deliverables:
D4.1) Choice of material for piston and ring: Preliminary report, with achieved scientific results for the search for the right materials for piston and piston rings [month 9, DONE on time, improved and re-submitted]
D4.2) PEO process: Development of PEO process [month 12, DONE on time]
D4.3) Integration of ZrO2: Integration of ZrO2 into the PEO process [month 18, DONE on time]
WP5: Development of DLC for piston
Progress summary towards objective:
The objective of WP5 was to develop a diamond-like carbon (DLC) coating that has a tailored interaction hereunder perfect low friction towards nanodiamond particles integrated into the dispersion-plated Ni or Co/Ni matrix. At the same time, it is mandatory that the DLC is temperature- stable enough to withstand the conditions inside a combustion engine.
Results:
The development has been optimised along two tracks creating an optimised W-DLC coating and Si-DLC coating. The aim was to develop DLC coatings with a higher temperature stability and at the same time low friction and, if possible, also low friction towards dispersion-coated nickel-containing nanodiamonds. The coatings have been characterized by Raman, SEM, XRD, adhesion, nano-indentation and RBS. Especially the Si-coating revealed high temperature stability, higher hardness and interesting friction properties evaluated both in an engine applications at Husqvarna and in pin-on-disk experiments in cooperation with Tekniker in Spain. The Si-doped DLC will be further perused and introduced as a product on the market.
The coatings have shown promising results at tests both at Husqvarna and at Radne. Both end-users are interested in perusing additional tests in order to provide further evidence of the beneficial use of coatings in two-stroke engines.
Especially the Si-DLC appears to have a market potential based on its interesting friction properties, higher hardness and stability at higher temperatures.
Task 5.1: Development of superior adhesion layer between DLC-coating and the underlying piston.
The task has addressed the development and optimization of a Si- and W-doped DLC layer on top of a base layer based on optimized CrN or WC. The adhesion was found to be very good.
Task 5.2: Development of tailored low-friction PVD DLC-coating
Different versions of especially the Si-doped DLC was characterized and selected for engine test at DTI, Radne and Husqvarna.
The friction coefficient of the Si-doped DLC has been compared by Tekniker in Spain and found to be lower than other in-house DLC references (e.g. DLC-TR (DLC and IBAD-DLC) sliding against Al2O3. The friction properties have not been evaluated against electroplated Nikasil or a dispersion-plated Ni coating containing nanodiamonds since the coating will be worn off when sliding a Ni-plated pin against a DLC-plated disk or vice versa. Nevertheless, the feedback from Husqvarna and Radne is a lowering of the friction when a DLC coated piston and piston rings are sliding against a standard Nikasil-plated cylinder in real engine tests.
Deliverables:
D5.1) Combustion engine conditions: Report describing the working conditions for piston and piston rings inside a combustion engine [month 9, DONE on time]
D5.2) Combined WC and DLC coating: First version of combined WC and DLC coating [month 18, DONE on time]
D5.3) Optimized DLC/WC coating: Optimized DLC/WC coating [month 24, DONE, delayed 2-3 months]
WP6: Field Test
Progress summary towards objective:
The main objective for this Work Package was to evaluate and verify the developed coatings in a realistic but controlled environment. Through various tests of standard and modified engines, the achievements should be compared. The primary test set-up will be based on laboratory configurations and will be compared with conditions used at Radne and Husqvarna.
Results:
This work package is dealing with test and evaluation of the fabricated coating (PEO, electroplating and DLC) in real engines. It was planned to test and evaluate the solutions both at DTI, Husqvarna and at Radne. A new test facility was planned to be constructed at DTI since the capacity at Husqvarna and at Radne for R&D tests was rather limited.
During the period, engine tests were made at DTI, Husqvarna and at Radne. The amount of tests at DTI was limited by several breakdowns, limited at Husqvarna due to capacity and limited at Radne due to the racing season.
When comparing all tests, it appears that the Si-DLC on worn-in piston is interesting, revealing according to Husqvarna a 3% lower friction. DLC-coated Ti-rings behaved surprisingly good and Ni-containing nanodiamonds failed in the runs at Husqvarna and showed similar performance at Radne. The Ni nanodiamond coating failed at DTI due to too high wear. PEO-treated standard piston coated with W-DLC did not reveal better performance. Interesting and promising results have been obtained when running a Si-DLC-coated cylinder against a worn in piston and worn in piston rings decreasing the fuel/air mixture to a lower value that normally possible. The CO level was lower and the temperature was lower which in principle should also lower the NOx level. Husqvarna has agreed to continue these experiments after project termination.
Task 6.1: Performance test
The engine performance is measured on computer-controlled dyno setup. Under this task, DTI constructed a new test facility, enabling test of two-stroke engines based on Husqvarna chainsaw. This task turned out to be significantly more complicated than anticipated and everything that could go wrong went wrong due to the extreme vibrations of the chainsaw at high RPM – besides there were a number of other delays and failures such as e.g.:
• The new dymo test unit was delayed
• When finally assembled, the first rubber-metal couplings for the driveshaft broke down
• The outlets for the emission measurement broke off several times
• The new dymo broke down and was sent for repair
• The top of the cylinder was too soft to be mounted again; it was cut off for facilitating homogenous electroplating
• New and more ridge heads were fabricated
• Sealing of the head failed and new aluminium gaskets were fabricated
• The chain saw broke down – a new was replaced by Husqvarna.
Nevertheless, the test team at DTI now has a test facility for two-stroke engines, and has learned how to solve and handle the above-mentioned issues.
Task 6.2: Wear / Life-time test
Based on the developed test-setup a number of plated pistons and cylinders were tested and the outcome of the tests were used to guide the developed electroplating. This worked very well in the last half year of the project.
Task 6.3: Real-Life-test
Different configurations of plated piston and cylinders were tested at Radne and also at Odder honing service. The conclusion from Radne is that the developed solutions perform nearly as a standard engine. If anything, the Si-DLC coated systems appear to have a lower friction. At odder honing service, all the pistons seized. This was most likely due to a too small tolerance between the piston and cylinder, when adding the DLC coating.
Deliverables:
D6.1) Test process description: A detailed plan for the test process must be made. [month 9, DONE on time]
D6.2) Graphical data: Graphical data showing performance, consumption and emissions of engines [month 16, DONE on time]
D6.3) Wear and real life test analysis results: Analytical report with wear and real life test results [month 24, DONE delayed 2 months]
WP7: Dissemination and Exploitation
Progress summary towards objective:
The main objective of WP7 was to ensure IPR protection of the obtained results and develop a business plan for the exploitable results, and ensure dissemination and publication of project results both internally in the project by educating the SMEs and, externally, for a wider audience.
Results:
The obtained results have been publicly disseminated at various locations:
1. Nordtrib 2014, DTI Aarhus, Denmark, 10th – 13th June 2014
2. ATV-Semapp, DTI Taastrup, Denmark, 17th February 2014
3. SUR/FIN 2014, Cleveland Convention Center, Ohio, USA, June 9th -11th (Electroplating Seminar)
4. SUR/FIN 2014, Cleveland Convention Center, Ohio, USA, June 9th -11th (Sustainability Seminar)
5. Materialica 2014, München, Germany, 21st -23rd October, 2014 (Electroplating Seminar)
6. Sur/Fin Asia-Pacific in Singapore, December 9th – 12th 2014.
7. The 13th European Vacuum Conference, Aveiro, Portugal, 8th -12th September 2014.
8. Kokkola Material Week, Kokkola City Hall, Finland, 23rd – 26th September 2014.
9. The 20th Small Engine Technology Conference & Exhibition, 11th -13th Pisa, Italy, November, 2014.
Besides, a number of exhibitions and fair trades have been visited by the project partners and a video presentation of the development has been produced.
Internal training has been performed at several of the project meetings (see the list in section 3.2.3) and especially the electroplating knowledge has been transferred to new in-house electroplating facilities built up at Carbodeon’s facilities in Finland through extended visits at IPU in Copenhagen.
Some project results have been protected through Carbodeon’s IPR portfolio and a report on this has been made including a business plan for entering the electroplating market by supplying the developed nanodiamonds. A list of potential exploitable results has been listed in deliverable 7.3.
The involved partners have identified the following exploitable results:
• Electroless dispersion plating of nickel-containing nanodiamonds (ND) at the in-house facilities at the Adec SME partner Carbodeon – focus on customer paid development and new R&D projects.
• Electroplating of nickel and chrome coatings containing nanodiamonds at in-house facilities at Carbodeon – focus on customer paid development and new R&D projects.
• Worldwide market exploitation. Continue market push of different surface-functionalized nanodiamonds for various applications. Especially the single-digit ND with D90 = 4.9 nm revealing Zeta potentials up to +68 mV developed under the AdEC project.
• Industrial implementation of Si-doped DLC coatings.
• Industrial implementation of W-DLC coatings.
• Product-near application-oriented projects in connection with further optimization of Si- and W-doped DLC coatings.
• New R&D projects in connection with PEO treatment and commercial product-near PEO treatments.
• Product-near dispersion plating on a commercial level.
• More experiments concerning the Si-doped DLC-coated cylinder and piston capable at running at low O2/fuel ratio without ceasing.
• Commercial test facilities have been built up at the AdEC RTD-partner Danish Technological Institute.
• Ongoing dissemination along the entire value chain from R&D to end-user level generating new business leads.
Task 7.1: Protection of project results
The developed, application specific nanodiamond dispersion was patented. A report has been generated listing title and abstract of filed patents. This overview contains 2 granted patents and 16 patent applications filed in the project period.
Task 7.2: Development of an Exploitation Strategy for exploitable results
All the identified exploitable results have been listed and filed in deliverable 7.3
Task 7.3: Identifying financial opportunities for supporting post-project activities
Carbodeon, DTI and IPU have in the project period submitted one EUROSTARs application, which failed. This will most likely be re-submitted in the September 2015 round. Carbodeon, DTI and IPU are working closely together and the team is quite positive that they will find suitable funding for continuing the work. Especially Husqvarna is interested in continuing the close cooperation in the future.
Task 7.4: Dissemination of project results
The project has been disseminated at 9 occasions and a project video has been made and uploaded on the website (http://www.adecoating.dk/project-results.aspx). Hereto comes a number of trade fairs, where Carbodeon has displayed their nanodiamond portfolio.
Task 7.5: Internal dissemination of project results and training of SME partners in the use of them
Task Leader: CHROM
Dissemination and training have been conducted and aligned with several project meetings but also through dedicated and extended visits especially by Carbodeon at IPU.
