Final Report Summary - SHYMAN (Sustainable Hydrothermal Manufacturing of Nanomaterials)
Executive Summary:
In 2008 Lux Research predicted that nanoparticles would “touch” $3.1 trillion worth of products across the value chain by 2015, with the intermediates market reaching a net worth of $432 billion. Transparent conductive films alone would be worth $3.5 billion by 2020. However, it is almost impossible to find credible predictions for the market potential of the nano-enabled industry beyond 2025. Hence in 2016, it is also fair to say that nanotechnology is still a developing market with many emerging sectors. There are many different methods for producing nanomaterials to meet market demands, and dry methods (despite all the ensuing issues over safety) have been the most successful to date. As alternatives emerge, it is likely that industry will turn away from these dry products and engage with process technologies that can produce a dispersion based, higher quality and easy to formulate product. The real challenges for new alternatives are clearly around material quality, scale up, formulation and (most importantly) the cost of production.
Continuous hydrothermal synthesis is relatively new technology and would offer a true alternative to other production methods because it is a genuinely continuous process which is also chemically more benign. Continuous hydrothermal synthesis produces nanoparticulate materials by mixing superheated or supercritical water flow with an aqueous flow containing a dissolved metal salt. i.e. rather than slowly heating the entire contents of a batch vessel (batch hydrothermal synthesis), two fluids are continuously mixed together. The problems around this process were solved during research work at The University of Nottingham and the reactor configuration necessary for continuous production was demonstrated at bench (g/hr) and pilot scale (kg/day) prior to the start of the project.
Through the SHYMAN project and the interaction of the 17 partners from across Europe, the process has now been scaled to 1000 tons per year production (dry weight equivalent) which makes the plant the largest multi nanomaterial production facility in the world. Sustainability credentials and cost analysis were also assessed, to compare the process against alternative methods and against existing products in the market place. The process was shown to be highly sustainable, and cost effective with OPEX costs of below 10 euros per kilo (and less than 5 euros, in some cases). A water treatment strategy was devised and implemented that would allow the plant to operate continuously whilst formulating products, ready for sale.
Case studies were part of the project in order to validate the products in the context of real products. These products were selected to demonstrate the efficacy of the process in different areas from healthcare to printed electronics. Each area required particularly performance criteria that would test how controllable the process was in terms of product quality. Bone materials (such as Hydroxapatite) with metal nanoparticles (such as Pt, Ag, Au) for medical diagnostics, printed electronics materials (such as indium tin oxide and quantum dots), functional lubricants (such as sulphides), ceramic and catalysts nanoadditives for polymers (such as titania, and silica), doped luminescent ceramics (such as YAG:Ce), superhydrophobic materials (such as ceria and silica), and functional polymer additives (e.g. UV resistant materials like zinc oxide and flame retardants).
Continuous hydrothermal synthesis is still in its infancy, in terms of the scope of materials that can be produced and the control over particle size and shape. The project also allowed researchers to specifically focus on expanding the ‘repertoire’ of the process. Partners were able to demonstrate how metals, mixed metal oxides, sulphides, perovskites, phosphates and even metal organic frameworks could be produced. In addition to simple ‘production’, much of the work was around how the size and shape of the products themselves could be altered by changing process variables e.g. pressure, temperature, flow, concentration and precursor type. Most of this work is now published, with a significant number of publications in preparation.
Project Context and Objectives:
SHYMAN was a large scale integrating project focussed on the scale up and development of continuous hydrothermal synthesis for the manufacture of high quality nanomaterials.
Project Context
The production technologies for nanomaterials are critical in the success of nanotechnology as a whole. There are many different methods for manufacturing nanomaterials, both wet and dry, the latter being more visible in today’s market. However, it is likely that manufacturing methods will change as more emphasis is placed on health and safety and the sustainability of processes. This was highlighted recently at the 4th Annual Nano Safety for Success Dialogue Meeting (Brussels March 2011) where regulatory concern was focussed on the hazards of exposure with dry nanopowders. Therefore, for economic and environmental reasons it is vital that manufacturing routes that will facilitate the forecasted increase in production are;
1. Green – using reduced levels of solvents, sourcing the most environmentally friendly feed materials
2. Sustainable – with efficient energy recovery, low temperature processing and recycling
3. Low cost – through process optimisation to minimise the number of downstream processes prior to use
4. High Quality – the process should be capable of generating high quality materials with superior control over particle size, size distribution, formulation etc...
Routes that can succeed in one or two of these areas will not be enough in the future meaning that Industry will have to look for ways to achieve all of these targets.
Dry methods - Currently the most commercially used techniques for producing nanomaterials are considered to be ‘bottom up’ approaches that are dry based technologies. Many of these technologies often generate low specification dry powders (wide particle size distribution, highly agglomerated particles of basic materials) that have to be re-processed before use. Combustion synthesis or Flame pyrolysis methods are dry techniques that use a high temperature zone to convert dissolved metal species into nanoparticles. The metal salts are dissolved in a suitable organic fuel that burns in the flame to produce a spray of dry nanoparticles that are collected downstream. Plasma Synthesis is a similar process where the metal precursors travel in a spray through a plasma under vacuum to form nanoparticles. These techniques are relatively simple and easily scalable, hence their overall appeal to industries that require large quantities of material. The cost of manufacture is also relatively low which is why these techniques have been fairly widely used. However, there are issues over the quality of the product and since these are dry techniques, they will also require downstream processing steps to redisperse and formulate the particles.
Wet Methods - Hydrothermal synthesis is an alternative route to manufacture that offers unique opportunities for the synthesis of high quality nanoparticles and their formulation. In contrast to other technologies, hydrothermal synthesis;
• Does not tend to use noxious chemicals – with water soluble precursors and water as a solvent
• Uses relatively simple chemistry – generally following hydrolysis and dehydration stages
• Allows straightforward downstream processing - the process is dispersion based
• Uses relatively cheap chemical precursors – acetates, nitrates and phosphates
• Can produce stoichiometric compounds like YAG or BaTiO3
• Can produce non-stoichiometric materials where precise alloying or doping can be achieved
• Can avoid agglomeration - the dispersed materials can be stabilised with additives, in situ.
• Size and shape distribution can be narrow and well controlled
The historical drawback has been in scaling up hydrothermal synthesis away from batch systems. In batch systems dissolved metal salts are heated in autoclaves at relatively slow ramp rates. Processing times can be hours or days for the larger systems. The step from batch to continuous hydrothermal synthesis has been held back by engineering issues around mixing the heated fluid and the aqueous metal salt flow. T piece reactors were originally used but these are now, generally accepted as unworkable with good reason. An optimum configuration was invented and developed by UNOTT (coordinator) to allow the two fluids to mix in a controlled and efficient way. The superheated fluid passes down an inner nozzle pipe against an up flow of cold metal salt. Nanoparticles form at the interface of the two fluids and the buoyancy of the heated flow causes the nanoparticle slurry to be carried upwards (downstream) for cooling and collection. See www.prometheanparticles.co.uk for video of the process. This was the first reactor design to successfully eliminate blockages, whilst creating high quality nanomaterials, thus representing a step-change for hydrothermal technology. UNOTT demonstrated that the lab scale reactor (5g/hour) could be scaled 30 times (150g/hour) to produce a 1 tn/annum system.
As such, continuous hydrothermal synthesis was seen as an enabling and underpinning technology that is ready to prove itself at industrial scale, to over 100 tons per annum. Academic specialists with international reputations in reactor modelling and kinetics and metrology were assembled to develop the ‘know how’ needed to scale up the current pilot scale system. Selected project partners with expertise in sustainability modelling and life cycle assessment quantified the environmental impact and benefits of a process that uses water as a recyclable solvent, whilst producing the highest quality, dispersed and formulated products. In addition to scale up production, the process will be improved through four case studies with industrial end users, namely – printed electronics; surface coatings; healthcare and medical; hybrid polymers and materials. Further value was added to the project by working on new materials that have been identified as key future targets but cannot be currently made, or made in significant quantities. The consortium was founded on the principle that the whole value chain (from nanoparticle production to final product) must be involved in the development of the technology. This not only informed the development stages of the production process but also maximised ‘market pull’, rather than simply relying on subsequent ‘technology push’.
Main Objectives
The main objectives of the SHYMAN project were to investigate;
i - Scale up – what are the limits for scale up? How can these limits be impacted by better process design?
ii - Formulation – how flexible is the process to allow online pre-treatment of the nanoproduct?
iii - Weight loading – how can the concentration of the final product be increased from 1% to 30%?
iv - Cost – how low can opex be driven to make this one of the most sustainable manufacturing processes of the future?
v - Sustainability – what are the environmental benefits of the process?
Project Structure - The work packages covered key areas of research and development but the overall effort were grouped as follows.
i- Nanoparticle manufacture on bench, pilot and full scale WP1, WP2 and WP7
ii- Scale up design and build WP5, WP8-9
iii- Formulation Research WP3 and WP2
iv- End User product development via case studies WP4
v- Process Life Cycle Analysis and safety assessment WP6
www.nottingham.ac.uk/~eczehl/SHYMANFR/Figures1.html
Specific Objectives around Scale Up (Workpackages 5,8-9)
The real challenge was to find the optimum reactor design that can manufacture 100 tons/annum (dry weight equivalent) of formulated nanomaterials. The initial system at the start of the project was operating at 1 tn/annum. The system would need to be capable of sustained operation at a range of superheated conditions from sub-critical (starting at 100oC+ and 10 bar) to near critical and supercritical conditions (>374oC and >218 atmospheres).
Specific Objectives around Formulation and Weight Loading (Work Packages 3,5)
Continuous hydrothermal synthesis tends to produce aqueous suspensions of nanomaterials at relatively low concentrations (<1% wt loading) which is a critical issue that will be addressed in the project. The key challenge for formulation was to create a flexible system that could produce nanomaterials with a specific coating, in a specific aqueous or non-aqueous fluid, at a specific weight loading.
Specific Objectives around New Materials, Metrology and Development (Work Packages 2,7)
Underpinning the work around scale up and improved formulation of nanomaterials was the characterisation of nanomaterials and development of materials with enhanced properties for specific applications.
Specific Objectives around Sustainability and Manufacturing Costs (WP6,8)
In order for Continuous hydrothermal synthesis to become a popular route for nanomanufacturing (in addition to its product flexibility and scaled manufacture) also meant demonstrating its green credentials in terms of sustainable and safe manufacture with low operating costs, capital costs and CO2 footprint.
Specific Objectives around Dissemination and Engagement with Industry (WP4, 10)
The integration of end users in the project was deliberately designed to improve the development of the process and provide evidence of the suitability of the products for a wide range of applications. The dissemination by all partners in the most appropriate forums (academic, industrial, trade) ensured the widest possible promotion of the project and project aims and objectives.
Concluding remarks on completion of the SHYMAN Project
We have succeeded in this ambitious project with the design, build and operation of the world’s largest multi-material continuous hydrothermal plant in the world. This plant is capable of making high quality nanomaterials including metals, metal oxides, hydroxides, solid solutions, carbonates, sulphides as well as more complex nanoporous materials including MOFs, ZIFs and COFs. This project has only been possible through the close collaboration of 18 partners across Europe with world-class expertise in numerous disciplines including chemical engineering, chemistry, physics, life cycle assessment and materials engineering.
Many of the case studies have shown that the process can produce nanomaterials with a clearly defined technical and economic edge in the marketplace. Many new nanomaterials have also been produced using this platform technology.
It has been proven to be a flexible, economic and environmentally sustainable technology with the capacity for scale up, well beyond lab scale to full industrial scale production.