Deliverables:
D7.1) Website: External and internal project website to be updated every 3 months [month 3, DONE on time]
D7.2) Interim Plan for use and dissemination of knowledge: [month 9, DONE on time]
D7.3) Final plan for use and dissemination of knowledge: [month 22, DONE delayed 4 month]
D7.4) Business Plan: Business plan for each exploitable result [month 20, DONE delayed 7 months]
D7.5) Public dissemination: After protection - public dissemination of scientific and commercial results [month 22, DONE delayed 3 months]
D7.6) Internal dissemination and training workshops: [month 24, DONE report delayed 2 months]
D7.7) Video presentation: [month 22, DONE delayed 2 month]
________________________
Concerning the milestones, the following can be summarized:
MS1: Project go/no go (month 9)
Decision based on deliverables. Based on the obtained results – especially the development of functional diamonds, electroplating results and DLC results - it was decided by the consortium to continue the development
MS2: There is no MS2
MS3: Functional nanodiamonds (month 24)
On shelf available product suitable for large-scale dispersion plating
Fulfilled
Carbodeon has increased the portfolio of ND with a new fully hydrogenated version
See e.g.: http://www.carbodeon.net/index.php/en/nanomaterials/udiamond-liquid-dispersions/udiamond-hydrogen-d-2nd-gen
MS4: End user plating (month 24)
Final prototypes plated at end-user site
Fulfilled: Final prototype plated and report on MS4 has been sent to project officer.
MS5: WC/DLC onto PEO (month 16)
Demonstrator comprising WC/DLC onto PEO-treated Ti piston rings
Fulfilled: Demonstration comprising WC/DLC made and report on MS5 has been sent to project officer.
MS6: WC/DLC on ZrO2 doped PEO (month 18)
Demonstrator comprising WC/DLC on ZrO2-doped PEO-treated Ti piston rings
Fulfilled: Demonstrator ZrO2-doped PEO-treated Ti piston rings and report has been sent to project officer.
MS7: End-user test DLC/WC coating (month 18)
First DLC/WC coating
Ready for test at end-users
MS8: Production ready DLC/WC coating (month 18)
First DLC/WC coating ready for test at end-users
Fulfilled: DLC/WC coating has been delivered for test at end-user
MS9: Test set-up described (month 4)
Test set up for performance and real time test described
Fulfilled: Test protocol has been written
MS10: Real time tests (month 24)
Conclusion on wear and real time tests
Fulfilled: Conclusion is included in report D6.3
MS11: Protection of project breakthroughs (month 20)
Relevant documents
Fulfilled: Report on IPR protected results has been written and sent to project officer
MS12: Business plans (month 20)
Business plans for Execution
Fulfilled: Business plan written for nanodiamonds and submitted as D7.4
Potential Impact:
Potential Impact and exploitation of results:
This section will highlight some of the ongoing actions pin-pointed by the consortium concerning exploitation of the obtained results.
Electroless dispersion plating:
Carbodeon is continuously exploring potential market possibilities for nano diamonds. As shown in the business plan in delivery D7.4 Carbodeon is targeting the electroless plating market – especially with the developed Single Digit (SD) hydrogen terminated nano diamonds. The electroless market is expected to be smaller than the 13.6 B$ large electroplating market. With the knowledge achieved within this project concerning electroplating, Carbodeon has built its own plating facilities in order to be able to fabricate demonstrators and perform test-coatings for customers. In the area of Electroless dispersion plating the focus is on customer paid development and new R&D projects to generate market access.
Electroplating of nickel and chrome coatings containing ND:
The maket potential for electroplating is significantly larger than electroless plating. The development of electroplated nickel with embedded nano diamonds performed in the AdEC project has opened up to companies such as e.g. Atotech, Coventia, CCT, Bales Mold and several others which Carbodeon is currently in direct negotiation with. Hereto comes additional companies that are interested in adding nano-diamonds into their chrome chemistry (both chrome +VI and +III). The dialogue with these and other companies is ongoing. The scientific development and the demonstrators made within the AdEC project is a very important prerequisite when initiating a dialogue with potential customers.
Worldwide market exploitation of nano diamonds:
Carbodeon is continuously exploring industrial use of nano diamonds both in electroplating and electroless plating as mentioned above but also in connection with other industrial applications such as thermal management, improved performance of polymers, scratch resistant surfaces, etc. The IPR portfolio has expanded during the project period as reported in MS11: Protection of Project breakthroughs. In the coming 2-3 years, it is expected that the hydrogen-terminated single-digits 4-6 nm large ND will make several commercial successes both in connection with electroplating but also in connection with e.g. thermal management issues in electronics. Focus is direct customer visits facilitated by agents, ongoing market dissemination through exhibitions/fairtrades etc. primarily in USA and Asia.
Industrial implementation of Si-doped DLC coatings:
The developed Si-doped DLC has been coated both on the piston, the piston rings as well as on the inside of the cylinder (see deliverable 5.3: Optimized DLC/WC coating and deliverable 6.3: Wear and real life test analysis results). The Si-doped DLC-system deposited on the piston, the piston rings and the cylinder, was tested at DTI revealing surprising performance at high O/fuel-ratio where the piston-cylinder normally would cease – this did not happen. Apparently, it is possible to run the coated piston/cylinder system at these much higher O/fuel-ratios without crashing the engine and even achieving a lower wall temperature. Running at a higher O/fuel ratio at a lower temperature is expected to generate less NOx. This hypothesis will be further tested together by Husqvarna, which is very interested in these new findings.
In addition, the Si-DLC is also interesting due to the improved stability at higher temperature.
The friction properties of the Si-DLC coating has been investigated together with Tekniker in Spain. The performance of the new Si-DLC is also interesting from its better friction properties. Danish Technological Institute is currently exploring possible ways to get the DLC tested in other industrial applications.
Industrial implementation of W-doped DLC coatings:
After successfully market introduction of the Si-doped DLC, it is the aim to find support for a development project on the W-doped DLC as a second priority.
PEO treatment of Al, Ti and Mg:
The Adec RTD partner IPU will utilize the build up PEO (Plasma Electrolytic Oxidation) treatment facilities to engage in both commercial development projects involving companies and R&D-project based on improved PEO treatment hereunder also doping with e.g. ZrO2 in the PEO treatments. Based on the AdEC project, IPU has gained experience in PEO treatment of Al, Ti and even Mg.
Commercial dispersion plating:
IPU has gained knowledge in dispersion plating based on both electroless and electroplating involving particles of nano diamonds, CaF2, NB, SiC. This knowledge and expertise will be made available on a commercial level.
Ongoing test at Husqvarna:
More engine tests are being made concerning the Si-doped DLC coated cylinder, (piston and piston rings) capable at running at low fuel to air ratio without seizure. Husqvarna has agreed to continue these experiments after project termination
Commercial motor test at DTI:
Danish Technological Institute has buildup test facilities for two-stroke engines within the AdEC project. Small engine- and emission testing will be made commercially available.
SME partners:
Both SME partners, Radne Motor AB and Å.K. Chrom A/S, are positive to the results achieved and disseminate the results within their different market scopes: Cart Racing engines and electroplating of surfaces in industrial applications. The higher engine performance achieved due to lower friction and the potential lower emissions draws attention within the engine community of cart racing. Within industrial applications surface treatments Å.K. Crom find interest from the market in treatment which can substitute the present Nikasil application. Within both the markets that the SME Adec partners are facing the dissemination is ongoing and gaining attention.
Dissemination:
Dissemination activities has been divided into external dissemination activities and internal teaching and dissemination activities.
External/open dissemination activities:
The AdEC Consortium participants have presented highlights generated by the AdEC project on a number of occasions during the project period of January 2013 to December 2014.
In summary, the public dissemination of AdEC objectives and preliminary results conducted, amounts to seven oral presentations where project partners have presented results from the project.
1. Nordtrib 2014, DTI Aarhus, Denmark, 10th – 13th June 2014
2. ATV-Semapp, DTI Taastrup, Denmark, 17th February 2014
3. SUR/FIN 2014, Cleveland Convention Center, Ohio, USA, June 9th -11th (Electroplating Seminar)
4. SUR/FIN 2014, Cleveland Convention Center, Ohio, USA, June 9th -11th (Sustainability Seminar)
5. Materialica 2014, München, Germany, 21st -23rd October, 2014 (Electroplating Seminar)
6. Sur/Fin Asia-Pacific in Singapore, December 9th – 12th 2014.
7. The 13th European Vacuum Conference, Aveiro, Portugal, 8th -12th September 2014.
8. Kokkola Material Week, Kokkola City Hall, Finland, 23rd – 26th September 2014.
9. The 20th Small Engine Technology Conference & Exhibition, 11th -13th Pisa, Italy, November, 2014.
Besides these presentation a number of exhibitions and fair trades has been visited by the project partners and a video presentation of the development has been produced.
Below is summarised presenters of the AdEC-project objectives and preliminary results on the above-mentioned occasions.
1) Nordtrib 2014:
The 16th Nordic Symposium on Tribology - NORDTRIB 2014
Place and date: Danish Technological Institute, DK-8000 Aarhus, June 10th – 13rd
At the Nordtrib 2014, held in Aarhus at The Danish Technological Institute and at the Congres Center, the AdEC-partner IPU, presented a paper authored by the project participants Anette Alsted Rasmussen, Io Mizushima and Per Møller: “Investigation on frition properties of nickel ceramic electrodeposits”. The key issues presented were electrodeposits on cylinder wall coating, friction, wear, lubricant and oil affinity.
The presented content were results optained through the AdEC-project WP 4 and 5. The ADEC-project was duly acknowledges at the presentation and the within the paper text.
The NORDTRIP symposium is held biennially since 1984 in one of the Nordic countries: Finland, Sweden, Norway and Denmark. The Symposium is a highly regarded venue for the international tribology community. NORDTRIP is intended as a forum where researchers and developers from universities, research institutes and industry can present their latest contributions and discuss field-related issues.
2) ATV-SEMAPP
ATV-SEMAPP conference on Friction and Lubrication
Place and date: Danish Technological Institute, DK-2630 Taastrup, February 17th 2014
At the ATV-SEMAPP conference «Friction and Lubrication», a paper on the AdEC project objectives and application of «Diamond-Like Carbon (DLC) – a family of self-lubricating low-friction surfaces» were present by AdEC WP5 leader Sascha Louring.
Danish Academy of Technical Sciences (ATV) is an independent institution which aims at furthering technical and scientific research. ATV also aims at ensuring the application of research results in order to increase wealth and welfare in Danish society. SEMAPP is one of several sociaties attached to the ATV. It focuses on Engineering Manufacturing Techniques in Process and Production.
3)+4) SUR/FIN Manufacturing & Technology Trade Show & Conference 2014
Place and date: Cleveland Convention Center, Ohio, USA June 9-11, 2014
At the Electroplating Seminar of the conference, the AdEC WP2 leader Carbodeon’s US sales agent presented a paper by Niko Rostedt entitled: «Coatings with improved properties using detonation nanodiamonds as plating additives».
At the Sustainability Seminar of the conference, the AdEC WP3 and WP4 technical manager Per Møller presented at paper on “A Comprehensive Look at Surface Finishing & Its Processes: Advanced Surface Technology, Volumes I & II - Per Møller and Lars Pleth Nielsen”. The oral presentation included results form the ADEC project.
SUR/FIN Manufacturing & Technology Trade Show & Conference is an annual three day event aiming at surface finishing professionals to the industry’s best business opportunities, latest innovations and most influential leaders.
5) Materialica 2014, München, Germany, 21st -23rd October, 2014 (Electroplating Seminar)
At the Trade Fair the AdEC WP2, WP3 and WP4 participant Niko Rostedt of Carbodeon Ltd, Finland, showed there product portfolio.