Project Results:
SHYMAN PROJECT RESULTS AND HIGHLIGHTS
www.nottingham.ac.uk/~eczehl/SHYMANFR/SANDT.html
This section shows some of the S and T highlights and technical breakthroughs for each of the key objectives for the SHYMAN project.
I. Scale Up – from reactor modelling to chemical engineering designs to the final plant
II. Formulation and Weight Loading – increasing the weight loadings of the products and formulating them for use in target applications
III. Sustainability and Production Cost – proving that the SHYMAN process is a highly sustainable alternative and an economic opportunity for the nano-enabled market
IV. New Materials, Metrology and Development – increasing the scope of the process to manufacture an even wider portfolio of materials
V. Dissemination and Engagement with Industry - 7 case studies that demonstrate the performance and flexibility of the SHYMAN process in producing high quality nanomaterials
1 MODELLING AND REACTOR SCALE UP
Modelling was a crucial part of the project because it directly informed the design process for the scale up plant. The mixing regimes inside the reactor are crucial for the quality of the nanomaterials produced and to ensure that plant can operate continuously without blockages. Two different approaches were taken to understand mixing dynamics and how the mixing of the aqueous metal salt flow with the superheated water flow might be optimised at small scale, bench scale and full scale.
1.1 Pseudo Fluid Modelling
Continuous hydrothermal synthesis requires high pressures and high temperatures and therefore uses steel fittings and components, making visualisation of the flow mixing regimes impossible. However, visualisation is possible if transparent reactors seek to reproduce the mixing (mimicking the flow regime and flow ratios) but at ambient pressure and temperature. This process used sugar water to represent the denser (relatively) cold metal salt flow and methanol was used to simulate the less dense, super buoyant superheated flow. This approach allowed multiple flow rates and flow ratios to be observed and quantified2. Dye was dissolved into the downflow to enhance the contrast between the two liquids and enable image analysis processing to quantify mixing efficiency.
During the project the pseudo reactor modelling was adapted further to use ‘2D’ rubber templates inserted between sheets of polycarbonate plastic. One of the sheets of polycarbonate was custom fabricated with ports to allow the inlet and outlet of the pseudo fluids into the volume between the two sheets. This pseudo reactor represents a cross-sectional slice of a typical stainless steel supercritical reactor; the path length is constant in all regions which could then give improved detail of the mixing dynamics. it was discovered during testing that water, sugar water flows gave the same patterns and results as methanol, sugar water flows so methanol was no longer used (which made the modelling work cheaper and ‘greener’)
This modelling work allowed optimal conditions to be found for all scale of operation as well as an approximation of the jetting distance to be established. This jetting distance equates to the penetration of the superheated flow into the up-flow of cold metal salt solution. This is a critical part of understanding what might happen with the much higher flow rates (and Reynolds numbers) present in the final reactor configuration.
1.2 Computational Fluid Modelling
The counter current reactor was virtually recreated for the computational fluid modelling. In order to produce a workable computational model the geometry was simplified slightly before the mesh was employed in the computations. The number of cells was carefully analysed and optimized for size, minimizing computational expense while assuring the results are mesh-independent.
Pseudo fluid modelling is one of several methods for directly visualising the flow dynamics in reactors which involve different mixing geometries. In most cases, the flow and mixing of fluids under supercritical conditions are governed by fundamental equations for conservation of mass, momentum and energy. When dealing with turbulent flow, a suitable averaging method must be used. The density averaging technique, or Favre averaging, applies fluctuation to average values in lieu of actual flow parameter in order to derive a time averaged solution. To consolidate interdependent variables and reduce the number of unknowns, turbulent closure must be employed. There are different approaches to predicting turbulent flows ranging from RANS (Reynolds-averaged Navier–Stokes) to LES (Large Eddy Simulation) and DNS (Direct Numerical Simulation). This work is now published in Nano Research which is a high impact journal.
The jetting phenomenon was predicted using this new the CFD model which was particularly useful when considering the size of the reactor on the actual plant.
www.nottingham.ac.uk/~eczehl/SHYMANFR/SANDT.html
1.3 Neutron Beam Reactor Tests
As mentioned in the pseudo fluids section, it is impossible to visualise inside the steel reactor using standard techniques. However, after the start of the SHYMAN project, a Japanese group started to publish on the use of neutron beam imaging with supercritical water reactors. This work validated early work on reactor design (by the SHYMAN team). An opportunity presented itself during the project to collaborate with the Japanese group using the Nuclear reactor facility in Kyoto in January 2013. This approach was particularly effective in visualising the changes in mixing dynamics at different flow rates and flow ratios. The jetting distance was also visible using this reactor and this, in turn, validated the findings from the CFD and pseudo fluid model.
1.4 Final Validation of the Modelling Work
The models were all brought for validation and empirical work demonstrated that the models were indeed accurate. After this stage real nanoparticle samples were produced at bench scale and characterised carefully using HRTEM and additional image analysis tests to see how particle size was impacted by process conditions. Various process conditions were the simulated using the CFD and available kinetics data to create a predicted particle size distribution. This work was part of the Nano Research paper (DOI:10.1007/s12274-016-1215-6)
HIGHLIGHTS
• Neutron Beam work in Japan – to calculate jetting distances and fluid behaviour
• Two new reactor designs patented – with some potential advantages for high speed mixing
• CFD model completed – with specific mixing regimes mapped for higher flow rates
• Validation of the CFD-Pseudo fluid models – with good agreement
2 PLANT DESIGN, ASSEMBLY, COMMISSIONING AND OPERATION
The process itself can be represented in a simplified way as a pump-heat-mix-cool-depressurise-collect procress. This process was designed to operate under continuous conditions for a variety of inlet species and process conditions resulting in a wide range of potential products. Sustainability was optimised through water recovery (where possible), use of gas heaters (rather than electric), and by minimising the consumed energy (using a heat recovery network).
The following design criteria were used for the plant
Flow rate Maximum: 4.8 m3/hr Minimum: 1 m3/hr
Pressure Operating Pressure: 250 bar
Temperature Maximum: 450oC Minimum: 150oC
Capacity Minimum product concentration: 0.1 wt% Maximum product concentration: 1 wt%
Maximum capacity: 48 kg/hr dry nanomaterials Minimum capacity: 1 kg/hr dry nanomaterials
Target capacity for 100 tn/annum @ 6000hr/annum: 17 kg/hr
A hazards and operability study (HAZOP) is a structured and systematic examination of a planned or existing process in order to identify and evaluate problems that may represent risks to personnel or equipment, or prevent efficient operation. This study was paramount in producing the final P&ID and provided a large number of revisions to create a safer and more robust process. The method uses existing design information (PFD, P&ID, Mass and Energy Balances) to determine the causes, consequences, existing safeguards and action to be taken for deviations from the design intention. This process takes place at various ‘nodes’ throughout the process. This was the final stage before the initiation of the plant build. The initial site for this plant was in Warrington but due to restructuring and changes in priority with the host partner, a new site was found in Nottingham.
HIGHLIGHTS
• Design and construction of a CE marked high pressure gas boiler and heat exchanger system – necessary for the insurance of the plant
• Establishing a suitable site in Nottingham - mitigating against the withdrawal of Solvays Warrington site
• Construction of a chemical plant- at almost half the normal cost of a normal plant build
• Optimisation of the plants sustainability and process economics – with excellent OPEX values
• Potential maximum output of a plant at 1800 tons per year for some materials- +>100 tons with all materials
3 SUSTAINABILITY MODELLING
Assessment of sustainability and impacts on the environment of SHYMAN technology was an integral part of the SHYMAN project. In the framework of this assessment Life Cycle Assessment (LCA) method has played a pivotal role alongside CCALC© which is a methodology specifically for calculating the CO2 footprint of any given material or product. Life Cycle Assessment (LCA) is the most important analytical-information tool and allows users to assess the potential impacts product systems have on the environment throughout their entire life cycle. All associated factors are incorporated in the assessment, from raw material excavation, through the production and use phases, and until final disposal. No other tool provides such a comprehensive view of the product, or could prevent the transfer of environmental impacts from one stage of the life cycle to another. LCA methodology was standardised in 1997 by the International Standardisation Organization (ISO) in its ISO-14040 series. This tool is particularly valuable when seeking to improve the environmental impact of a given process, or when comparing the impact of one process over another for the same products.
The benefits of developed technical solution applications are quantified via various impact categories e.g. Cumulative Energy Demand (CED), Global Warming Potential (GWP), etc. This study has made extensive use of SimaPro© which, when connected to large life cycle inventory databases (e.g. Ecoinvent), can quantification of environmental impacts and the modelling of various scenarios within defined business case studies.
One specific example of where life cycle assessment was used for a selected material case study was for Self-Cleaning Coatings (SCC). ZnO nanoparticles enhance the hydrophobicity of the surface and photocatalytic coating applying photocatalysis for destroying undesirable microorganisms and airborne pollutants from the indoor environment. LCA was applied in the SHYMAN project on two levels, defined by the extent or reach of the evaluated system. The first level provides “cradle to gate analysis” of the SHYMAN process, which means from the raw feedstocks to the final nanomaterial product. The LCA approach allows any route to production of a given nanomaterial to be assessed against alternative routes and conditions (through the SHYMAN technology or with alternatives). In addition to the use of different precursors, mixing temperature was altered which can have a ‘knock on’ effect on the product quality and precursor conversion. In most cases (not just TiO2), higher temperature mean higher quality product and higher precursor conversion, but this will come at a higher environmental cost. Economic costs are not as easy to predict since quality of product may or may not impact on the final selling price. In most cases there will be an optimum process temperature whereby a majority precursor is converted and the product quality is relatively high (often quantified by crystalline/amorphous ratio), and in the case of the TiO2 precursors, the optimal conditions are quite varied.
The SHYMAN process is ranked among the methods with the medium energy consumption measured by means of CED (Cumulative energy demand) and takes into account the net energy for production of the feedstocks. The information from case study scenarios clearly shows how the choice of precursor can significantly affect the total environmental impact.
It should be pointed out that low variable technologies (e.g. sulphate and chloride process, Altair hydrochloride process) have lower CED than SHYMAN technology but in comparison with technologies with similar product flexibility (e.g. HT plasma, sol-gel...) the SHYMAN technology performs well in terms of CED and product quality. The same conclusion is valuable for Global warming potential. In general SHYMAN process has many advantages and overall has one of the lowest environmental burdens (when the best precursors are chosen).
The second, wider level of study provides a wider scope with “cradle to grave” LCA for selected product applications of nanomaterials. Besides CED and GWP, other criteria were defined for overall multi-criterion qualitative comparison of various production technologies. SHYMAN has high productivity, high quality, multiple material, medium/low costs and low consumption of process energy. The ability of the SHYMAN process to produce large volumes of multiple types of high quality nanomaterials at a reasonable cost makes this technology highly competitive on the market. The biggest challenge with a platform technology is therefore finding suitable applications for of these NPs and the second challenge (for LCA studies) is finding out process sensitive data from partners or industrial information for the compilation of a ‘cradle to grave’ study.
An example of such a cradle to grave study
Two very different possibilities of removal of undesirable microorganisms and airborne pollutants from the indoor environment of hospitals using air purifiers and photocatalytic coatings based on nano TiO2. Functional unit: Cleaning air in hospital – size of the room 300 m3 (100 m2) in one year.
For each cleaning alternative three variants were defined:
- For photocatalytic coating variants I, II, III represent different level of natural light in the room and the associated need for artificial lightning.