6) Sur/Fin Asia-Pacific
Place and date: Singapore, 9th – 12th December 2014
At the conference, Electro-plating session, the AdEC WP2, WP3 and WP4 participant Niko Rostedt of Carbodeon Ltd, Finland, presented a paper on “Improving the wear resistance of electroless Nickel coatings using detonation nano-diamonds”.
Sur/Fin Asia-Pacific is a bi annual exhibition and conference jointly organized by National Association for Surface Finishers (NASF) of USA and Singapore Surface Engineering Association (SSEA) with the support of National University of Singapore (NUS), Singapore Institute of Manufacturing Technology (SIMTECH) and other organisation.
7) The 13th European Vacuum Conference and 7th European Topical Conference on Hard Coatings
Place and date: Aveiro, Portugal on September 8th -12th 2014
At the conference, the AdEC coatings were presented at the Surface and Structure session on September 11th 2014 in a paper titled: “Tribological behavior of DLC coatings for vacuum applications” by Edurne Berriozabal, Amaya Igartua, of Fundación Tekniker, Eibar, Spain and the AdEC coordinator Lars Pleth Nielsen of Danish Technological Institute. The presentation included Si-DLC coatings developed in the ADEC project discussing friction and wear of DLC coatings.
The annual European Vacuum Conference commenced in 1988 as an off-spring of International Union for Vacuum Science, Technique and Applications (IUVSTA). Throughout the Europe region, it gathers numerous vacuum societies in a joint conference matching the American Vacuum Society’s annual symposium in the USA. EVC provides a useful and well-supported forum for scientists based in Europe to exchange latest data in vacuum technology and vacuum-related science.
8) Kokkola Material Week
Place and date: Kokkola City Hall, Finland, 23rd – 26th September 2014
At the conference, Carbodeon’s Business Development consultant Gavin Farmer of WP2, WP3 and WP4, presented a paper on: “Improving the Wear Resistance of Electroless Nickel Coatings Using Detonation NanoDiamonds”, at the session of MetalKokkla focusing on New functional and protective coatings, one of the six session themes.
Kokkola Material Week is an annual conference focusing on innovation and covers everything from education and basic research to R&D and commercialization services for businesses.
This is the opportunity for business developers and scientists to network and learn more about material science within six thematic sessions. In 2014 these were: Biobased products, Nanotechnology, Greener solution for industry, Leather production methods, New functional and protective coatings and Reuse/recycling though industrial symbiosis.
9) Small Engine Technology Conference & Exhibition
Place and date: Palazzo dei Congressi; Pisa, Italy, November 11th -13th 2014
At the 20th SETC conference, the AdEC WP6 participant Mikael Bergmann of Husquarna, presented Paper no 14SETC-2014-09-27 entitled: «Advanced Low Friction Engine Coating Applied to a 70cc High Performance Chainsaw».
The annual SETC Conference and Exhibition circulates between Asia, Europe and the United States. The conference and exhibition offers up-to-date information on the state of the economy and the status of emission regulations, alternative powertrains and the effects on the environment.
The vehicle product ranges from ATVs, scooters and motorcycles to portable power generators, lawnmowers and hand tools. We will be discussing the challenges and developments in small engine technology from OEMs, suppliers and academia from around the world.
Video
A video has been produced summarizing the development made within the AdEC project. The video will be made available on all the partners’ website: www.adecoating.dk. The video is also part of the deliverable D7.7.
Internal training and dissemination:
During the duration of the project, twelve internal dissemination and training workshops have been held all at the premises of the project participants. Five of these in conjunction with the formal Consortium Management Meetings.
At the scheduled consortium meetings, it was agreed from the project start, that each occasion should last for two days allocating the first day to internal dissemination of the project results and informal discussion on work, planning and procedures while the second day has been allocated for the formal decision making session including sufficient time for discussing, training and cross-fertilisation.
SME – RTD Crossfertilisation:
The project has embraces three SME and two RTD partners from whom the processes of applying DLC and results of surface treatments have been disseminated.
The project participant of SME Carbodeon have been working at the IPU lab for longer periods on four occasions during 2013 in order to learn how to make electroplating and especially dispersion plating incorporating nano diamonds into nickel. The periods included both teaching and training in electroless nickel and electroplating of nickel, pre-treatment, anode configuration, etc. The outcome has produced cross-fertilisation on plating knowledge and ND for both the SME and the RTD partner on how nano-diamond containing nickel based coatings can be apply for the project purpose using wet chemistry. The cross-fertilisation have been so successfully that Carbodeon has set up their own inhouse plating line.
IPU and the SME ÅK Chrom have on two occasions discussed the process of substituting Nikasil with nano diamond containing nickel in the industrial environment at ÅK Chrom and at the IPU Lab premises. ÅK Chrom’s upscaling experience has been made available for the consortium and especially IPU and Carbodeon have discussed technical issues concerning upscaling strategies.
Online sessions have been further elaborated by video-conference, skype meetings on progress and problem resolution.
The book Advanced Surface Technology written by Dr. Lars Pleth Nielsen (DTI) and Prof. Per Møller (DTU) have at several locations been used as teaching and training material.
Husquarna and SME partner Radne have both received a high number of DLC treated motor parts (piston, piston rings and even cylinders) from the RTD partners as well as electroplated cylinders as result of the RTD work performed, i.e. cylinders, pistons and rings for testing at their facilities. Husquarna and Radne has learned a lot about while, demonstrating the effect of low friction engine coatings in combination with standard Nikasil plated cylinders as well as new and novel nickel plating with imbedded nano diamonds and CaF2, BN, SiC particles and mixtures hereof. DTI has also provide for profound motor lab tests according to plan and in charge of WP6 motor testing building up a new test facility based on training and knowledge flow from Husquarna and Radne to DTI. The outcome has provided valuable results and learnings, which can be applied by the SMEs and also for the RTD partners to adjust parameters in the ongoing development of new and even better performing DLC coatings and electroplated solutions.
List of project meetings, dates and venues including internal training and dissemination:
The following list provides the number of occasions, where the project participants have physically met during the project period.
17th January 2013, DTI, Aarhus, Denmark
29th January, Chrom, Aarhus Denmark
21th February 2013, Radne, Sweden
13th May 2013, IPU, Denmark
18th February – 1st March – 2013, IPU, Denmark
18th – 22nd March 2013, IPU, Denmark
27th – 31st May 2013, IPU, Denmark
26th – 28th August 2013, IPU, Denmark
12th August 2013, Husquarna, Sweden
13th August 2013, Husquarna, Sweden
3rd December 2013, IPU, Denmark
4th December 2013, IPU, Denmark
13th May 2014, DTI, Denmark
14th May 2014, DTI, Denmark
20th August 2014, IPU, Denmark
21st August 2014, IPU, Denmark
3rd December 2014, Carbodeon, Finland
Exploitation Results
The following IPR has been generated:
US2014/0091253A1: Nanodiamonds containing thermoplastic thermal composites
US2014/0094546A1: Fluoropolymer coatings
The following patent applications has been filed:
WO 2013135305 A1: Detonation nanodiamond material purification method and product thereof
PCT/FI2013/050947: Nanodiamonds containing thermoplastic thermal composites
US 14/141779: Nanodiamonds containing thermoplastic thermal composites
PCT/FI2013/050947: Fluoropolymer coatings
US 14/041621: Fluoropolymer coatings
FI 20136324: Nanodiamond Containing Composite and Method for Producing the Same
JP 2013-272919: Nanodiamond Containing Composite and Method for Producing the Same
US 14/141779: Nanodiamond Containing Composite and Method for Producing the Same
List of Websites:
The project has established a homepage at the website http://www.adecoating.dk
A video presentation over the project has also available at the website (http://www.adecoating.dk/project-results.aspx).
The main contact persons behind the project and their organizations details are summarized below:
Partner 1:
Director Lars Pleth Nielsen
Danish Technological Institute (DTI)
Kongsvang Alle 29
DK-8000 Aarhus
Denmark
E-mail: lpn@teknologisk.dk
Phone: +4572201585
Web: www.teknologisk.dk
Partner 2:
CEO: Kim Sørensen
ÅK Chrom
Axel Kiers Vej 38
DK-8270 Højbjerg
Denmark
E-mail: info@aak-chrom.dk
Phone:+45 8629 6788
Web: www.aak-chrom.dk
Partner 3:
CEO Vesa Myllymäki
Carbodeon Ltd. Oy
Pakkalankuja 5
01510 Vantaa
Finland
E-mail: vesa.mylymaki@carbodeon.com
Phone: +358 50 555 9066
Web: www.carbodeon.net/index.php/en/
Partner 4:
CEO Leif Radne
Radne Motor AB
Markörgatan 2
SE-136 04 Hanninge
Sweden
E-mail: leif@radne.se
Phone: +46 8556 506 90
Web: http://www.radne.se/
Partner 5:
Project Manager Mikael Bergman
Husqvarna AB
SE-561 82 Huskvarna, Sweden
E-mail: mikael.bergman@husqvarnagroup.com
Phone: +46 7307 440 86
Web: http://www.husqvarna.com/us/home/
Partner 6:
Group manager Anette Rasmussen
IPU Technology Development
DK-2800 Kgs. Lyngby
Denmark
E-mail: aar@ipu.dk
Phone: +45 45 25 22 12
Web: http://www.ipu.dk/
The consortium behind the AdEC project (Advanced Low Friction Engine Coatings) has developed and implemented state-of-the-art surface technologies, improved existing advanced coating processes with the aim of increased two-stroke engines performance by the incorporation of coatings on piston, piston-rings and cylinder wall.
The partner focus was along the value chain spanning the entire way from the development of novel surface functional nano diamonds (Carbodeon), electroplating (AK Chrome, IPU, Carbodeon), coating and surface treatment based on Plasma Electrolytic Oxidation - PEO (IPU) and vacuum based thin film coatings (DTI), test and validation at lab-scale (DTI) to field test involving end-users (Husqvarna and Radne).
Development of nano diamonds fully re-functionalized with hydrogen atoms has been carried out. These highly zeta positive (+68 mV) nano diamonds are aqueous soluble up to 5 wt. %. The development nano diamonds have been IPR protected in 2 granted patents and 16 patent applications.
Dispersion plating based on both the developed nano diamonds and mixtures of nano diamonds, hexa-boron nitride (BN), CaF2 and traditional Nikasil (SiC) has been developed.
A number of different plasma electrolytic conversion coatings were developed and tested on aluminium pistons, Ti rings and Ti pistons. PEO processes were developed and optimized for both Ti and Al base materials. In addition, PEO including ZrO2 doping was developed resulting in higher hardness.
Si- and W-doped DLC coatings, which can tolerate higher temperatures, have been developed. The coatings have been characterized by Raman, SEM, XRD, adhesion, nano-indentation and RBS. The coating has been tested on piston and piston rings revealing a lower friction and allowing to run the engine in a configuration where the engine would normally seizure with significant reduction of the cylinder temperature to below 270 oC. Based on dyno tests at Husqvarna the friction has been found to be ~3% better.
In house plating facilities has been built at one of the consortium SME participants (Carbodeon).
All dispersion nickel-plated solutions based on nano diamonds, CaF2 or BN coated cylinders have only revealed same performance or marginally better as compared to reference piston, piston-rings and cylinder systems.
The results have been published in one article and disseminated at a number of conferences and trade fairs. A video presentation is made it is viewable at the ADEC website (http://www.adecoating.dk/project-results.aspx).
Project Context and Objectives:
The major research objectives are organised in five areas, corresponding to the structure of the project:
1. Development of Functional Nano-particles, aiming to improve surface functionalization of nanodiamonds including their dispersion and zeta-potential to enable the development of a unique dispersion hardened coating of engine component surfaces. The work will also optimize the particle distribution and push the costs down based on intelligent compromises concerning the size distribution of the used nanodiamond particles.
2. Development of Wet Chemistry and formulation of a new electroplating bath, capable of dispersion plating a host matrix material, containing different nanoparticles. A key focus in this context is that both the embedded ceramic particles as well as the host matrix material will have to be and remain stable under combusting conditions.
Further, it is the objective to improve the performance if the particles reveal a high affinity to oil enabling lower friction properties. The materials are selected upon thermodynamically consideration to avoid thermochemical reactions with the selected ceramic particles and degradation of the host metal matrix.
3. Selection & Optimisation of material for piston has the objective to develop the optimal material combination for constructing an engine piston system having optimal efficiency. Historically, steel and aluminium have been chosen but also magnesium has been suggested for the piston rings. Due to thermal management, it is important to work with materials with small or matched thermal expansion coefficients, while the materials must have sufficient wear resistance.
Selection of titanium for the piston material makes it possible to perform Plasma Electrolytic Oxidation (PEO) of the substrate forming a thick wear resistant coating consisting of TiO2 which might also involve the integration of ZrO2 in order to obtain a harder coating. This may also be combined with a suitable surface treatment like a metal nitride or Wolfram Carbide (WC) supported Diamond-Like-Carbon (DLC) coating deposited by Physical Vapour Deposition (PVD).
Combining optimized materials and coatings in a new way will most probably enable the development of engines of the future having a much higher durability and with much lower friction properties, which will lead to engines with superior fuel efficiency.
4. Development of Diamond-Like-Carbon (DLC) for piston coating that has a tailored interaction hereunder perfect low-friction towards nanodiamond particles integrated into the dispersion plated Ni or Co/Ni matrix. A major requirement (mandatory) is that the DLC is temperature stable enough to withstand the conditions inside a combustion engine.
5. Field tests are made to evaluate and verify the developed coatings in a realistic and controlled environment. Through various tests of standard and modified engines, the achievements towards the objectives are to be compared. The primary test set-up, will be laboratorial, where electronic and calibrated equipment will be used for registration and logging of measured data. Subsequently, real time, on-road test under various conditions will be included for all engine applications.
The overall success criteria can be summarised as:
Reduce cylinder wall temperature:
Si-doped DLC coatings have been developed which can tolerate higher temperatures. The coating has been tested deposited on piston, piston rings and tested both at DTI, Husqvarna and Radne. Husqvarna reports improved friction properties, and lower temperature, whereas Radne concludes that it is only marginally better. DTI reports that it is possible to run the engine in configurations where the engine would normally seizure with significant reduction of the cylinder temperature to below 270 oC.
Lower engine weight by allowing alternative materials:
The project has developed Ti-piston, Ti piston rings and Mg-piston to test the performance of alternative materials. Ti-rings have been tested and have shown to seize. However, Si-DLC coated Ti-rings behaved surprisingly well.
The one-one copy of the aluminum piston made in Ti-piston was too heavy to be tested.
Ti-rings and Ti-piston have been PEO-treated and PEO-ZrO2-doped.
Increase in the obtainable power by op to 20 %:
All tested solutions, ND-Ni coatings, CaF2, or BN coated cylinders, DLC-coated piston and piston rings have only revealed same performance or marginally better. Based on dyno tests at Husqvarna it was found to be ~3% better. It has not been possible to obtain a power increase of 20 %.
Improved fuel economy by more than 20 %:
Lower friction will increase the fuel economy, but 20 % is beyond what is feasible.
Lowering of oil consumption:
The tests performed with improved Si-DLC have shown that it is possible to run the engine under conditions where it will otherwise seize. This might open up for running the 2-stroke engine with a lower oil content in the fuel in the future.
Improved scuff and wear resistance on cylinder bores, piston and piston rings:
- Si-DLC coated pistons show that there is no scuffing for a DLC coated piston.
- Reduced friction:
- The Si-DLC coated piston has revealed lower friction.
Lower CO2, NOx and soot/particle emission:
Lean out of the engine will give less soot/particle formation. The addition of Si-DLC to the piston, piston rings and cylinder has revealed that it is possible to run the engine at much more lean condition. This will give rise to less NOx. Hereto comes that the lower temperature caused by less friction (heat) will also give less NOx. CO2 is linked to fuel consumption, which will be lower due to less energy going to friction. However, experiments only indicated marginally improved performance.
Improve the lifetime of the engine parts:
There is no indication of significantly improved lifetime of the different engine parts tested.
Enable the use of alternative lightweight materials such as e.g. Zr-doped alumina inside the engine:
The project has successfully developed PEO and Zr-doped PEO. The PEO-treated pistons have been tested with poor performance caused by narrow prison ring grooves. Also the temperature and friction were observed to increase due to narrow tolerances. Further improvement is needed.
Project objectives for the period:
The project has worked along 9 objectives and the result of these tracks are summarized below:
Objective 1: To develop functional micro or nanoparticles based on different compositions such as BN, functionalized nanodiamonds (ND) providing non-agglomeration capabilities and a developed high affinity to lubricants by adjusting their zeta potential.
Nanodiamonds with improved dispersion have been developed creating products free of agglomerates aligned with plating-relevant chemistries. Less agglomeration and improvement is obtained in the deposited products and the developed coatings’ technical performance is better than those with previous generation nanodiamond additives, seen in the literature. Moreover, due to improved dispersion stability, the coatings’ enhanced performance is now available with a fraction of nanodiamond additive loadings into the applied nickel electrolyte. Adjustable zeta potential of the ND has been done and proven. No major improved affinity for oil could be identified/documented. This might be linked to the very low nanodiamond concentrations applied in the developed coatings.
The developed ND formulations and surface hydrogen activation have been patented and marked exploration is in progress both in the field of electroplating but also alternative applications are investigated.
Objective 2: Arrive at a minimum cost-performance ratio for the nano-particle-coating targeting to be 10-20 % cheaper than existing technologies but at the same time outperforming the existing technologies by tailoring the purity and a size distribution of the involved nanoparticles.
It is estimated that nanodiamond-containing nickel can be made comparable or even cheaper than existing Nikasil technologies. This is of course dependent on the needed content of nanodiamonds. Breakeven compared to conventional Nikasil is found for a ND content around 0.22 wt. %. The wet chemistry has been optimized and ND can be incorporated into electroplated and electroless nickel.
Objective 3: Selection of materials for piston manufacture with thermal expansion coefficients to minimal mitch match and better than currently applied materials.
Work has been made on titanium. Titania rings work surprisingly good when they are DLC-coated. A fabricated Ti-piston was PEO-treated but was found too heavy to be tested.
Normal rings coated with TiN -> gave more wear. Zr-doped PEO treated aluminium piston coated with a hereto developed Si-DLC worked, but not as good as a standard piston-cylinder configuration.
Objective 4: Development of a scalable electrochemical plating system based on dispersion plating of Co/Ni with embedded nanocrystals.
Scalable plating technology and chemistry has been developed towards incorporation of nanodiamonds (ND), CaF2 and BN. Plating of test items and cylinders has been performed.
Objective 5: Tailored DLC coating with improved adhesion through a nanodesigned WC adhesion layer. Overall with improved adhesion and temperature resistance.
New types of DLC and WC supported DLC have been developed. Increased performance and increased temperature stability have been obtained. The results are very promising and will be followed up beyond project termination.
Objective 6: Elucidation of possible improvement through plasma-electrolytic oxidation and doping with Zr.
PEO of Al, Ti and Mg has been developed, and test samples of pistons and rings have been performed. ZrO2 doping during the PEO-treatment has been developed and it is shown that the addition of ZrO2 increases the hardness even further.
Objective 7: Overall engine performance with the new coatings of 5-10% increase in the dynamic/static power.
A new DLC has been developed and tested and was found to be 3% better – based on analysis of dyno tests.
Objective 8: Carry out thermodynamic calculations for constructing of predominance diagrams, with respect for selecting best combination of metal matrix and particle combination for designing coatings for high-temperature combustion processes in engines.
Thermodynamic evaluations of the metal matrix and particle system have been performed, and a number of metal matrix and particles combinations were found to be candidates for further development. It was decided to focus on BN, CaF2 and nanodiamonds in a Ni matrix.
Objective 9: Evaluation of surface functionalization of particles by modifying surfaces on nano-by grasping with different molecules to make them active in the electric field.
Different surface-functionalized nanodiamonds have been fabricated generating different zeta potentials by changing the surface charge. This resulted in less agglomeration in the acidic electrolyte.
Objective 10: Develop dispersion models based upon Ni, Co or Co/Ni plating based on nanodiamonds and/or BN.
Different electroplating parameters were investigated for Ni hereunder the particle content and the nickel chemistry, current density and temperature. The formulation was demonstrated for BN, nanodiamonds and CaF2.
Project Results:
The focus of the AdEC project was to develop and implement state-of-the-art surface technologies and improve existing advanced coating processes focusing on Ni-Co based dispersion coatings containing a mixture of nano-diamonds and hexa-boron nitride (BN) and develop improved solutions in relation to especially two-stroke engines at Husqvarna and Radne. This development was broken down into a number of work packages:
WP2: Development of functional nano-particles
WP3: Development of wet chemistry
WP4: Selection & Optimisation of Material for Piston
WP5: Development of DLC for piston
WP6: Field Test
WP7: Dissemination and Exploitation
The overall success criteria in the DOW can be summarised as:
Reduce cylinder wall temperature:
Si-doped DLC coatings have been developed which can tolerate higher temperatures. The coating has been tested deposited on piston, piston rings and tested both at DTI, Husqvarna and Radne. Husqvarna reports improved friction properties, and lower temperature, whereas Radne concludes that it is only marginally better. DTI reports that it is possible to run the engine in configurations where the engine would normally seizure with significant reduction of the cylinder temperature to below 270 oC.
Lower engine weight by allowing alternative materials:
The project has developed Ti-piston, Ti piston rings and Mg-piston to test the performance of alternative materials. Ti-rings have been tested and have shown to seize. However, Si-DLC coated Ti-rings behaved surprisingly well.
The one-to-one copy of the aluminum piston made in Ti-piston was too heavy to be tested.
Ti-rings and Ti-piston have been PEO-treated and PEO-ZrO2-doped.
Increase in the obtainable power by op to 20 %:
All tested solutions, ND-Ni coatings, CaF2, or BN coated cylinders, DLC-coated piston and piston rings have only revealed same performance or marginally better. Based on dyno tests at Husqvarna it was found to be ~3% better. It has not been possible to obtain a power increase of 20 %.
Improved fuel economy by more than 20 %:
Lower friction will increase the fuel economy, but 20 % is beyond what is feasible.