- for Air purifier variants I, II, III represent different combinations of air purifier regimes (heavy duty, light duty, economy) associated with different intensity of pollution and requirements for air purity. LCA study results show that environmental impact is highest for air purifier variant I (heavy duty regime) and lowest for photocatalytic coating variant III (minimal need for artificial lightning). There is a marked difference in environmental impact on the whole between the air purifier and the photocatalytic coating regardless of which variant is assessed. The major findings include: Photocatalytic coatings have an essentially lower environmental impact than air purifiers; Environmental impact levels in the use phase are significantly higher than in other phases; Environmental impact of photocatalytic coatings in the use phase can be lowered by the presence of sufficient natural light in the space; The impact of production of nano TiO2 from the SHYMAN process is negligible in comparison to impacts of the other life cycle phases for photocatalytic coatings, particularly the use phase. The benefits of nano TiO2 in lowering environmental impact are quite evident when compared to traditional air cleaning products such as an air purifier.
HIGHLIGHTS
• Development of a full cost model for the SHYMAN process - from cradle to gate
• LCA modelling of specific nano enabled case studies- from cradle to grave
• The favourable comparison of the SHYMAN process - against all other nanomanufacturing processes
4 CAPEX AND OPEX
CAPEX refers to capital expenditure and OPEX refers to operating expenditure. Both are important for new technologies since a high CAPEX (even with potentially low OPEX) would be considered to be a risky proposition for a company or investor. Low CAPEX and high OPEX could also be an issue for a manufacturer who would need to know that the products could be still manufactured at a competitive cost against other suppliers with different technologies.
In principle chemical plants can cost 4x times the value of the large capital equipment, which in the case of the SHYMAN project amounts process tanks, heat exchangers, pumps, heater, deionised water, blast cooler, filters, post processing pumps at approximately €715,000. There are more detailed methodologies for plant costings and from our calculations (a conservative estimate) €2 million euros would be needed to build the plant. In reality only €1.1 million was spent for the upstream and downstream sections of the plant, which meant that the design process was designed to be as cost effective as possible whilst maintaining safety. At the time of writing the initial proposal the cost of many items had to be estimated e.g. the boiler, since no such system previously existed. This does, however, have a positive message for potential end users who will see any new process with low CAPEX as a positive.
OPEX costs are material specific because all products require specific process conditions i.e. pressure, temperature, concentration, precursor type, conversion rate, flow rate, flow ratio. However, if precursor costs are removed from the calculation, it is possible to generate costs that take into account the variables of temperature and concentration. OPEX can be divided into different categories including gas (boiler), electricity (pumps) and water (the process fluid). These costs are affected by the use of heat recovery with a cooling tower, which changes the efficiency of the process significantly. However, it is the concentration of the process and the temperature of the reaction that have the most significant impacts. Clearly if the concentration of the final process flow (remember that continuous hydrothermal synthesis generates low weight loadings) is quite low i.e. 0.1% then the OPEX is €14/kg when operating at 380oC. If this concentration can be increased to 1%, which is more realistic for a process at this scale, then the OPEX drops to €1.4 per kilo, which make the process highly competitive against all other methods of nanomaterial manufacture. At 2.5wt% the cost per kilo falls to 50 cents.
At lower temperatures, the most significant cost is water. The water has to be deionised and this carried a net cost to the plant. As the reaction temperature increases, gas consumption becomes more significant than water. Overall OPEX appears to make a sudden increase around 360oC which is when near-critical water becomes supercritical and is caused by the changes in heat capacity and heat transfer at these conditions. It also highlights why all optimal conditions need to be set for any given material in order to minimise waste and environmental impact i.e. why run a reaction at 400oC for 100% conversion if operating at 350oC achieves 98% conversion?
5 DOWNSTREAM SEPARATION, CONCENTRATION AND EFFLUENT TREATMENT
One of the critical elements of the project was to ensure that waste water could be treated efficiently (in order to operate the upstream process continuously) whilst maintaining the ‘sustainable’ credentials of the process, but remaining within the project budget. Some of the initial ideas and designs for this stage were rejected as too costly and a refocus on the delivery of a more practical solution to problem. The process flow from the SHYMAN plant was designed to operate at flows of up to 1 wt % of solids, with the potential product specification being 10wt% or higher. The downstream or post-processing plant had to be capable of processing 4.8 m3h-1 and had to be designed to sit within a footprint of around 85m2 on the site of the SHYMAN plant at Genesis Park in Nottingham.
From observation of the behaviour of different nanomaterials produced hydrothermally at both lab and pilot scale, particles produced fall into one of two categories: ‘unstable’- particles that settle out from a liquid after a short period, and ‘stable’ – particles that remain evenly dispersed within a liquid after a sustained period. Two separate strategies therefore evolved during planning for stable and unstable product streams. For the unstable materials with higher settling velocities, the most cost and energy efficient separation method is settling by gravity. In order to keep the process completely continuous, a number of large volume settling tanks were required. The SHYMAN post-processing plant consists of three polyethylene 6.9 m3 settling tanks for normal operation during settling, as well as a fourth tank of the same size for contingency and overflow. This sizing means each tank takes around 90 minutes to fill when the plant is running at maximum output. All settling tanks are cone-bottomed, allowing for easy emptying of solid materials. Once a tank is filled, a high level of separation should be achieved in approximately 1.5 hours before being manually emptied to the product tank & waste by the operator. Initially the concentrated nanomaterial sediment is emptied out of the tank under gravity, before the waste water in supernatant is emptied, also via gravity. The arrangement on the tank outlet incorporates an in-line sight glass next to a manual three way switching valve, giving the operator a clear visual representation of when the effluent switches from concentrated material (for product tank) to waste water (for waste water treatment), so they can direct the flow accordingly.
Without testing the large scale tanks, it is difficult to predict accurate levels of separation, as this is based almost entirely on the visual representation of the flow as seen by the operator, however based on tests at smaller scale and current practices used at pilot scale, a final product weight loading of 10% should be easily achievable via settling alone.
Because stable products have very slow settling velocities, an alternative method of separation was required. After an early feasibility study, it was decided that filtration is the most cost and energy efficient choice for separating ‘stable’ particles from water. The SHYMAN post-processing plant consists of a six hollow fibre filter system. The filters use tangential flow technology, where water permeates through the pores in the filter fibres when the stream is under pressure of around 2.1 Bar. Filters pores are 5kD (1nm) in diameter, therefore allow nanomaterials to remain in the retentate.
In order to maintain sufficient pressure, a pneumatically actuated pinch mechanism pressure control valve is fitted on the retentate outlets of the filters. This is controlled via a pressure transducer on the pump-side of the filter. The calculations required for this final design relates to total flow rates, and surface area of the filters themselves.
Following the recommendation of project partners and the local water authority’s guidelines (Severn Trent Water), the main objective for the water treatment system is to provide achieve a neutral pH level in the effluent water from what could be potentially very acidic (i.e. Aluminium Oxide Hydroxide, pH<1) or basic (i.e. Silicon (IV) dioxide, pH~11) process water. The SHYMAN plant waste water treatment system consists of 4 tanks all of 1m3 capacity. This includes 1 buffer tank, and a triple stirred-tank weir system. The weir system allows for 2 rounds of dosing with 32% HCL and/or 32% NaOH as required and a final pH check before the waste water can be sent to the drain. Using LTH MXD73 pH monitoring and dosing technology, this system ensures all effluent leaves the plant within the required pH window (6-9).
Initial recommendations during the early stages of the SHYMAN project included vacuum evaporation and NH3 stripping which have not been implemented within the water treatment system for practical and environmental reasons. However the ability for re-direction of supernatant for filtering (should suspended solids be high) has been designed into the plant.
The final product tank is a 6.9m3 cone-bottomed tank, exactly the same as the settling tanks. Its purpose is to store concentrated material that has been through the post-processing system, and should theoretically be ready to be transferred into an IBC container via P-410 and shipped, or be taken for further processing.
Overall this project has shown that it is possible to build a universal down-stream product-refining system for the hydrothermally synthesized nanomaterial process on the SHYMAN WP8 plant’s scale, with a small budget.
HIGHLIGHTS
• Online DLS monitoring system – allowing real-time measurement of the nanoproducts
• Real time waste water effluent treatment – allowing continuous plant operation
• The ability to increase weight loading from 1% to 10% in real time during operation – to formulate products continuously without stopping production
• Cost effective water processing – simple and continuous neutralisation system prior to disposal
6 CASE STUDIES
6.1 Healthcare
The aim of WP4 Case Study 1 was to investigate the potential of the nano-hydroxyapatite (nHA) manufactured using hydrothermal synthesis for healthcare applications. In particular, the focus of this case study was to use nHA in the manufacture of synthetic bone graft substitutes in paste and block form. Synthesis protocols were adjusted in order to produce nHA particles within the threshold level for pH, conductivity and endotoxins for paste formulation. Several samples of bone pastes from nHA platelets were produced and these were then taken forward for indirect and direct biocompatibility assays in vitro in Rat Bone Marrow cells. It was demonstrated that the cells cultured in direct contact with the SHYMAN pastes had a reduced biocompatibility when compared to the commercial control (ReproBone® novo). It is important to note that in vitro data does not always reflect the in vivo response. Whereas, cells cultured with in-direct contact (use of pre-conditioned media) showed a much improved biocompatibility. It can therefore be concluded that the pastes have demonstrated potential for use in bone repair although further investigation would be needed to take this product forward prior to commercial production.
A second healthcare related case study manufactured samples of Platinum (Pt), Silver (Ag) and Gold (Au) nanoparticles which were then structurally characterised. The most promising samples were taken forward for in vitro cell testing. Samples of stabilised Ag NPs were produced by PROM and were found to pass through a syringe filter, which indicates that the particles are stable and not aggregated. The filtering process also sterilises the sample to a degree, by removing impurities. This sample was carried forward for in vitro cytotoxicity tests in two human cell lines - healthy cells (Human dermal fibroblasts) and tumour cells (Human Pancreatic Carcinoma cells). It was found that the Ag NPs were not toxic to these cells under the conditions tested.
6.2 Printed Electronics
A range of different materials for various aspects of printed electronics were tested within this Case Study. Initial tests investigated the use of sulfide materials with the aim of increasing the efficiency of organic photovoltaics. Subsequent tests focussed on Indium Tin Oxide (ITO) for the application of transparent electrodes. Here, promising sheet resistance values were obtained but the haze of the coating was above the accepted threshold. This could certainly be improved with changes to the formulation of the ITO slurry. Final tests focussed on the use of Zirconium Dioxide (ZrO2) for use in transparent coatings with a high refractive index. Three samples of ZrO2 in PGMEA (at up to 20 wt% concentration) were coated onto glass substrates. It was found that all samples produced transparent and homogeneous coatings, indicating that no particle agglomeration had occurred. At this stage, the spectra obtained from UV-Vis spectroscopy showed no differences to uncoated glass, indicating the coatings had not densified or percolated enough so further optimisation work is required to either increase the weight loading or increase primary particle size.
6.3 Enhanced Polymers
Initial tested focussed on introducing nanomaterials into polyurethane foams prior to the foaming process by dispersing nanoparticles into polyols. It was found that, by using a silane capping agent on the NPs, dispersion of SiO2 particles into the polyol could be achieved up to 2000 ppm. Homogeneous foams were produced but no improved effects were found for the properties tested. Higher weight loadings might have been an answer. The focus then changed to nano enhanced polyols for coatings, adhesive and sealants. Here, SiO2 particles were introduced into alternative polyols (used for coatings rather than foams).