Lowering of oil consumption:
The tests performed with improved Si-DLC have shown that it is possible to run the engine under conditions where it will otherwise seize. This might open up for running the 2-stroke engine with a lower oil content in the fuel in the future.
Improved scuff and wear resistance on cylinder bores, piston and piston rings:
Si-DLC coated pistons show that there is no scuffing for a DLC coated piston.
Reduced friction:
The Si-DLC coated piston has revealed lower friction.
Lower CO2, NOx and soot/particle emission:
Lean out of the engine will give less soot/particle formation. The addition of Si-DLC to the piston, piston rings and cylinder has revealed that it is possible to run the engine at much more lean condition. This will give rise to less NOx. Hereto comes that the lower temperature caused by less friction (heat) will also give less NOx. CO2 is linked to fuel consumption, which will be lower due to less energy going to friction. However, experiments only indicated marginally improved performance.
Improve the lifetime of the engine parts:
There is no indication of significantly improved lifetime of the different engine parts tested.
Enable the use of alternative lightweight materials such as e.g. Zr-doped alumina inside the engine:
The project has successfully developed PEO and Zr-doped PEO. The PEO-treated pistons have been tested with poor performance caused by narrow prison ring grooves. Also the temperature and friction were observed to increase due to narrow tolerances. Further improvement is needed.
Major achievements:
When asking the consortium partners, the following achievements have been highlighted:
• Development of PEO and Zr-doped PEO equipment and processes at RTO partner
• Development and patenting of new family of surface-functionalized nanodiamonds showing high zeta potential and stability in different electroplating chemistries
• Build-up of dispersion plating knowledge and capabilities at the SME
• Development of new Si-DLC and W-DLC
• Development of new test facilities at RTO partner
• Increased knowledge and network reaching beyond the project
• New business possibilities for the involved partners
• Development and test of interesting demonstrators
• Market growth possibilities of the developed nanodiamonds both in relation to electroplating as well as in other segments
• Market growth possibilities for the developed DLCs.
Exploitable results:
The involved partners have identified the following exploitable results:
• Electroless dispersion plating of nickel-containing nanodiamonds (ND) at the in-house facilities at Adec SME partner Carbodeon – focus on customer-paid development and new R&D projects
• Electroplating of nickel and chrome coatings containing nanodiamonds at the in-house facilities at Carbodeon – focus on customer-paid development and new R&D projects
• Worldwide market exploitation. Continue market push of different surface functionalized nanodiamonds for various applications. Hereunder especially the single-digit ND with D90 = 4.9 nm revealing Zeta potentials up to +68 mV developed under the AdEC project
• Industrial implementation of Si-doped DLC coatings
• Industrial implementation of W doped DLC coatings
• Product-near application-oriented projects in connection with further optimization of Si- and W-doped DLC coatings
• New R&D projects in connection with PEO treatment and commercial product near PEO treatments
• Product-near dispersion plating on commercial level
• More experiments concerning the Si-doped DLC-coated cylinder and piston capable at running at low O2/Fuel ratio without ceasing
• Commercial test facilities have been built up at AdEC RTD-partner Danish Technological Institute
The objective and the S/T results achieved in the different WPs has been summarized below.
WP2: Development of functional nano-particles
Progress summary towards objective:
The objective of WP2 was to improve the surface functionalization of nanodiamonds hereunder their dispersion and zeta potential to enable the development of a unique dispersion-hardened coating. The work also involved the optimization of the particle distribution, and pushes the costs down based on intelligent compromises concerning the size distribution of the used nanodiamond particles.
Results:
The first objective of WP2 was to optimize the surface functionalization of the nanodiamonds hereunder their dispersion and zeta-potential to result in a functionalized nanodiamond prototype. The purpose of producing the prototype is to enable the development of a unique dispersion-hardened coating. The development of the functionalized nanodiamond prototype has been carried out using two different kinds of Carbodeon’s proprietary technologies, namely surface re-functionalization and dispersion manufacturing technologies. The developed functionalized nanodiamond prototype is a highly zeta positive (up to +68 mV), essentially re-functionalized with hydrogen atoms only being fully aqueous soluble up to 5 wt.% nanodiamond. The developed nanodiamond material has been patented.
Plating tests have been conducted with the different types of nanodiamonds. The tested nanodiamond materials included a nanodiamond suspension uDiamond Vivace (nanodiamonds are in agglomerated form) and uDiamond Andante (the first generation nanodiamond dispersion, dispersion stable within pH range 3 to 6) and the highly zeta positive fully hydrogenated single digit nanodiamonds.
The second objective was an optimization of the price/value with respect to the performance of the dispersion-plated coating. It has been shown that the developed nanodiamond prototype can be applied in the nickel electrolytes without the need for ultrasonic treatments. The developed hydrogenated nanodiamond is thus much more stable and will not agglomerate improving the overall stability and economics of the process. A business plan has been developed and it is estimated that, with respect to Nikasil, the nanodiamond process will have equivalent costs at a nanodiamond content of 0.22 wt.%.
It was found that addition of nanodiamonds directly into the electrolyte provides an efficient method for making up industrially stable composite electrolytes. Furthermore, the hydrogenated nanodiamonds are highly dispersed and there is no need for ultrasonic agitation, which again makes it easier to implement on an industrial scale.
2 patents have been granted and 16 patent applications has been filed.
Task 2.1: Developing surface functionalization of nanodiamonds
Different surface functionalization chemistries will be elucidated to improve the dispersion of Carbodeon’s nanodiamonds. This task will be highly intertwined with WP3 enabling plating of second-to-none dispersion platings based on the developed surface functionalities.
Three types of nanodiamonds have been tested hereunder a developed nanodiamond type being fully terminated by hydrogen zeta positive (up to +68 mV), essentially re-functionalized with hydrogen atoms being fully aqueous soluble up to 5 wt. % nanodiamond content. The developed nanodiamond material has been patented.
Task 2.2: Price/value optimization with respect to the performance of the dispersion-plated coating
The particle distribution should be optimized in order to achieve the optimal dispersion plating with respect to the price. It is evident that the more narrow the size distribution and the more pure the nanodiamond suspension, the more expensive the product will be.
Based on the result obtained it will be possible to add the developed fully hydrogenated nanodiamonds directly into conventional electroplating formulations without changing the chemistry and without adding expensive ultrasound agitation equipment in order to prevent agglomeration. The developed hydrogenated surface formulation has been patented.
Deliverables:
D2.1) Preliminary results for nanodiamonds: Preliminary test results, indicating the possibility of finding the right surface functionalization of nanodiamonds [month 9, DONE on time, improved and re-submitted].
D2.2) Functionalised nanodiamonds: Optimal surface functionalization of nanodiamonds suitable for WP3
[month 12, DONE on time, improved and re-submitted with more results included].
D2.3) Results summary: Summary of results suitable for inclusion on organization website, press releases etc. excluding any results not yet protected [month 13, DONE on time].
WP3: Development of wet chemistry
Progress summary towards objective:
The objective of the work package on Wet Chemistry is to develop the chemistry and formulation of a new electroplating bath capable of dispersion plating a host matrix material containing different micro/nanoparticles. Evidently, both the co-deposited ceramic particles as well as the host matrix material will have to be stable under combusting conditions and the particles preferentially must reveal a high affinity to oil enabling lower friction properties. The selected particles to be embedded were guided by thermodynamic calculations.
Results:
A first generation of particles/matrix chemistry suitable for coating cylinder sleevings has been developed based on a scalable electrochemical dispersion plating system. To this chemistry various types of micro- and/or nanoparticles can be and have been added. Additionally, a first generation of an electroless dispersion plating system has been developed and tested with nanodiamonds as particle material.
The first generation of particles/matrix chemistry developed in the present project is based on a Ni sulphate electrolyte with the following composition: 500 g/L Scanimet Nickel Salt, 40 g/L boric acid, 40 g/L Scanimet SiC and 16.5 mL/L Scanimet TA. Based upon thermodynamic considerations and literature studies it was chosen to focus the experimental work with co-deposition of the following particles: Various types of nanodiamonds, SiC, Si3N4, B4C, BN, Ca2F and CeO2. These powders showed an acceptable affinity to oil (SiC and B4C) or offers good dry lubrication properties (CaF2 and BN). Prototypes of coated cylinders prepared with this first generation of particle/matrix chemistry have been produced. CaF2 and nanodiamonds (ND) are promising particles to provide better performance in wear resistance compared to conventional Ni-SiC-based coatings. A new type of hydrogenated diamond, which enables easier formation of a stable electrolyte, was tested. The performance of the resulting coating was comparable to the coatings obtained from an electrolyte containing the conventional nanodiamond dispersion named Andante. From an economical point of view, the amount of nanodiamond used must be optimised in order to limit the consumption and keeping the cost/benefit as high as possible. Results from engine tests show that the adhesion of the dispersion-plated Ni is critical. Two tests at Husqvarna revealed delamination and a third passed at Radne with similar performance as a standard engine. The ND test at DTI revealed good adhesion but increased wear. Additionally, a setup for deposition of a top layer of electroless plated Ni-diamond on a Nikasil coated Husqvarna cylinder was successfully developed. This new type of layer will be subjected to future engine field tests.
To the best of the knowledge of the consortium, the developed chemistry is beyond state-of-the-art in the following formulations:
• It is the first time that Carbodeon’s new type of nanodiamonds (Andante or hydrogenated nanodiamonds) has been incorporated into a nickel plating suitable for cylinders.
• It is the first time that BN and CaF2 have been incorporated into a nickel plating simultaneously being suitable for cylinder plating.
• A setup and chemistry for performing electroless plating of Ni-diamond on a Nikasil-coated Husqvarna cylinder were successfully developed.
• Temperature stability, friction coefficient, wear resistance, oil affinity of the developed platings have been elucidated.
• It is the first time engine cylinders have been plated at IPU.
• Plating knowledge and capabilities have been transferred to Carbodeon building up inhouse plating facilities.
Task 3.1: Selection of particle type and size with high-stability affinity to oil for cylinder wall
The task involves thermodynamic calculation of stability diagram for different nanoparticles. Among the considered parties were: SiC, Si3N4, B4C, BN, CaF2, CeO2 and nanodiamonds. Test platings were fabricated and the affinity to oil was characterized by wetting angle measurements. Hardness was measured both before and after heating. Friction properties were studied by pin-on-disk measurements.
Task 3.2: Selection of metal matrix for coating at cylinder wall or cylinder sleeving
This task deals with the selection of a suitable host material. The stability of the Ni-P-O and the Co-Ni-O systems was compared. Co3O4 can appear at the surface of a NiCo alloy coating. The Co3O4 is a unique compound, which has a spinel structure with a mixture of Co2+ and Co3+. The matrices of NiP and NiCo are therefore candidates to replace the Ni-matrix if a Ni-based coating does not offer better performance as compared to the current Nikasil coating.
Task 3.3: Developing of process technology for the plating engine cylinders
This task deals with the development of a dispersion plating process for both electrolytic and
electroless processes. The outcome of the word was electroless and electroplating processes including CaF2, BN, ND and SiC particles.