6.4 Optical Devices
This case study focussed on the potential use of nanomaterials with photoluminescent properties for use in car headlights. The aim in this study was to produce nanopowders which emitted visible light covering the entire white light spectrum, when excited with light in the UV range. Samples of Yttrium Aluminium Garnet (YAG), Cerium-doped YAG, Europium-doped ZrO2, Gadolinium-doped ZrO2, ZnO, and Copper-doped ZnO were produced and tested. The most promising result was found for Europium-doped ZrO2 particles, where emission in the visible light range was detected. Nevertheless, the emission intensity was still lower than that of commercial phosphors which probably relates to the particle size and the problems with obtaining high intensity emissions from nanoparticles. One solution might be through the sintering of the SHYMAN materials to create large clustered particles. Sintering is not an expensive or complex step so a route to market with these nanomaterials definitely exists but with some small post processing stages prior to use.
6.5 Coatings
This Case Study looked into the introduction inorganic nanomaterials into PVDF paints to increase the hydrophobicity, in order to produce self-cleaning coatings for architectural surfaces (e.g. bridges, building facades). Samples of hydroxyapatite, TiO2, SiO2, CeO2 and ZnO were manufactured and then incorporated both the treated and untreated particles into their paints. The paints were coated onto panels and tested for abrasion, adhesion, thermal stability and weathering. All samples met the requirements under the standard adhesion and abrasion tests (set out by the American Architectural Association, AAMA 2605) but the HA, TiO2 and CeO2 samples showed poor thermal stability. The most promising results were observed for surface-treated ZnO particles which were thermally stable and significantly improved the water contact angle of the paint, so were tested under weathering conditions. The weathering data showed no significant changes to the gloss or colour of the paint after 5000 hours of UV and humidity exposure (simulated in a weatherometer). SiO2 and TiO2 particles were also tested in a different PVDF paint formulations (water based rather than solvent based). The TiO2 particles showed yellowing in the paint but the SiO2 particles were shown to significantly improve the WCA of the paint even without any surface modification. A second coatings case study studies a wide range of nanomaterials, with the aim of improving the chemical or mechanical properties or automotive coatings. These have included SiO2, ZrO2, Ce-doped ZrO2, Fe2O3, BaTiO3 and hydroxyapatite. With the exception of SiO2, these materials were introduced with the aim of imparting anti-corrosion properties to the paint; unfortunately, it was found that, at the concentrations tested (up to 500 ppm), no differences in these properties were seen. Nano SiO2 was also introduced into the automotive clearcoats to increase the hardness and scratch resistance of the coating. Initial SiO2 samples were produced in methanol and xylene but these samples gelled before they could be tested. A formulation route was achieved through phase transfer of SiO2 particles into xylene. This material was successfully incorporated into a coating formulation without any particle sedimentation observed. Nevertheless, the haze of the resulting dispersion was too high (i.e. not transparent for a clearcoat) so could not be tested further. A final polymer based case study introduced nanomaterials into polypropylene (PP) to produce nanocomposites which have enhanced flame-retardancy or UV-resistance properties, for use in vehicle dashboards. PROM produced several samples of coated and uncoated Titanium Dioxide (TiO2), Zinc Oxide (ZnO), Aluminium Oxide Hydroxide (AlOOH) and Layered Double Hydroxides (LDHs), which were then compounded and tested. The most promising results for UV-resistance was found to result from a 2.5 weight loading of nano TiO2 in PP. For flame retardancy, when Mg-Al-CO3 LDHs were added into PP with a graft stabiliser at a concentration of 2.5 wt%, the burn rate improved by over 50 % compared to blank PP.
HIGHLIGHTS
• The SHYMAN process was shown to be highly flexible - creating new materials and new formulations for each case study
• A majority of the case studies were able to successfully create a commercially viable product - with all case studies providing a way forward for a materials in development
• A successful shift from bench to pilot to full scale manufacture for each target material – all materials have proved to be scalable
7 NEW MATERIALS DEVELOPMENT
The SHYMAN project also provided the opportunity to create new materials using continuous hydrothermal and solvothermal synthesis. The main objective of this activity was to increase the scope or potential impact of the process by increasing the scope of range of materials that were possible through the technology. The list below show materials been made (for the first time) using continuous hydrothermal/solvothermal routes.
I. Sulphides – including CdS, CuS, FeS2, PbS, Bi2S3, ZnS and MoS2
II. Metal Organic Frameworks – including ZIF8, MIL53, MIL101, HKUST-1, NOTT300 UiO-66.
III. Mixed metal oxides – BaTiO3, SrxBa1-xTiO3,
IV. Doped Metal Oxides - Co-TiO2, Ni-TiO2
V. Phosphates – including LiFePO4, LiMnPO4
VI. Layered double hydroxides – including Ca2Al-NO3, Mg3Al-C3O, Mg2Al-CO3, Co3-Al-CO3, Co3-Al-NO3, Hybrids, TiO2@Mg2Al-CO3, TiO2@Co2Al-CO3, Co3O4@Mg2Al-CO3
VII. Metals – including Ag, Pt, Pd, Au, Ni, Cu
7.1 Sulphides
As mentioned above, many different metal sulphides have been produced and in different morphologies from 2D hexagonal platelets to 3D tetrapods during the course of the project. This was achieved by altering the process flow setup to either allow both precursors (the metal and sulphur source) to mix before the reactor, or by preheating the sulphur source in the superheated downflow. With Cd++ and thiourea in the upflow into the reactor resulted in cadmium sulphide with a mixture of 11% cubic hawleyite and 89% hexagonal greenockite phase CdS,. The TEM images of this product reveal a mixture of rod and multipodal morphologies, with several clearly defined tetrapodal nanoparticles with 40 nm diameter cores and 100 nm long arms.
www.nottingham.ac.uk/~eczehl/SHYMANFR/SANDT.html
7.2 Metal Organic Frameworks
In recent years novel methods for synthesising MOFs have been reported such as microwaves, ultrasound, and mechanochemical synthesis which can benefit from reduced synthesis times and easier post-processing of products; however, none of these techniques have been adapted for the continuous production of MOFs. There are stil only a few reports for the continuous production of MOFs. A first article was published in 2012 (at the start of the SHYMAN project) showing the continuous synthesis of HKUST-1 and CPO-27(Ni). Since then Schoenecker et al. have reported a continuous process for the synthesis of UiO-66 using their patented reactor which uses batch technology with an integrated flow system to allow for the removal of products and introduction of reagents in situ.
Many groups have reported the hydrothermal synthesis and continuous synthesis of ZIF-8, but to the best of our knowledge, none have reported the continuous hydrothermal synthesis of ZIF-8. We used the SHYMAN reactor technology to synthesise HKUST-1 and CPO-27. We also used the continuous process for ZIF-8 in a purely hydrothermal system. This lab-scale process was shown to be capable of producing over 200 g per day of activated ZIF-8. Using the internal volume of the rig (55 mL), the space-time yield for this method was calculated to be 3,875 kg m-3 per day, which is a significant increase on values which have been reported for other process technologies. The SHYMAN pilot system was then used to demonstrate production at ~6 kg per day. Characterisation of the products synthesised using this technology showed that the materials have similar properties as batch-produced materials, making this a viable industrial method for producing ZIF-8. We have now published a review of the progress made by researchers across the world in using continuous reactors to produce MOFs, since its inception at the start of the SHYMAN project.
As mentioned in the initial section, different MOFs have been produced in the last 3 years using the SHYMAN process but in addition to the MOF work, other work was undertaken to see if MOFs could be manufactured and activated in a single process. Activation remains one of the major hurdles to scale up and industrial take up. The use of ethanol, instead of diluting with more water, was necessary as the as-synthesised ZIF-8 forms a very stable suspension in pure water which cannot be centrifuged efficiently. The successful activation of all the ZIF-8 samples and the fact that the activation rig can be easily connected to the synthesis rig shows that this method is a viable technique for industrial production which could dramatically cut post-processing times. This report demonstrates the large-scale production of ZIF-8in a continuous hydrothermal system. More importantly this work shows a route to the one-step continuous synthesis and activation of these materials. The ability to activate the material in situ will reduce time and cost of full-scale production. This method represents a viable industrial method for the production of activated ZIF-8.
7.3 Doped Oxide Materials
Doping oxides (away from their pure form) can drastically alter properties such as particle size, crystal structure and UV absorbance properties. Some work was undertaken to see how the photocatalytic performance of TiO2 could be improved through doping. The crystallite diameter of pure anatase TiO2, as calculated using the Scherrer equation, is 15 nm. Doping TiO2 with cobalt or nickel resulted in sizes of ~ 6 nm. Surface area analysis of the samples showed all three samples to have typical Type IV isotherms with H2 type hysteresis loops indicative of mesoporous aggregates. The calculated BET surface area of the undoped anatase was 128 m2 g-1 while the smaller doped samples both showed surface areas of ~ 230 – 250 m2 g-1, consistent with the smaller particle sizes calculated from the XRD and observed by TEM.
The absorbance profile of the undoped titania was as expected, showing a sharp decrease in absorbance immediately below 400 nm, corresponding to the anatase band-edge, followed by a tail off in absorbance with increasing wavelength. The 1% cobalt doped sample showed a similar profile at low wavelengths; however it also exhibits additional absorbances across the 400 nm to 700 nm range, due to the d-d transitions of the cobalt ions. Similarly the 1% nickel doped sample showed gentler tail-off up to 540 nm and an additional absorbance at 720 nm arising from the characteristic 3A2g → 3T1g transition of octahedrally coordinated Ni(II). These materials were also tested for applicability as nanocatalysts for the photoreduction of a dye. The doped ceramics were shown to have a higher activity that the non-doped TiO2.
Barium Titanate was discovered in the early 1940s as a capacitor material to replace mica. The flexibility of the perovskite structure is such that a wide range of metal cations may be accommodated, particularly in the A position. With respect to barium titanate this allows significant variation in composition, with barium easily replaced by alternative M2+ ions. One of the most common substituents is strontium – a smaller Group 2 metal ion. The full phase diagram of Ba(1-x)SrxTiO3 from x = 0 to x = 1 is known. It has been shown that increasing strontium content stabilises the cubic phase (as mentioned above SrTiO3 itself adopts the cubic perovskite structure at room temperature). This substitution has the effect of altering the ferroelectric properties of the base BaTiO3, allowing fine tuning to suit the desired application. Elemental analysis by ICP shows that, in all cases, the total M2+:Ti ratio is significantly lower than desired, varying between 0.8 and 0.9. Given that presence of MCO3 species were observed in each material and removed in the washing step this lowered M2+ content is to be expected. It is also worth noting that the strontium is seemingly more prone to being incorporated into the perovskite structure than barium, with all mixed Ba(1-x)SrxTiO3 samples showing significantly higher higher Sr:Ba ratios than expected, suggesting that where both M2+ ions are available barium is more likely to form the carbonate and be removed. The pure SrTiO3 sample does still show a low Sr:Ti ratio of 0.81; however, which indicates that carbonate formation remains an issue for the generation of strontium titanate.
A final area for the new materials discovery was in battery materials, which lead to the development of lithium iron phosphate (LFP) and lithium manganese phosphate (LMP). Opportunities arose for collaboration with Tohoku University in Japan on batch synthesis and additives to assist particle formation (Jan 2014) and also Sungkyunkwan University on coin cell development and testing (April 2015) which meant that the SHYMAN materials could be fully evaluated. The use of additives such as citric acid, and ascorbic acid was found to improve and control particle size and shape during batch experiments and this was carried forward to continuous tests on the SHYMAN rig. The lithiation process was found to be a key controlling step in the production of LFP whereby residence time was the key to ensuring that all iron phosphate is converted to lithium iron phosphate.
These two factors (additives) and the use of a longer reactor were used to create LFP that was taken forwards for coin cell testing. The experiments demonstrated a clear correlation between increasing residence time (in the reactor) and performance. This linked to the findings around residence time and degree of lithiation. An optimal residence time was identified to create the best LFP and a rig was purpose built to produce this material. Coin cell tests are ongoing.
One additional finding was the improvement in capacity with increasing crystallinity and carbon-coating. This suggests that the new materials (with an increased residence time) with an additional formulation step to allow in situ carbon-coating may allow the direct and scalable synthesis of high performance lithium iron phosphate nanopowders.
HIGHLIGHTS
• An increase in the portfolio of materials - including sulphides and metals
• Work on the mechanisms of LFP and LMP formation - and subsequent performance testing of materials
• Expansion of the portfolio of MOFs – and development of online activation of the MOFs
• Pilot scale and full scale production of new materials- all developed initially at bench scale
• Demonstration of the doped metal oxide nanomaterials - as UV photocatalysts and battery materials
Potential Impact:
IMPACT ASSESSMENT
The main aims of the SHYMAN project were to;
A. Scale up the continuous hydrothermal process – the output has increased 1000x from the pilot reactor scale.
B. Reduce the carbon footprint – LCA has shown the process to be highly sustainable compared with alternative technology
C. Reduce processing costs - the process can now operate and produce a 10wt% solution continuously and manufacture at approximately 5 euros per kilo
D. Create new materials – the materials portfolio has increased to include, metals, metal sulphides, metal organic frameworks and hybrid nanomaterials.
E. Increase efficiency of application - decreasing the need for excess nanomaterials with high dispersion rates
F. Improve nano-manufacturing safety – toxicology results are excellent, product formulation has been established to allow liquid dispersions to be maintained during processing, thus avoiding the need for handling of any dry powders.
The SHYMAN has achieved all these aims during the course of the project as highlighted in the S and T section.
www.nottingham.ac.uk/~eczehl/SHYMANFR/IMPACT
SOCIO ECONOMIC IMPACT
The ambition was to extend a proven platform technology (at bench scale) in the form of continuous hydrothermal synthesis and scale the process to industrial scale. This scale would have to be a minimum of 100 tons per annum to demonstrate industrial relevance. In reality the project has been able to push a high value low volume process into the industrial region (nominally low value and low quality) by creating a high quality lower value proposition. The plant will never compete with the nano-TiO2 pigments market, at €2 per kg, but it does increase the ‘reach’ well beyond the anticipated €30-50 per kg market.
A more interesting quantitative economic analysis, is the impact on cost of production from the bench scale system (that was available at the start of the SHYMAN project) compared to the development and optimisation of the pilot scale, the pilot+ scale and the final full scale SHYMAN plant. The production costs for each scale of the SHYMAN technology has been approximated and shows the net improvement in techno-economic ‘reach’ for production vs the over commoditised pigments sector. The SHYMAN process enabled us to increase the scale of production 1000x beyond the state of the art (pilot) and 50,000x beyond the original bench scale production.
The impact on the market made possible by the SHYMAN project, will be seen over the next 3-5 years as commercial production begins. Commercial operation was clearly not possible during the lifetime of the project, but the ability of the process to manufacture materials that are relevant to diverse market sectors now provides a significant opportunity. The production of metals, metal oxides, sulphides, phosphates, hydroxides, carbonates, metal organic frameworks all prove that the process is a platform technology. Promethean Particles has estimated a 2 fold increase in staff in the next 18 months as a result of the SHYMAN project. The use of case studies has also shone a spotlight on the opportunities in markets that include: healthcare – through diagnostics and bone materials; printed electronics – through conductives, semi-conductives and high refractive index materials; polymers – through flame retardant, scratch proof materials; photonics – through luminescent materials; coatings and lubricants – through UV resistant and superhydrophobic materials.
Nano enabled markets are still rapidly increasing; In coatings the current global smart coatings market ($363 million) is expected to grow at almost a 50% Compound Annual Growth Rate. It is therefore expected that this market will reach almost $3 billion by 2018, and $6 billion by 2020. Two of the sectors where superhydrophobic coatings can be applied, self-cleaning and anti-corrosion, are expected to reach $1.4 billion and $449 million, respectively, by 2018. The global market for printed and thin film electronics was estimated at around $9.5 billion in 2012 (42.5% of that will be predominately organic electronics - such as OLED display modules). By 2022 the market will be worth an estimated $63 billion, with 45% printed and 33% on flexible substrates. In 2009 the global battery market was estimated at $47.5 billion and predicted to rise to $74 billion by 2015. This predicted growth was attributed to the high demand for secondary or rechargeable batteries. Lithium-ion batteries account for the largest market share of the secondary battery market with an estimated 37.9%. This figure is expected to increase into 2020 as new improved environmentally friendly lithium-ion batteries with decreasing costs replace older technologies which have maximised their potential. In relation to healthcare the global market for synthetic bone graft substitutes is expanding and is expected to rise from $2.1 billion in 2013 to approximately $2.7 billion by 2021. This is due to an increase in procedures due to the aging population and a shift to the use of synthetic materials over autograft (the patient’s own bone). Cancer treatment and nano-enhanced diagnostics, where the value of the products enhanced with nanoparticles will almost equal the oncology market estimation for that period, has been estimated to reach €117-147 billion by 2018. In nano-enhanced polymer systems such as flame retardant polymers the market is still developing and demand is growing; global demand for conventional flame retardants is projected to expand 4.6 percent per year through to 2018 to 2.8 million metric tons, valued at £4.5 billion (Freedonia, 2015). The world-total LED revenue will be saturated soon and may even start decreasing as a result of a significant increase of LED efficiency, long life-time of the devices and price-drop.
SHYMAN has indeed had an impact on the SMEs within the consortium, from two significant aspects: Internally, the access to the network of excellence of the main partners in the project allowed these small companies to be in direct contact with the most advanced developments and knowledge in the field; the potential gains -both tangible and intangible- could not be expected by the sum of all the individuals partners activity. Externally, partnering such a relevant consortium has added value to all 7 SME’s. Each SME has been able to promote their involvement in the project this increasing the confidence any third party could request for our capability of managing complex projects. Both aspects are really difficult to achieve for a spin-off company with no track record as an organization. Also, in essence participating in this project has placed many of the SMEs on the map of European nanotechnology research.
Before the SHYMAN project started, there was only one global competitor using hydrothermal synthesis called Hanhwa. This Korean company developed a 600 ton per year plant for LFP production, for battery applications. The plant (seemingly) was only able to manufacture LFP and the markets became highly competitive over the last four years with Chinese manufacturers dominating the market, either for cost or quality reasons. This plant is no longer in operation. If the SHYMAN plant proves to have an output of over 1000 tons per year, then it will remain the world’s largest continuous hydrothermal plant for many years to come. As such, the SHYMAN project has placed an EU consortium at the forefront of world nanomanufacturing and given the technology sufficient traction to create considerable global interest. This has generated EU jobs in an emerging market place where new IP generation (around the process and products) now form a strong platform for global manufacturing. The SHYMAN project has enabled the technology to be scaled to an industrially meaningful level whilst demonstrating that it is a low cost, high quality alternative to existing nanomanufacturing processes. As a result, the SHYMAN project has guaranteed EU jobs and not just income for EU companies.
WIDER SOCIETAL IMPACTS
As mentioned above, the scope or reach of the technology means that many materials and products can be made using nanomaterials from the SHYMAN plant. The diversity of market sectors that have direct societal implications, from cancer therapies to sunscreens and enhanced fabrics to flexible electronics. All these market sectors impact on society on a daily basis. The most significant impact of the SHYMAN project is probably the creation of a new industrial scale plant that can create high quality nanomaterials using a highly sustainable process i.e. using water as a solvent, high levels of recycling ad with very efficient heat recovery. All of these aspects make the process and the plant environmentally sound for a society that desperately needs to ‘do more but use less’.
Fortunately nanotechnology hasn’t been identified by the general public as the next ‘GMO scare story’ i.e. something that creates an irrational fear that overshadows any net benefit. As mentioned previously the wider societal impact is measured by a positive attitude towards nanotechnology as a potential means of achieving more effective products, processes in a more sustainable society. A positive public perception of the benefits of nanotechnology can only be achieved through better education about nanotechnology, and the measures that are taken to ensure that nanotechnology is safe and sustainable. The SHYMAN project has allowed many promotional videos, public lectures (to adults and children), blogs and tweets to promote nanotechnology. The videos have had over 250,000 hits during the lifetime of the SHYMAN project predominantly from the general public.
Through attendance at many conferences, tradeshows, the publication of conference and journal articles and student participation (through interns, design projects, R&D projects) the SHYMAN project has have a significant impact on the academic community This should be regarded as seminal work that forms the foundations on which further progress can be made i.e. it is probably true to say that continuous hydrothermal synthesis is still in its infancy with the potential to move from first generation nanomaterials to second generation (more complex, hybrid, multifunctional) production.
The use of the case studies within the SHYMAN project has been an effective means to assess and create impact within the business community. Each case study has allowed key nano-enabled markets to be evaluated and a plan of action to be established. The creation of the plant itself has created considerable interest and curiosity outside the project within the business community. The end of the project will see more engagement with these potential end-users.
MAIN DISSEMINATION ACTIVITIES
Partners have attended around 30 conferences during the course of the project and around 50 papers have been presented on the technology, the scale up developments, the products from continuous hydrothermal synthesis, the life cycle assessment of the process and examples of where LCA has shown the SHYMAN process to be highly sustainable. Many of these presentations were given as invited, keynote or plenary lectures. Around 15 new animations and videos were created to explain the technology and how continuous hydrothermal synthesis works. Academic partners have been successfully publishing journal articles and writing conference proceedings (with acknowledgement to the SHYMAN funding). This has resulted in around 20 journal publications with as many again in preparation for submission in the next 12 months.
Partners from the SHYMAN project have published more than 25 papers across a diverse set of disciplines and many as joint publications, with many more in the pipeline (so to speak). These include Reactor Design and Simulation; New Materials Discovery; Characterisation and metrology; Life Cycle Analysis;
The SHYMAN website (www.shyman.eu) has had over 10,000 visits during the 4 years and the videos posted on the video diary page (mainly accessed via YouTube links) have had over 250,000 views. The Project coordinator gave several radio interviews on nanotechnology and it’s significant in society. PR produced a private data basing site for the SHYMAN project to store the details of all metrology data for all the samples produced by all the partners. He also produced a public facing website that has had over 140,000 hits for scientists seeking to use his XRD interpretation program.
VLCI presented some of their WP3 work at the European coating congress, gaining a lot of interest. The audience was around 100 people, including people from Evonik (they have the nano-TiO2 on the market and was benchmarked). Exploitation potential for VLCI has also been furthered through contact with Lubrizol, the supplier of the stabilizer for the new nano-TiO2 used in the WP3/4 case study with Repsol.
During the course of the project we estimate that over 1000 students (chemists and chemical engineers) have engaged with the SHYMAN project through workshops, lectures, and design tasks relating to the design of the full scale process. One of the early design challenges for the chemical engineers was a preliminary heat and mass balance of the SHYMAN process at the same flow and production rates for making nano ceramics. A week long summer school was run in May 2014 at the University of Valladolid attended by 31 participants from 9 countries. 18 lecturers from 6 different countries attended and presented at the summer school. Some attendees actually went on to take up positions as interns, placement students and were involved in the SHYMAN project directly as researchers.
EXPLOITATION OF THE RESULTS
The most significant exploitable result from the SHYMAN project is the full scale plant in addition to some successful case studies. PROM has been involved with the build and operation of the full-scale plant. It is now fully operational with significant exploitation potential in the plant which will be used to manufacture large quantities of nanomaterials for consortium partners and external users. Furthermore, the research and development work being conducted at PROM at bench and pilot scales can be disseminated to the wider scientific community to publicise PROM’s capabilities. PROM has a full commercial plan to exploit the outcomes of the SHYMAN project by using the data generated during the project in sales and marketing activities; using technical progress to inform new product lines and using the full scale plant as a commercial manufacturing facility.