Deliverables:
D3.1) Preliminary chemistry: Preliminary configuration of the expected particle / matric chemistry [month 9, DONE on time, improved and re-submitted with more results included]
D3.2) Particle / matrix chemistry: Development of first generation of particle/matrix chemistry to use [month 12 DONE on time, improved and re-submitted with more results included]
WP4: Selection & Optimisation of Material for Piston
Progress summary towards objective:
The objective of WP4 was to find the optimal material combination for constructing an engine piston system with optimal efficiency improving the engine performance going beyond steel and aluminum. The use of e.g. Ti titanium for the piston material makes it possible to perform plasma electrolytic oxidation (PEO) of the substrate forming a thick wear-resistant coating consisting of TiO2 which might also involve the integration of ZrO2 in order to obtain a harder coating. This may also be combined with a suitable surface treatment like a metal nitride or wolfram carbide (WC) supported DLC coating deposited by PVD (WP5)
Results:
From an analysis of temperature stability, mechanical properties, availability and applicability of the materials to the PEO and PVD processes, it was together with the involved engine companies (Husqvarna and Radne) concluded to employ the aluminium alloys (M145 and M138) used by Husqvarna and Radne for the piston and cylinder, respectively, supplied by Mahle. For the piston rings it was suggested to use grey cast iron. However, unlike the pistons employed at Husqvarna and Radne, no Sn coating should be applied to the pistons prior to coating and the piston rings should not be phosphatised. These obstacles were solved.
Task 4.1: Selections of material for the piston ring
Aluminium alloy M145 and M138 was selected for the piston and cylinder and grey cast iron for the piston rings. Later a parallel tract was initiated working with titanium piston and piston rings.
Task 4.2: Selection and development of coatings for piston rings
A number of different coatings were developed and tested on aluminium pistons, grey cast piston rings, Ti rings and Ti pistons. PEO processes were developed and optimized for both Ti and Al base materials. In addition, PEO including ZrO2 doping was developed and demonstrated. New DLC coatings were developed for piston and piston rings and even used on the interior of the cylinder.
Deliverables:
D4.1) Choice of material for piston and ring: Preliminary report, with achieved scientific results for the search for the right materials for piston and piston rings [month 9, DONE on time, improved and re-submitted]
D4.2) PEO process: Development of PEO process [month 12, DONE on time]
D4.3) Integration of ZrO2: Integration of ZrO2 into the PEO process [month 18, DONE on time]
WP5: Development of DLC for piston
Progress summary towards objective:
The objective of WP5 was to develop a diamond-like carbon (DLC) coating that has a tailored interaction hereunder perfect low friction towards nanodiamond particles integrated into the dispersion-plated Ni or Co/Ni matrix. At the same time, it is mandatory that the DLC is temperature- stable enough to withstand the conditions inside a combustion engine.
Results:
The development has been optimised along two tracks creating an optimised W-DLC coating and Si-DLC coating. The aim was to develop DLC coatings with a higher temperature stability and at the same time low friction and, if possible, also low friction towards dispersion-coated nickel-containing nanodiamonds. The coatings have been characterized by Raman, SEM, XRD, adhesion, nano-indentation and RBS. Especially the Si-coating revealed high temperature stability, higher hardness and interesting friction properties evaluated both in an engine applications at Husqvarna and in pin-on-disk experiments in cooperation with Tekniker in Spain. The Si-doped DLC will be further perused and introduced as a product on the market.
The coatings have shown promising results at tests both at Husqvarna and at Radne. Both end-users are interested in perusing additional tests in order to provide further evidence of the beneficial use of coatings in two-stroke engines.
Especially the Si-DLC appears to have a market potential based on its interesting friction properties, higher hardness and stability at higher temperatures.
Task 5.1: Development of superior adhesion layer between DLC-coating and the underlying piston.
The task has addressed the development and optimization of a Si- and W-doped DLC layer on top of a base layer based on optimized CrN or WC. The adhesion was found to be very good.
Task 5.2: Development of tailored low-friction PVD DLC-coating
Different versions of especially the Si-doped DLC was characterized and selected for engine test at DTI, Radne and Husqvarna.
The friction coefficient of the Si-doped DLC has been compared by Tekniker in Spain and found to be lower than other in-house DLC references (e.g. DLC-TR (DLC and IBAD-DLC) sliding against Al2O3. The friction properties have not been evaluated against electroplated Nikasil or a dispersion-plated Ni coating containing nanodiamonds since the coating will be worn off when sliding a Ni-plated pin against a DLC-plated disk or vice versa. Nevertheless, the feedback from Husqvarna and Radne is a lowering of the friction when a DLC coated piston and piston rings are sliding against a standard Nikasil-plated cylinder in real engine tests.
Deliverables:
D5.1) Combustion engine conditions: Report describing the working conditions for piston and piston rings inside a combustion engine [month 9, DONE on time]
D5.2) Combined WC and DLC coating: First version of combined WC and DLC coating [month 18, DONE on time]
D5.3) Optimized DLC/WC coating: Optimized DLC/WC coating [month 24, DONE, delayed 2-3 months]
WP6: Field Test
Progress summary towards objective:
The main objective for this Work Package was to evaluate and verify the developed coatings in a realistic but controlled environment. Through various tests of standard and modified engines, the achievements should be compared. The primary test set-up will be based on laboratory configurations and will be compared with conditions used at Radne and Husqvarna.
Results:
This work package is dealing with test and evaluation of the fabricated coating (PEO, electroplating and DLC) in real engines. It was planned to test and evaluate the solutions both at DTI, Husqvarna and at Radne. A new test facility was planned to be constructed at DTI since the capacity at Husqvarna and at Radne for R&D tests was rather limited.
During the period, engine tests were made at DTI, Husqvarna and at Radne. The amount of tests at DTI was limited by several breakdowns, limited at Husqvarna due to capacity and limited at Radne due to the racing season.
When comparing all tests, it appears that the Si-DLC on worn-in piston is interesting, revealing according to Husqvarna a 3% lower friction. DLC-coated Ti-rings behaved surprisingly good and Ni-containing nanodiamonds failed in the runs at Husqvarna and showed similar performance at Radne. The Ni nanodiamond coating failed at DTI due to too high wear. PEO-treated standard piston coated with W-DLC did not reveal better performance. Interesting and promising results have been obtained when running a Si-DLC-coated cylinder against a worn in piston and worn in piston rings decreasing the fuel/air mixture to a lower value that normally possible. The CO level was lower and the temperature was lower which in principle should also lower the NOx level. Husqvarna has agreed to continue these experiments after project termination.
Task 6.1: Performance test
The engine performance is measured on computer-controlled dyno setup. Under this task, DTI constructed a new test facility, enabling test of two-stroke engines based on Husqvarna chainsaw. This task turned out to be significantly more complicated than anticipated and everything that could go wrong went wrong due to the extreme vibrations of the chainsaw at high RPM – besides there were a number of other delays and failures such as e.g.:
• The new dymo test unit was delayed
• When finally assembled, the first rubber-metal couplings for the driveshaft broke down
• The outlets for the emission measurement broke off several times
• The new dymo broke down and was sent for repair
• The top of the cylinder was too soft to be mounted again; it was cut off for facilitating homogenous electroplating
• New and more ridge heads were fabricated
• Sealing of the head failed and new aluminium gaskets were fabricated
• The chain saw broke down – a new was replaced by Husqvarna.
Nevertheless, the test team at DTI now has a test facility for two-stroke engines, and has learned how to solve and handle the above-mentioned issues.
Task 6.2: Wear / Life-time test
Based on the developed test-setup a number of plated pistons and cylinders were tested and the outcome of the tests were used to guide the developed electroplating. This worked very well in the last half year of the project.
Task 6.3: Real-Life-test
Different configurations of plated piston and cylinders were tested at Radne and also at Odder honing service. The conclusion from Radne is that the developed solutions perform nearly as a standard engine. If anything, the Si-DLC coated systems appear to have a lower friction. At odder honing service, all the pistons seized. This was most likely due to a too small tolerance between the piston and cylinder, when adding the DLC coating.
Deliverables:
D6.1) Test process description: A detailed plan for the test process must be made. [month 9, DONE on time]
D6.2) Graphical data: Graphical data showing performance, consumption and emissions of engines [month 16, DONE on time]
D6.3) Wear and real life test analysis results: Analytical report with wear and real life test results [month 24, DONE delayed 2 months]
WP7: Dissemination and Exploitation
Progress summary towards objective:
The main objective of WP7 was to ensure IPR protection of the obtained results and develop a business plan for the exploitable results, and ensure dissemination and publication of project results both internally in the project by educating the SMEs and, externally, for a wider audience.
Results:
The obtained results have been publicly disseminated at various locations:
1. Nordtrib 2014, DTI Aarhus, Denmark, 10th – 13th June 2014
2. ATV-Semapp, DTI Taastrup, Denmark, 17th February 2014
3. SUR/FIN 2014, Cleveland Convention Center, Ohio, USA, June 9th -11th (Electroplating Seminar)
4. SUR/FIN 2014, Cleveland Convention Center, Ohio, USA, June 9th -11th (Sustainability Seminar)
5. Materialica 2014, München, Germany, 21st -23rd October, 2014 (Electroplating Seminar)
6. Sur/Fin Asia-Pacific in Singapore, December 9th – 12th 2014.
7. The 13th European Vacuum Conference, Aveiro, Portugal, 8th -12th September 2014.
8. Kokkola Material Week, Kokkola City Hall, Finland, 23rd – 26th September 2014.
9. The 20th Small Engine Technology Conference & Exhibition, 11th -13th Pisa, Italy, November, 2014.
Besides, a number of exhibitions and fair trades have been visited by the project partners and a video presentation of the development has been produced.
Internal training has been performed at several of the project meetings (see the list in section 3.2.3) and especially the electroplating knowledge has been transferred to new in-house electroplating facilities built up at Carbodeon’s facilities in Finland through extended visits at IPU in Copenhagen.
Some project results have been protected through Carbodeon’s IPR portfolio and a report on this has been made including a business plan for entering the electroplating market by supplying the developed nanodiamonds. A list of potential exploitable results has been listed in deliverable 7.3.
The involved partners have identified the following exploitable results:
• Electroless dispersion plating of nickel-containing nanodiamonds (ND) at the in-house facilities at the Adec SME partner Carbodeon – focus on customer paid development and new R&D projects.
• Electroplating of nickel and chrome coatings containing nanodiamonds at in-house facilities at Carbodeon – focus on customer paid development and new R&D projects.
• Worldwide market exploitation. Continue market push of different surface-functionalized nanodiamonds for various applications. Especially the single-digit ND with D90 = 4.9 nm revealing Zeta potentials up to +68 mV developed under the AdEC project.
• Industrial implementation of Si-doped DLC coatings.
• Industrial implementation of W-DLC coatings.
• Product-near application-oriented projects in connection with further optimization of Si- and W-doped DLC coatings.
• New R&D projects in connection with PEO treatment and commercial product-near PEO treatments.
• Product-near dispersion plating on a commercial level.
• More experiments concerning the Si-doped DLC-coated cylinder and piston capable at running at low O2/fuel ratio without ceasing.
• Commercial test facilities have been built up at the AdEC RTD-partner Danish Technological Institute.