Connected to the point above, the tangible potential gain is the possibility to promote current products and applications inside the consortium and to identify new opportunities to exploit. Thanks to the diversity of the partner's activity in the project, unexpected areas of applications have arisen including, new lubricants, flame retardant materials and metal organic frameworks. Additionally, possible collaborations for new projects to be exploited together with other SMEs in the consortium can be explored for complementary know-how that we would not have considered without the close and durable communication that partnering facilitates. A H2020 project around the production and use of nanoporous materials was submitted 18 months ago (called SPONGE) which proposed 6 new pilot line production facilities, all enabled by the SHYMAN plant and PROM. The project was highly rated and considered ‘fundable’ but did not proceed. Many of the SHYMAN partners were part of this proposal.
Exploitation of any information on nano safety protocols, which arise from SHYMAN, or in collaboration with the FP7 project NanoMILE and H2020 NanoFase, will come through the European Commission and hopefully used to inform governing bodies particularly in the field of nanosafety and nanotoxicology. There is increasing interest from industry in the SHYMAN plant and associated technology and as policy makers include many industrial partners e.g. the BASF Dialogforum events, it is hoped that further exposure will be possible. The XRD ‘translator’ and database system from PR will hopefully be able to highlight (to EC policy makers) that experimental data created using taxpayers money should be made public, in the same way as open access journals.
With Ceramisys there is potential to exploit the use of nano-hydroxyapatite particles in pastes and porous blocks however at present they have not yet been proven to provide added benefit over the current products manufactured by Ceramisys. In addition, the in vivo data required to verify any significant benefit was not proposed as part of the SHYMAN project. If, at the close of the project, it is decided that there is sufficient potential for the new materials CERA would have the expertise in regulatory approvals and commercialisation of medical devices to take products to market, however, this would be a lengthy process (approximately 2-4 years post project) as additional studies (including in-vivo studies) would need to be carried out. One of the main benefits of the CERA case study would be that PROM have made improvements to their HA manufacturing process, in particular in water quality and post-processing, in order to achieve a suitable medical grade product for implantable devices. This will allow PROM to approach medical device manufacturers in a number of clinical areas to exploit the high quality nano-hydroxyapatite slurries.
At present, TopGaN is moving towards pilot line construction, what then would lead to the formation of a factory. Such a factory would be essential for mass-manufacturing of white-lamps. In parallel, TopGaN is applying for the EU Project (ECSEL) leading a consortium of lighting manufacturers (including the big company Valeo). This Project (WhiteGaN) has a goal to make a feasibility study if solid-state lighting can be based on LDs, instead of LEDs. If both (large LD factory construction and showing an advantage of LDs over LEDs) plans are realized (2017-18), TopGaN would need a large scale supplier of the luminophore for the white-lamps. Promethean Particles could be such a supplier in future, however, still some further research is necessary to get luminophore luminosity at least as good as it is for the commercial products from the Far East.
Pielaszek research may expand its database services and characterisation tools to become an EU platform. It was already proposed to be used by Eu JRC in Ispra and discussions are underway with EC officials towards establishing a database for experimental data gained during EC-funded projects. It is unfortunate that the vast majority of experimental evidence is wasted, except for a small fraction that is used in scientific papers. We think experimental data obtained from public money should be made available back to the public, after IP concerns are resolved. Sample DataStore is a possible solution here (it may handle IP relations), so it’s possible that the scale of exploitation may appear much larger than expected.
The main objective of the Shyman project was the development and operation of a full scale nanoparticle reactor for industrial exploitation alongside several case studies with end user partners. This plant is going to be crucial for the future needs of any partner requiring large quantities of our nanomaterials, so most partners in WP4 are the same time collaborators and future users of the foreground of the project. Promethean will assess the use of foreground developed on the manufacturing process in line with commercial priorities. Case study partners who have developed foreground IP on particular materials may well wish to exploit their results by commissioning commercial manufacture of those materials using PROMs facilities including the large scale manufacturing facility at the end of the project.
PROM’s main role in SHYMAN has been the production of nanomaterials for case study partners (in WP4) to test. As such, the main users or stakeholders have been the case study partners themselves, or partners analysing and characterising the materials, so has not required the involvement of groups outside the consortium in this respect. Dissemination of the work and results through journal papers or presentations and trade shows have drawn the attention of other potential users in the future; in this scenario, they’re involvement will be considered and the whole Consortium will be informed. Other stakeholders such as policy makers, regulators and trade associations are being kept informed as the project develops through informal networks and meetings. In addition PROM have interacted more formally with the wider community as outlined below. Dissemination of the project outcomes to the general public has largely been the responsibility of UNOTT; however, PROM have actively participated in the production of a number of YouTube videos designed for a lay audience
TopGaN is just one of potential users of nanopowder luminophores produced by Promethean Particles. The others are LED manufacturers include Osram, Nichia, Cree, Lumileds, Samsung, etc. This market is now being evaluated and will be presented in Deliverable 4.7. IHPP is already collaborating with a company to use ZnO nanoparticles as an antibacterial agent. Success in the development of such fabrics would require scale up of production. This would be through SHYMAN partners and PROM in particular. ENDOR is also partnering a Tempus project (http://www.wimb.fink.rs/) to disseminate nanotechnology through university degree students in three Balkan countries, granted by the European Union. In their presentations the SHYMAN project has been used as an example of how academia and industry collaboration can lead to the technology transfer of know-how into society.
In addition to SHYMAN, PROM is a Consortium partner of the FP7 project NanoMILE. Co-ordinated by The University of Birmingham, NanoMILE is focussing on the interactions of nanomaterials with living systems and the environment. In particular, NanoMILE assesses any adverse effects on living organisms or the environment when they’re exposed to a range of doses of nanomaterials. From this, the pathways and mechanisms can also be studied. PROM has bridged a link between the two projects, by sending nanomaterial samples and waste water samples produced for SHYMAN to partners in NanoMILE for analysis. Any toxicity data generated from this can then be fed back into SHYMAN, to better understand how the nanomaterials should be handled, treated and disposed of. This work has also led to broader interaction with the NanoSafety cluster and through these projects PROM is an active partner in the NanoFASE consortium (H2020; project kick off Sep 2015) looking at the environmental fate of nanomaterials. TopGaN submitted the WhiteGaN proposal (and is starting work with UK companies (Optocap, CST) the Eurostar project GaNbar, which will develop highly efficient laser diode arrays (bars) which could be used for producing white-light emitters.
UNOTT, PROM and CERA are all now working in a Medical Devices Network called The Centre for Innovative Manufacturing in Medical Devices researchers and develops advanced design and manufacturing methods for the Class III, musculoskeletal medical device sector. (www.mede-innovation.ac.uk). This project has allowed information and know-how from the SHYMAN project to be exploited through the development of new formulation hydroxyapatite products that are bio-resorbable or 3D printable.
List of Websites:
www.shyman.eu is the public facing website to promote the project during the 4 years. This site has also been secured for the next 2 years in order to continue to act as a source of information for any interested viewer.
It provides a public facing site with a number of webpages to inform and educate.
· Home page – an introduction to SHYMAN project, highlighting the benefits of the technology. Funding sources are clearly marked and the link to the coordinators homepage.
· The Project – this explains the purpose of the project, the technologies involved and the partners. The specific areas for the wp4 case studies are also discussed.
· SHYMAN Process – this explains the concepts and principles of continuous hydrothermal synthesis and the possibilities
· Our Partners – this page explains who the partners in the SHYMAN project are, and a link to their own website.
· Nanotechnology – this page gives some useful links for viewers who are interested in learning more about nanotechnology and the concepts of ultrafine materials for industrial applications.
· Video Diary – this is a live page that allows users to see how the project has developed during the four years from bench scale innovations to pilot scale trials to full scale operation and breakthrough. We have had over 250000 hits on the various videos linked to this page via YouTube.
In 2008 Lux Research predicted that nanoparticles would “touch” $3.1 trillion worth of products across the value chain by 2015, with the intermediates market reaching a net worth of $432 billion. Transparent conductive films alone would be worth $3.5 billion by 2020. However, it is almost impossible to find credible predictions for the market potential of the nano-enabled industry beyond 2025. Hence in 2016, it is also fair to say that nanotechnology is still a developing market with many emerging sectors. There are many different methods for producing nanomaterials to meet market demands, and dry methods (despite all the ensuing issues over safety) have been the most successful to date. As alternatives emerge, it is likely that industry will turn away from these dry products and engage with process technologies that can produce a dispersion based, higher quality and easy to formulate product. The real challenges for new alternatives are clearly around material quality, scale up, formulation and (most importantly) the cost of production.
Continuous hydrothermal synthesis is relatively new technology and would offer a true alternative to other production methods because it is a genuinely continuous process which is also chemically more benign. Continuous hydrothermal synthesis produces nanoparticulate materials by mixing superheated or supercritical water flow with an aqueous flow containing a dissolved metal salt. i.e. rather than slowly heating the entire contents of a batch vessel (batch hydrothermal synthesis), two fluids are continuously mixed together. The problems around this process were solved during research work at The University of Nottingham and the reactor configuration necessary for continuous production was demonstrated at bench (g/hr) and pilot scale (kg/day) prior to the start of the project.
Through the SHYMAN project and the interaction of the 17 partners from across Europe, the process has now been scaled to 1000 tons per year production (dry weight equivalent) which makes the plant the largest multi nanomaterial production facility in the world. Sustainability credentials and cost analysis were also assessed, to compare the process against alternative methods and against existing products in the market place. The process was shown to be highly sustainable, and cost effective with OPEX costs of below 10 euros per kilo (and less than 5 euros, in some cases). A water treatment strategy was devised and implemented that would allow the plant to operate continuously whilst formulating products, ready for sale.
Case studies were part of the project in order to validate the products in the context of real products. These products were selected to demonstrate the efficacy of the process in different areas from healthcare to printed electronics. Each area required particularly performance criteria that would test how controllable the process was in terms of product quality. Bone materials (such as Hydroxapatite) with metal nanoparticles (such as Pt, Ag, Au) for medical diagnostics, printed electronics materials (such as indium tin oxide and quantum dots), functional lubricants (such as sulphides), ceramic and catalysts nanoadditives for polymers (such as titania, and silica), doped luminescent ceramics (such as YAG:Ce), superhydrophobic materials (such as ceria and silica), and functional polymer additives (e.g. UV resistant materials like zinc oxide and flame retardants).
Continuous hydrothermal synthesis is still in its infancy, in terms of the scope of materials that can be produced and the control over particle size and shape. The project also allowed researchers to specifically focus on expanding the ‘repertoire’ of the process. Partners were able to demonstrate how metals, mixed metal oxides, sulphides, perovskites, phosphates and even metal organic frameworks could be produced. In addition to simple ‘production’, much of the work was around how the size and shape of the products themselves could be altered by changing process variables e.g. pressure, temperature, flow, concentration and precursor type. Most of this work is now published, with a significant number of publications in preparation.
Project Context and Objectives:
SHYMAN was a large scale integrating project focussed on the scale up and development of continuous hydrothermal synthesis for the manufacture of high quality nanomaterials.