• Ongoing dissemination along the entire value chain from R&D to end-user level generating new business leads.
Task 7.1: Protection of project results
The developed, application specific nanodiamond dispersion was patented. A report has been generated listing title and abstract of filed patents. This overview contains 2 granted patents and 16 patent applications filed in the project period.
Task 7.2: Development of an Exploitation Strategy for exploitable results
All the identified exploitable results have been listed and filed in deliverable 7.3
Task 7.3: Identifying financial opportunities for supporting post-project activities
Carbodeon, DTI and IPU have in the project period submitted one EUROSTARs application, which failed. This will most likely be re-submitted in the September 2015 round. Carbodeon, DTI and IPU are working closely together and the team is quite positive that they will find suitable funding for continuing the work. Especially Husqvarna is interested in continuing the close cooperation in the future.
Task 7.4: Dissemination of project results
The project has been disseminated at 9 occasions and a project video has been made and uploaded on the website (http://www.adecoating.dk/project-results.aspx). Hereto comes a number of trade fairs, where Carbodeon has displayed their nanodiamond portfolio.
Task 7.5: Internal dissemination of project results and training of SME partners in the use of them
Task Leader: CHROM
Dissemination and training have been conducted and aligned with several project meetings but also through dedicated and extended visits especially by Carbodeon at IPU.
Deliverables:
D7.1) Website: External and internal project website to be updated every 3 months [month 3, DONE on time]
D7.2) Interim Plan for use and dissemination of knowledge: [month 9, DONE on time]
D7.3) Final plan for use and dissemination of knowledge: [month 22, DONE delayed 4 month]
D7.4) Business Plan: Business plan for each exploitable result [month 20, DONE delayed 7 months]
D7.5) Public dissemination: After protection - public dissemination of scientific and commercial results [month 22, DONE delayed 3 months]
D7.6) Internal dissemination and training workshops: [month 24, DONE report delayed 2 months]
D7.7) Video presentation: [month 22, DONE delayed 2 month]
________________________
Concerning the milestones, the following can be summarized:
MS1: Project go/no go (month 9)
Decision based on deliverables. Based on the obtained results – especially the development of functional diamonds, electroplating results and DLC results - it was decided by the consortium to continue the development
MS2: There is no MS2
MS3: Functional nanodiamonds (month 24)
On shelf available product suitable for large-scale dispersion plating
Fulfilled
Carbodeon has increased the portfolio of ND with a new fully hydrogenated version
See e.g.: http://www.carbodeon.net/index.php/en/nanomaterials/udiamond-liquid-dispersions/udiamond-hydrogen-d-2nd-gen
MS4: End user plating (month 24)
Final prototypes plated at end-user site
Fulfilled: Final prototype plated and report on MS4 has been sent to project officer.
MS5: WC/DLC onto PEO (month 16)
Demonstrator comprising WC/DLC onto PEO-treated Ti piston rings
Fulfilled: Demonstration comprising WC/DLC made and report on MS5 has been sent to project officer.
MS6: WC/DLC on ZrO2 doped PEO (month 18)
Demonstrator comprising WC/DLC on ZrO2-doped PEO-treated Ti piston rings
Fulfilled: Demonstrator ZrO2-doped PEO-treated Ti piston rings and report has been sent to project officer.
MS7: End-user test DLC/WC coating (month 18)
First DLC/WC coating
Ready for test at end-users
MS8: Production ready DLC/WC coating (month 18)
First DLC/WC coating ready for test at end-users
Fulfilled: DLC/WC coating has been delivered for test at end-user
MS9: Test set-up described (month 4)
Test set up for performance and real time test described
Fulfilled: Test protocol has been written
MS10: Real time tests (month 24)
Conclusion on wear and real time tests
Fulfilled: Conclusion is included in report D6.3
MS11: Protection of project breakthroughs (month 20)
Relevant documents
Fulfilled: Report on IPR protected results has been written and sent to project officer
MS12: Business plans (month 20)
Business plans for Execution
Fulfilled: Business plan written for nanodiamonds and submitted as D7.4
Potential Impact:
Potential Impact and exploitation of results:
This section will highlight some of the ongoing actions pin-pointed by the consortium concerning exploitation of the obtained results.
Electroless dispersion plating:
Carbodeon is continuously exploring potential market possibilities for nano diamonds. As shown in the business plan in delivery D7.4 Carbodeon is targeting the electroless plating market – especially with the developed Single Digit (SD) hydrogen terminated nano diamonds. The electroless market is expected to be smaller than the 13.6 B$ large electroplating market. With the knowledge achieved within this project concerning electroplating, Carbodeon has built its own plating facilities in order to be able to fabricate demonstrators and perform test-coatings for customers. In the area of Electroless dispersion plating the focus is on customer paid development and new R&D projects to generate market access.
Electroplating of nickel and chrome coatings containing ND:
The maket potential for electroplating is significantly larger than electroless plating. The development of electroplated nickel with embedded nano diamonds performed in the AdEC project has opened up to companies such as e.g. Atotech, Coventia, CCT, Bales Mold and several others which Carbodeon is currently in direct negotiation with. Hereto comes additional companies that are interested in adding nano-diamonds into their chrome chemistry (both chrome +VI and +III). The dialogue with these and other companies is ongoing. The scientific development and the demonstrators made within the AdEC project is a very important prerequisite when initiating a dialogue with potential customers.
Worldwide market exploitation of nano diamonds:
Carbodeon is continuously exploring industrial use of nano diamonds both in electroplating and electroless plating as mentioned above but also in connection with other industrial applications such as thermal management, improved performance of polymers, scratch resistant surfaces, etc. The IPR portfolio has expanded during the project period as reported in MS11: Protection of Project breakthroughs. In the coming 2-3 years, it is expected that the hydrogen-terminated single-digits 4-6 nm large ND will make several commercial successes both in connection with electroplating but also in connection with e.g. thermal management issues in electronics. Focus is direct customer visits facilitated by agents, ongoing market dissemination through exhibitions/fairtrades etc. primarily in USA and Asia.
Industrial implementation of Si-doped DLC coatings:
The developed Si-doped DLC has been coated both on the piston, the piston rings as well as on the inside of the cylinder (see deliverable 5.3: Optimized DLC/WC coating and deliverable 6.3: Wear and real life test analysis results). The Si-doped DLC-system deposited on the piston, the piston rings and the cylinder, was tested at DTI revealing surprising performance at high O/fuel-ratio where the piston-cylinder normally would cease – this did not happen. Apparently, it is possible to run the coated piston/cylinder system at these much higher O/fuel-ratios without crashing the engine and even achieving a lower wall temperature. Running at a higher O/fuel ratio at a lower temperature is expected to generate less NOx. This hypothesis will be further tested together by Husqvarna, which is very interested in these new findings.
In addition, the Si-DLC is also interesting due to the improved stability at higher temperature.
The friction properties of the Si-DLC coating has been investigated together with Tekniker in Spain. The performance of the new Si-DLC is also interesting from its better friction properties. Danish Technological Institute is currently exploring possible ways to get the DLC tested in other industrial applications.
Industrial implementation of W-doped DLC coatings:
After successfully market introduction of the Si-doped DLC, it is the aim to find support for a development project on the W-doped DLC as a second priority.
PEO treatment of Al, Ti and Mg:
The Adec RTD partner IPU will utilize the build up PEO (Plasma Electrolytic Oxidation) treatment facilities to engage in both commercial development projects involving companies and R&D-project based on improved PEO treatment hereunder also doping with e.g. ZrO2 in the PEO treatments. Based on the AdEC project, IPU has gained experience in PEO treatment of Al, Ti and even Mg.
Commercial dispersion plating:
IPU has gained knowledge in dispersion plating based on both electroless and electroplating involving particles of nano diamonds, CaF2, NB, SiC. This knowledge and expertise will be made available on a commercial level.
Ongoing test at Husqvarna:
More engine tests are being made concerning the Si-doped DLC coated cylinder, (piston and piston rings) capable at running at low fuel to air ratio without seizure. Husqvarna has agreed to continue these experiments after project termination
Commercial motor test at DTI:
Danish Technological Institute has buildup test facilities for two-stroke engines within the AdEC project. Small engine- and emission testing will be made commercially available.
SME partners:
Both SME partners, Radne Motor AB and Å.K. Chrom A/S, are positive to the results achieved and disseminate the results within their different market scopes: Cart Racing engines and electroplating of surfaces in industrial applications. The higher engine performance achieved due to lower friction and the potential lower emissions draws attention within the engine community of cart racing. Within industrial applications surface treatments Å.K. Crom find interest from the market in treatment which can substitute the present Nikasil application. Within both the markets that the SME Adec partners are facing the dissemination is ongoing and gaining attention.
Dissemination:
Dissemination activities has been divided into external dissemination activities and internal teaching and dissemination activities.
External/open dissemination activities:
The AdEC Consortium participants have presented highlights generated by the AdEC project on a number of occasions during the project period of January 2013 to December 2014.
In summary, the public dissemination of AdEC objectives and preliminary results conducted, amounts to seven oral presentations where project partners have presented results from the project.
1. Nordtrib 2014, DTI Aarhus, Denmark, 10th – 13th June 2014
2. ATV-Semapp, DTI Taastrup, Denmark, 17th February 2014
3. SUR/FIN 2014, Cleveland Convention Center, Ohio, USA, June 9th -11th (Electroplating Seminar)
4. SUR/FIN 2014, Cleveland Convention Center, Ohio, USA, June 9th -11th (Sustainability Seminar)
5. Materialica 2014, München, Germany, 21st -23rd October, 2014 (Electroplating Seminar)
6. Sur/Fin Asia-Pacific in Singapore, December 9th – 12th 2014.
7. The 13th European Vacuum Conference, Aveiro, Portugal, 8th -12th September 2014.
8. Kokkola Material Week, Kokkola City Hall, Finland, 23rd – 26th September 2014.
9. The 20th Small Engine Technology Conference & Exhibition, 11th -13th Pisa, Italy, November, 2014.
Besides these presentation a number of exhibitions and fair trades has been visited by the project partners and a video presentation of the development has been produced.
Below is summarised presenters of the AdEC-project objectives and preliminary results on the above-mentioned occasions.
1) Nordtrib 2014:
The 16th Nordic Symposium on Tribology - NORDTRIB 2014
Place and date: Danish Technological Institute, DK-8000 Aarhus, June 10th – 13rd
At the Nordtrib 2014, held in Aarhus at The Danish Technological Institute and at the Congres Center, the AdEC-partner IPU, presented a paper authored by the project participants Anette Alsted Rasmussen, Io Mizushima and Per Møller: “Investigation on frition properties of nickel ceramic electrodeposits”. The key issues presented were electrodeposits on cylinder wall coating, friction, wear, lubricant and oil affinity.
The presented content were results optained through the AdEC-project WP 4 and 5. The ADEC-project was duly acknowledges at the presentation and the within the paper text.
The NORDTRIP symposium is held biennially since 1984 in one of the Nordic countries: Finland, Sweden, Norway and Denmark. The Symposium is a highly regarded venue for the international tribology community. NORDTRIP is intended as a forum where researchers and developers from universities, research institutes and industry can present their latest contributions and discuss field-related issues.