Project Context
The production technologies for nanomaterials are critical in the success of nanotechnology as a whole. There are many different methods for manufacturing nanomaterials, both wet and dry, the latter being more visible in today’s market. However, it is likely that manufacturing methods will change as more emphasis is placed on health and safety and the sustainability of processes. This was highlighted recently at the 4th Annual Nano Safety for Success Dialogue Meeting (Brussels March 2011) where regulatory concern was focussed on the hazards of exposure with dry nanopowders. Therefore, for economic and environmental reasons it is vital that manufacturing routes that will facilitate the forecasted increase in production are;
1. Green – using reduced levels of solvents, sourcing the most environmentally friendly feed materials
2. Sustainable – with efficient energy recovery, low temperature processing and recycling
3. Low cost – through process optimisation to minimise the number of downstream processes prior to use
4. High Quality – the process should be capable of generating high quality materials with superior control over particle size, size distribution, formulation etc...
Routes that can succeed in one or two of these areas will not be enough in the future meaning that Industry will have to look for ways to achieve all of these targets.
Dry methods - Currently the most commercially used techniques for producing nanomaterials are considered to be ‘bottom up’ approaches that are dry based technologies. Many of these technologies often generate low specification dry powders (wide particle size distribution, highly agglomerated particles of basic materials) that have to be re-processed before use. Combustion synthesis or Flame pyrolysis methods are dry techniques that use a high temperature zone to convert dissolved metal species into nanoparticles. The metal salts are dissolved in a suitable organic fuel that burns in the flame to produce a spray of dry nanoparticles that are collected downstream. Plasma Synthesis is a similar process where the metal precursors travel in a spray through a plasma under vacuum to form nanoparticles. These techniques are relatively simple and easily scalable, hence their overall appeal to industries that require large quantities of material. The cost of manufacture is also relatively low which is why these techniques have been fairly widely used. However, there are issues over the quality of the product and since these are dry techniques, they will also require downstream processing steps to redisperse and formulate the particles.
Wet Methods - Hydrothermal synthesis is an alternative route to manufacture that offers unique opportunities for the synthesis of high quality nanoparticles and their formulation. In contrast to other technologies, hydrothermal synthesis;
• Does not tend to use noxious chemicals – with water soluble precursors and water as a solvent
• Uses relatively simple chemistry – generally following hydrolysis and dehydration stages
• Allows straightforward downstream processing - the process is dispersion based
• Uses relatively cheap chemical precursors – acetates, nitrates and phosphates
• Can produce stoichiometric compounds like YAG or BaTiO3
• Can produce non-stoichiometric materials where precise alloying or doping can be achieved
• Can avoid agglomeration - the dispersed materials can be stabilised with additives, in situ.
• Size and shape distribution can be narrow and well controlled
The historical drawback has been in scaling up hydrothermal synthesis away from batch systems. In batch systems dissolved metal salts are heated in autoclaves at relatively slow ramp rates. Processing times can be hours or days for the larger systems. The step from batch to continuous hydrothermal synthesis has been held back by engineering issues around mixing the heated fluid and the aqueous metal salt flow. T piece reactors were originally used but these are now, generally accepted as unworkable with good reason. An optimum configuration was invented and developed by UNOTT (coordinator) to allow the two fluids to mix in a controlled and efficient way. The superheated fluid passes down an inner nozzle pipe against an up flow of cold metal salt. Nanoparticles form at the interface of the two fluids and the buoyancy of the heated flow causes the nanoparticle slurry to be carried upwards (downstream) for cooling and collection. See www.prometheanparticles.co.uk for video of the process. This was the first reactor design to successfully eliminate blockages, whilst creating high quality nanomaterials, thus representing a step-change for hydrothermal technology. UNOTT demonstrated that the lab scale reactor (5g/hour) could be scaled 30 times (150g/hour) to produce a 1 tn/annum system.
As such, continuous hydrothermal synthesis was seen as an enabling and underpinning technology that is ready to prove itself at industrial scale, to over 100 tons per annum. Academic specialists with international reputations in reactor modelling and kinetics and metrology were assembled to develop the ‘know how’ needed to scale up the current pilot scale system. Selected project partners with expertise in sustainability modelling and life cycle assessment quantified the environmental impact and benefits of a process that uses water as a recyclable solvent, whilst producing the highest quality, dispersed and formulated products. In addition to scale up production, the process will be improved through four case studies with industrial end users, namely – printed electronics; surface coatings; healthcare and medical; hybrid polymers and materials. Further value was added to the project by working on new materials that have been identified as key future targets but cannot be currently made, or made in significant quantities. The consortium was founded on the principle that the whole value chain (from nanoparticle production to final product) must be involved in the development of the technology. This not only informed the development stages of the production process but also maximised ‘market pull’, rather than simply relying on subsequent ‘technology push’.
Main Objectives
The main objectives of the SHYMAN project were to investigate;
i - Scale up – what are the limits for scale up? How can these limits be impacted by better process design?
ii - Formulation – how flexible is the process to allow online pre-treatment of the nanoproduct?
iii - Weight loading – how can the concentration of the final product be increased from 1% to 30%?
iv - Cost – how low can opex be driven to make this one of the most sustainable manufacturing processes of the future?
v - Sustainability – what are the environmental benefits of the process?
Project Structure - The work packages covered key areas of research and development but the overall effort were grouped as follows.
i- Nanoparticle manufacture on bench, pilot and full scale WP1, WP2 and WP7
ii- Scale up design and build WP5, WP8-9
iii- Formulation Research WP3 and WP2
iv- End User product development via case studies WP4
v- Process Life Cycle Analysis and safety assessment WP6
www.nottingham.ac.uk/~eczehl/SHYMANFR/Figures1.html
Specific Objectives around Scale Up (Workpackages 5,8-9)
The real challenge was to find the optimum reactor design that can manufacture 100 tons/annum (dry weight equivalent) of formulated nanomaterials. The initial system at the start of the project was operating at 1 tn/annum. The system would need to be capable of sustained operation at a range of superheated conditions from sub-critical (starting at 100oC+ and 10 bar) to near critical and supercritical conditions (>374oC and >218 atmospheres).
Specific Objectives around Formulation and Weight Loading (Work Packages 3,5)
Continuous hydrothermal synthesis tends to produce aqueous suspensions of nanomaterials at relatively low concentrations (<1% wt loading) which is a critical issue that will be addressed in the project. The key challenge for formulation was to create a flexible system that could produce nanomaterials with a specific coating, in a specific aqueous or non-aqueous fluid, at a specific weight loading.
Specific Objectives around New Materials, Metrology and Development (Work Packages 2,7)
Underpinning the work around scale up and improved formulation of nanomaterials was the characterisation of nanomaterials and development of materials with enhanced properties for specific applications.
Specific Objectives around Sustainability and Manufacturing Costs (WP6,8)
In order for Continuous hydrothermal synthesis to become a popular route for nanomanufacturing (in addition to its product flexibility and scaled manufacture) also meant demonstrating its green credentials in terms of sustainable and safe manufacture with low operating costs, capital costs and CO2 footprint.
Specific Objectives around Dissemination and Engagement with Industry (WP4, 10)
The integration of end users in the project was deliberately designed to improve the development of the process and provide evidence of the suitability of the products for a wide range of applications. The dissemination by all partners in the most appropriate forums (academic, industrial, trade) ensured the widest possible promotion of the project and project aims and objectives.
Concluding remarks on completion of the SHYMAN Project
We have succeeded in this ambitious project with the design, build and operation of the world’s largest multi-material continuous hydrothermal plant in the world. This plant is capable of making high quality nanomaterials including metals, metal oxides, hydroxides, solid solutions, carbonates, sulphides as well as more complex nanoporous materials including MOFs, ZIFs and COFs. This project has only been possible through the close collaboration of 18 partners across Europe with world-class expertise in numerous disciplines including chemical engineering, chemistry, physics, life cycle assessment and materials engineering.
Many of the case studies have shown that the process can produce nanomaterials with a clearly defined technical and economic edge in the marketplace. Many new nanomaterials have also been produced using this platform technology.
It has been proven to be a flexible, economic and environmentally sustainable technology with the capacity for scale up, well beyond lab scale to full industrial scale production.
Project Results:
SHYMAN PROJECT RESULTS AND HIGHLIGHTS
www.nottingham.ac.uk/~eczehl/SHYMANFR/SANDT.html
This section shows some of the S and T highlights and technical breakthroughs for each of the key objectives for the SHYMAN project.
I. Scale Up – from reactor modelling to chemical engineering designs to the final plant
II. Formulation and Weight Loading – increasing the weight loadings of the products and formulating them for use in target applications
III. Sustainability and Production Cost – proving that the SHYMAN process is a highly sustainable alternative and an economic opportunity for the nano-enabled market
IV. New Materials, Metrology and Development – increasing the scope of the process to manufacture an even wider portfolio of materials
V. Dissemination and Engagement with Industry - 7 case studies that demonstrate the performance and flexibility of the SHYMAN process in producing high quality nanomaterials
1 MODELLING AND REACTOR SCALE UP
Modelling was a crucial part of the project because it directly informed the design process for the scale up plant. The mixing regimes inside the reactor are crucial for the quality of the nanomaterials produced and to ensure that plant can operate continuously without blockages. Two different approaches were taken to understand mixing dynamics and how the mixing of the aqueous metal salt flow with the superheated water flow might be optimised at small scale, bench scale and full scale.
1.1 Pseudo Fluid Modelling
Continuous hydrothermal synthesis requires high pressures and high temperatures and therefore uses steel fittings and components, making visualisation of the flow mixing regimes impossible. However, visualisation is possible if transparent reactors seek to reproduce the mixing (mimicking the flow regime and flow ratios) but at ambient pressure and temperature. This process used sugar water to represent the denser (relatively) cold metal salt flow and methanol was used to simulate the less dense, super buoyant superheated flow. This approach allowed multiple flow rates and flow ratios to be observed and quantified2. Dye was dissolved into the downflow to enhance the contrast between the two liquids and enable image analysis processing to quantify mixing efficiency.
During the project the pseudo reactor modelling was adapted further to use ‘2D’ rubber templates inserted between sheets of polycarbonate plastic. One of the sheets of polycarbonate was custom fabricated with ports to allow the inlet and outlet of the pseudo fluids into the volume between the two sheets. This pseudo reactor represents a cross-sectional slice of a typical stainless steel supercritical reactor; the path length is constant in all regions which could then give improved detail of the mixing dynamics. it was discovered during testing that water, sugar water flows gave the same patterns and results as methanol, sugar water flows so methanol was no longer used (which made the modelling work cheaper and ‘greener’)
This modelling work allowed optimal conditions to be found for all scale of operation as well as an approximation of the jetting distance to be established. This jetting distance equates to the penetration of the superheated flow into the up-flow of cold metal salt solution. This is a critical part of understanding what might happen with the much higher flow rates (and Reynolds numbers) present in the final reactor configuration.
1.2 Computational Fluid Modelling
The counter current reactor was virtually recreated for the computational fluid modelling. In order to produce a workable computational model the geometry was simplified slightly before the mesh was employed in the computations. The number of cells was carefully analysed and optimized for size, minimizing computational expense while assuring the results are mesh-independent.
Pseudo fluid modelling is one of several methods for directly visualising the flow dynamics in reactors which involve different mixing geometries. In most cases, the flow and mixing of fluids under supercritical conditions are governed by fundamental equations for conservation of mass, momentum and energy. When dealing with turbulent flow, a suitable averaging method must be used. The density averaging technique, or Favre averaging, applies fluctuation to average values in lieu of actual flow parameter in order to derive a time averaged solution. To consolidate interdependent variables and reduce the number of unknowns, turbulent closure must be employed. There are different approaches to predicting turbulent flows ranging from RANS (Reynolds-averaged Navier–Stokes) to LES (Large Eddy Simulation) and DNS (Direct Numerical Simulation). This work is now published in Nano Research which is a high impact journal.