2) ATV-SEMAPP
ATV-SEMAPP conference on Friction and Lubrication
Place and date: Danish Technological Institute, DK-2630 Taastrup, February 17th 2014
At the ATV-SEMAPP conference «Friction and Lubrication», a paper on the AdEC project objectives and application of «Diamond-Like Carbon (DLC) – a family of self-lubricating low-friction surfaces» were present by AdEC WP5 leader Sascha Louring.
Danish Academy of Technical Sciences (ATV) is an independent institution which aims at furthering technical and scientific research. ATV also aims at ensuring the application of research results in order to increase wealth and welfare in Danish society. SEMAPP is one of several sociaties attached to the ATV. It focuses on Engineering Manufacturing Techniques in Process and Production.
3)+4) SUR/FIN Manufacturing & Technology Trade Show & Conference 2014
Place and date: Cleveland Convention Center, Ohio, USA June 9-11, 2014
At the Electroplating Seminar of the conference, the AdEC WP2 leader Carbodeon’s US sales agent presented a paper by Niko Rostedt entitled: «Coatings with improved properties using detonation nanodiamonds as plating additives».
At the Sustainability Seminar of the conference, the AdEC WP3 and WP4 technical manager Per Møller presented at paper on “A Comprehensive Look at Surface Finishing & Its Processes: Advanced Surface Technology, Volumes I & II - Per Møller and Lars Pleth Nielsen”. The oral presentation included results form the ADEC project.
SUR/FIN Manufacturing & Technology Trade Show & Conference is an annual three day event aiming at surface finishing professionals to the industry’s best business opportunities, latest innovations and most influential leaders.
5) Materialica 2014, München, Germany, 21st -23rd October, 2014 (Electroplating Seminar)
At the Trade Fair the AdEC WP2, WP3 and WP4 participant Niko Rostedt of Carbodeon Ltd, Finland, showed there product portfolio.
6) Sur/Fin Asia-Pacific
Place and date: Singapore, 9th – 12th December 2014
At the conference, Electro-plating session, the AdEC WP2, WP3 and WP4 participant Niko Rostedt of Carbodeon Ltd, Finland, presented a paper on “Improving the wear resistance of electroless Nickel coatings using detonation nano-diamonds”.
Sur/Fin Asia-Pacific is a bi annual exhibition and conference jointly organized by National Association for Surface Finishers (NASF) of USA and Singapore Surface Engineering Association (SSEA) with the support of National University of Singapore (NUS), Singapore Institute of Manufacturing Technology (SIMTECH) and other organisation.
7) The 13th European Vacuum Conference and 7th European Topical Conference on Hard Coatings
Place and date: Aveiro, Portugal on September 8th -12th 2014
At the conference, the AdEC coatings were presented at the Surface and Structure session on September 11th 2014 in a paper titled: “Tribological behavior of DLC coatings for vacuum applications” by Edurne Berriozabal, Amaya Igartua, of Fundación Tekniker, Eibar, Spain and the AdEC coordinator Lars Pleth Nielsen of Danish Technological Institute. The presentation included Si-DLC coatings developed in the ADEC project discussing friction and wear of DLC coatings.
The annual European Vacuum Conference commenced in 1988 as an off-spring of International Union for Vacuum Science, Technique and Applications (IUVSTA). Throughout the Europe region, it gathers numerous vacuum societies in a joint conference matching the American Vacuum Society’s annual symposium in the USA. EVC provides a useful and well-supported forum for scientists based in Europe to exchange latest data in vacuum technology and vacuum-related science.
8) Kokkola Material Week
Place and date: Kokkola City Hall, Finland, 23rd – 26th September 2014
At the conference, Carbodeon’s Business Development consultant Gavin Farmer of WP2, WP3 and WP4, presented a paper on: “Improving the Wear Resistance of Electroless Nickel Coatings Using Detonation NanoDiamonds”, at the session of MetalKokkla focusing on New functional and protective coatings, one of the six session themes.
Kokkola Material Week is an annual conference focusing on innovation and covers everything from education and basic research to R&D and commercialization services for businesses.
This is the opportunity for business developers and scientists to network and learn more about material science within six thematic sessions. In 2014 these were: Biobased products, Nanotechnology, Greener solution for industry, Leather production methods, New functional and protective coatings and Reuse/recycling though industrial symbiosis.
9) Small Engine Technology Conference & Exhibition
Place and date: Palazzo dei Congressi; Pisa, Italy, November 11th -13th 2014
At the 20th SETC conference, the AdEC WP6 participant Mikael Bergmann of Husquarna, presented Paper no 14SETC-2014-09-27 entitled: «Advanced Low Friction Engine Coating Applied to a 70cc High Performance Chainsaw».
The annual SETC Conference and Exhibition circulates between Asia, Europe and the United States. The conference and exhibition offers up-to-date information on the state of the economy and the status of emission regulations, alternative powertrains and the effects on the environment.
The vehicle product ranges from ATVs, scooters and motorcycles to portable power generators, lawnmowers and hand tools. We will be discussing the challenges and developments in small engine technology from OEMs, suppliers and academia from around the world.
Video
A video has been produced summarizing the development made within the AdEC project. The video will be made available on all the partners’ website: www.adecoating.dk. The video is also part of the deliverable D7.7.
Internal training and dissemination:
During the duration of the project, twelve internal dissemination and training workshops have been held all at the premises of the project participants. Five of these in conjunction with the formal Consortium Management Meetings.
At the scheduled consortium meetings, it was agreed from the project start, that each occasion should last for two days allocating the first day to internal dissemination of the project results and informal discussion on work, planning and procedures while the second day has been allocated for the formal decision making session including sufficient time for discussing, training and cross-fertilisation.
SME – RTD Crossfertilisation:
The project has embraces three SME and two RTD partners from whom the processes of applying DLC and results of surface treatments have been disseminated.
The project participant of SME Carbodeon have been working at the IPU lab for longer periods on four occasions during 2013 in order to learn how to make electroplating and especially dispersion plating incorporating nano diamonds into nickel. The periods included both teaching and training in electroless nickel and electroplating of nickel, pre-treatment, anode configuration, etc. The outcome has produced cross-fertilisation on plating knowledge and ND for both the SME and the RTD partner on how nano-diamond containing nickel based coatings can be apply for the project purpose using wet chemistry. The cross-fertilisation have been so successfully that Carbodeon has set up their own inhouse plating line.
IPU and the SME ÅK Chrom have on two occasions discussed the process of substituting Nikasil with nano diamond containing nickel in the industrial environment at ÅK Chrom and at the IPU Lab premises. ÅK Chrom’s upscaling experience has been made available for the consortium and especially IPU and Carbodeon have discussed technical issues concerning upscaling strategies.
Online sessions have been further elaborated by video-conference, skype meetings on progress and problem resolution.
The book Advanced Surface Technology written by Dr. Lars Pleth Nielsen (DTI) and Prof. Per Møller (DTU) have at several locations been used as teaching and training material.
Husquarna and SME partner Radne have both received a high number of DLC treated motor parts (piston, piston rings and even cylinders) from the RTD partners as well as electroplated cylinders as result of the RTD work performed, i.e. cylinders, pistons and rings for testing at their facilities. Husquarna and Radne has learned a lot about while, demonstrating the effect of low friction engine coatings in combination with standard Nikasil plated cylinders as well as new and novel nickel plating with imbedded nano diamonds and CaF2, BN, SiC particles and mixtures hereof. DTI has also provide for profound motor lab tests according to plan and in charge of WP6 motor testing building up a new test facility based on training and knowledge flow from Husquarna and Radne to DTI. The outcome has provided valuable results and learnings, which can be applied by the SMEs and also for the RTD partners to adjust parameters in the ongoing development of new and even better performing DLC coatings and electroplated solutions.
List of project meetings, dates and venues including internal training and dissemination:
The following list provides the number of occasions, where the project participants have physically met during the project period.
17th January 2013, DTI, Aarhus, Denmark
29th January, Chrom, Aarhus Denmark
21th February 2013, Radne, Sweden
13th May 2013, IPU, Denmark
18th February – 1st March – 2013, IPU, Denmark
18th – 22nd March 2013, IPU, Denmark
27th – 31st May 2013, IPU, Denmark
26th – 28th August 2013, IPU, Denmark
12th August 2013, Husquarna, Sweden
13th August 2013, Husquarna, Sweden
3rd December 2013, IPU, Denmark
4th December 2013, IPU, Denmark
13th May 2014, DTI, Denmark
14th May 2014, DTI, Denmark
20th August 2014, IPU, Denmark
21st August 2014, IPU, Denmark
3rd December 2014, Carbodeon, Finland
Exploitation Results
The following IPR has been generated:
US2014/0091253A1: Nanodiamonds containing thermoplastic thermal composites
US2014/0094546A1: Fluoropolymer coatings
The following patent applications has been filed:
WO 2013135305 A1: Detonation nanodiamond material purification method and product thereof
PCT/FI2013/050947: Nanodiamonds containing thermoplastic thermal composites
US 14/141779: Nanodiamonds containing thermoplastic thermal composites
PCT/FI2013/050947: Fluoropolymer coatings
US 14/041621: Fluoropolymer coatings
FI 20136324: Nanodiamond Containing Composite and Method for Producing the Same
JP 2013-272919: Nanodiamond Containing Composite and Method for Producing the Same
US 14/141779: Nanodiamond Containing Composite and Method for Producing the Same
List of Websites:
The project has established a homepage at the website http://www.adecoating.dk
A video presentation over the project has also available at the website (http://www.adecoating.dk/project-results.aspx).
The main contact persons behind the project and their organizations details are summarized below:
Partner 1:
Director Lars Pleth Nielsen
Danish Technological Institute (DTI)
Kongsvang Alle 29
DK-8000 Aarhus
Denmark
E-mail: lpn@teknologisk.dk
Phone: +4572201585
Web: www.teknologisk.dk
Partner 2:
CEO: Kim Sørensen
ÅK Chrom
Axel Kiers Vej 38
DK-8270 Højbjerg
Denmark
E-mail: info@aak-chrom.dk
Phone:+45 8629 6788
Web: www.aak-chrom.dk
Partner 3:
CEO Vesa Myllymäki
Carbodeon Ltd. Oy
Pakkalankuja 5
01510 Vantaa
Finland
E-mail: vesa.mylymaki@carbodeon.com
Phone: +358 50 555 9066
Web: www.carbodeon.net/index.php/en/
Partner 4:
CEO Leif Radne
Radne Motor AB
Markörgatan 2
SE-136 04 Hanninge
Sweden
E-mail: leif@radne.se
Phone: +46 8556 506 90
Web: http://www.radne.se/
Partner 5:
Project Manager Mikael Bergman
Husqvarna AB
SE-561 82 Huskvarna, Sweden
E-mail: mikael.bergman@husqvarnagroup.com
Phone: +46 7307 440 86
Web: http://www.husqvarna.com/us/home/
Partner 6:
Group manager Anette Rasmussen
IPU Technology Development
DK-2800 Kgs. Lyngby
Denmark
E-mail: aar@ipu.dk
Phone: +45 45 25 22 12
Web: http://www.ipu.dk/