The jetting phenomenon was predicted using this new the CFD model which was particularly useful when considering the size of the reactor on the actual plant.
www.nottingham.ac.uk/~eczehl/SHYMANFR/SANDT.html
1.3 Neutron Beam Reactor Tests
As mentioned in the pseudo fluids section, it is impossible to visualise inside the steel reactor using standard techniques. However, after the start of the SHYMAN project, a Japanese group started to publish on the use of neutron beam imaging with supercritical water reactors. This work validated early work on reactor design (by the SHYMAN team). An opportunity presented itself during the project to collaborate with the Japanese group using the Nuclear reactor facility in Kyoto in January 2013. This approach was particularly effective in visualising the changes in mixing dynamics at different flow rates and flow ratios. The jetting distance was also visible using this reactor and this, in turn, validated the findings from the CFD and pseudo fluid model.
1.4 Final Validation of the Modelling Work
The models were all brought for validation and empirical work demonstrated that the models were indeed accurate. After this stage real nanoparticle samples were produced at bench scale and characterised carefully using HRTEM and additional image analysis tests to see how particle size was impacted by process conditions. Various process conditions were the simulated using the CFD and available kinetics data to create a predicted particle size distribution. This work was part of the Nano Research paper (DOI:10.1007/s12274-016-1215-6)
HIGHLIGHTS
• Neutron Beam work in Japan – to calculate jetting distances and fluid behaviour
• Two new reactor designs patented – with some potential advantages for high speed mixing
• CFD model completed – with specific mixing regimes mapped for higher flow rates
• Validation of the CFD-Pseudo fluid models – with good agreement
2 PLANT DESIGN, ASSEMBLY, COMMISSIONING AND OPERATION
The process itself can be represented in a simplified way as a pump-heat-mix-cool-depressurise-collect procress. This process was designed to operate under continuous conditions for a variety of inlet species and process conditions resulting in a wide range of potential products. Sustainability was optimised through water recovery (where possible), use of gas heaters (rather than electric), and by minimising the consumed energy (using a heat recovery network).
The following design criteria were used for the plant
Flow rate Maximum: 4.8 m3/hr Minimum: 1 m3/hr
Pressure Operating Pressure: 250 bar
Temperature Maximum: 450oC Minimum: 150oC
Capacity Minimum product concentration: 0.1 wt% Maximum product concentration: 1 wt%
Maximum capacity: 48 kg/hr dry nanomaterials Minimum capacity: 1 kg/hr dry nanomaterials
Target capacity for 100 tn/annum @ 6000hr/annum: 17 kg/hr
A hazards and operability study (HAZOP) is a structured and systematic examination of a planned or existing process in order to identify and evaluate problems that may represent risks to personnel or equipment, or prevent efficient operation. This study was paramount in producing the final P&ID and provided a large number of revisions to create a safer and more robust process. The method uses existing design information (PFD, P&ID, Mass and Energy Balances) to determine the causes, consequences, existing safeguards and action to be taken for deviations from the design intention. This process takes place at various ‘nodes’ throughout the process. This was the final stage before the initiation of the plant build. The initial site for this plant was in Warrington but due to restructuring and changes in priority with the host partner, a new site was found in Nottingham.
HIGHLIGHTS
• Design and construction of a CE marked high pressure gas boiler and heat exchanger system – necessary for the insurance of the plant
• Establishing a suitable site in Nottingham - mitigating against the withdrawal of Solvays Warrington site
• Construction of a chemical plant- at almost half the normal cost of a normal plant build
• Optimisation of the plants sustainability and process economics – with excellent OPEX values
• Potential maximum output of a plant at 1800 tons per year for some materials- +>100 tons with all materials
3 SUSTAINABILITY MODELLING
Assessment of sustainability and impacts on the environment of SHYMAN technology was an integral part of the SHYMAN project. In the framework of this assessment Life Cycle Assessment (LCA) method has played a pivotal role alongside CCALC© which is a methodology specifically for calculating the CO2 footprint of any given material or product. Life Cycle Assessment (LCA) is the most important analytical-information tool and allows users to assess the potential impacts product systems have on the environment throughout their entire life cycle. All associated factors are incorporated in the assessment, from raw material excavation, through the production and use phases, and until final disposal. No other tool provides such a comprehensive view of the product, or could prevent the transfer of environmental impacts from one stage of the life cycle to another. LCA methodology was standardised in 1997 by the International Standardisation Organization (ISO) in its ISO-14040 series. This tool is particularly valuable when seeking to improve the environmental impact of a given process, or when comparing the impact of one process over another for the same products.
The benefits of developed technical solution applications are quantified via various impact categories e.g. Cumulative Energy Demand (CED), Global Warming Potential (GWP), etc. This study has made extensive use of SimaPro© which, when connected to large life cycle inventory databases (e.g. Ecoinvent), can quantification of environmental impacts and the modelling of various scenarios within defined business case studies.
One specific example of where life cycle assessment was used for a selected material case study was for Self-Cleaning Coatings (SCC). ZnO nanoparticles enhance the hydrophobicity of the surface and photocatalytic coating applying photocatalysis for destroying undesirable microorganisms and airborne pollutants from the indoor environment. LCA was applied in the SHYMAN project on two levels, defined by the extent or reach of the evaluated system. The first level provides “cradle to gate analysis” of the SHYMAN process, which means from the raw feedstocks to the final nanomaterial product. The LCA approach allows any route to production of a given nanomaterial to be assessed against alternative routes and conditions (through the SHYMAN technology or with alternatives). In addition to the use of different precursors, mixing temperature was altered which can have a ‘knock on’ effect on the product quality and precursor conversion. In most cases (not just TiO2), higher temperature mean higher quality product and higher precursor conversion, but this will come at a higher environmental cost. Economic costs are not as easy to predict since quality of product may or may not impact on the final selling price. In most cases there will be an optimum process temperature whereby a majority precursor is converted and the product quality is relatively high (often quantified by crystalline/amorphous ratio), and in the case of the TiO2 precursors, the optimal conditions are quite varied.
The SHYMAN process is ranked among the methods with the medium energy consumption measured by means of CED (Cumulative energy demand) and takes into account the net energy for production of the feedstocks. The information from case study scenarios clearly shows how the choice of precursor can significantly affect the total environmental impact.
It should be pointed out that low variable technologies (e.g. sulphate and chloride process, Altair hydrochloride process) have lower CED than SHYMAN technology but in comparison with technologies with similar product flexibility (e.g. HT plasma, sol-gel...) the SHYMAN technology performs well in terms of CED and product quality. The same conclusion is valuable for Global warming potential. In general SHYMAN process has many advantages and overall has one of the lowest environmental burdens (when the best precursors are chosen).
The second, wider level of study provides a wider scope with “cradle to grave” LCA for selected product applications of nanomaterials. Besides CED and GWP, other criteria were defined for overall multi-criterion qualitative comparison of various production technologies. SHYMAN has high productivity, high quality, multiple material, medium/low costs and low consumption of process energy. The ability of the SHYMAN process to produce large volumes of multiple types of high quality nanomaterials at a reasonable cost makes this technology highly competitive on the market. The biggest challenge with a platform technology is therefore finding suitable applications for of these NPs and the second challenge (for LCA studies) is finding out process sensitive data from partners or industrial information for the compilation of a ‘cradle to grave’ study.
An example of such a cradle to grave study
Two very different possibilities of removal of undesirable microorganisms and airborne pollutants from the indoor environment of hospitals using air purifiers and photocatalytic coatings based on nano TiO2. Functional unit: Cleaning air in hospital – size of the room 300 m3 (100 m2) in one year.
For each cleaning alternative three variants were defined:
- For photocatalytic coating variants I, II, III represent different level of natural light in the room and the associated need for artificial lightning.
- for Air purifier variants I, II, III represent different combinations of air purifier regimes (heavy duty, light duty, economy) associated with different intensity of pollution and requirements for air purity. LCA study results show that environmental impact is highest for air purifier variant I (heavy duty regime) and lowest for photocatalytic coating variant III (minimal need for artificial lightning). There is a marked difference in environmental impact on the whole between the air purifier and the photocatalytic coating regardless of which variant is assessed. The major findings include: Photocatalytic coatings have an essentially lower environmental impact than air purifiers; Environmental impact levels in the use phase are significantly higher than in other phases; Environmental impact of photocatalytic coatings in the use phase can be lowered by the presence of sufficient natural light in the space; The impact of production of nano TiO2 from the SHYMAN process is negligible in comparison to impacts of the other life cycle phases for photocatalytic coatings, particularly the use phase. The benefits of nano TiO2 in lowering environmental impact are quite evident when compared to traditional air cleaning products such as an air purifier.
HIGHLIGHTS
• Development of a full cost model for the SHYMAN process - from cradle to gate
• LCA modelling of specific nano enabled case studies- from cradle to grave
• The favourable comparison of the SHYMAN process - against all other nanomanufacturing processes
4 CAPEX AND OPEX
CAPEX refers to capital expenditure and OPEX refers to operating expenditure. Both are important for new technologies since a high CAPEX (even with potentially low OPEX) would be considered to be a risky proposition for a company or investor. Low CAPEX and high OPEX could also be an issue for a manufacturer who would need to know that the products could be still manufactured at a competitive cost against other suppliers with different technologies.
In principle chemical plants can cost 4x times the value of the large capital equipment, which in the case of the SHYMAN project amounts process tanks, heat exchangers, pumps, heater, deionised water, blast cooler, filters, post processing pumps at approximately €715,000. There are more detailed methodologies for plant costings and from our calculations (a conservative estimate) €2 million euros would be needed to build the plant. In reality only €1.1 million was spent for the upstream and downstream sections of the plant, which meant that the design process was designed to be as cost effective as possible whilst maintaining safety. At the time of writing the initial proposal the cost of many items had to be estimated e.g. the boiler, since no such system previously existed. This does, however, have a positive message for potential end users who will see any new process with low CAPEX as a positive.
OPEX costs are material specific because all products require specific process conditions i.e. pressure, temperature, concentration, precursor type, conversion rate, flow rate, flow ratio. However, if precursor costs are removed from the calculation, it is possible to generate costs that take into account the variables of temperature and concentration. OPEX can be divided into different categories including gas (boiler), electricity (pumps) and water (the process fluid). These costs are affected by the use of heat recovery with a cooling tower, which changes the efficiency of the process significantly. However, it is the concentration of the process and the temperature of the reaction that have the most significant impacts. Clearly if the concentration of the final process flow (remember that continuous hydrothermal synthesis generates low weight loadings) is quite low i.e. 0.1% then the OPEX is €14/kg when operating at 380oC. If this concentration can be increased to 1%, which is more realistic for a process at this scale, then the OPEX drops to €1.4 per kilo, which make the process highly competitive against all other methods of nanomaterial manufacture. At 2.5wt% the cost per kilo falls to 50 cents.
At lower temperatures, the most significant cost is water. The water has to be deionised and this carried a net cost to the plant. As the reaction temperature increases, gas consumption becomes more significant than water. Overall OPEX appears to make a sudden increase around 360oC which is when near-critical water becomes supercritical and is caused by the changes in heat capacity and heat transfer at these conditions. It also highlights why all optimal conditions need to be set for any given material in order to minimise waste and environmental impact i.e. why run a reaction at 400oC for 100% conversion if operating at 350oC achieves 98% conversion?
5 DOWNSTREAM SEPARATION, CONCENTRATION AND EFFLUENT TREATMENT
One of the critical elements of the project was to ensure that waste water could be treated efficiently (in order to operate the upstream process continuously) whilst maintaining the ‘sustainable’ credentials of the process, but remaining within the project budget. Some of the initial ideas and designs for this stage were rejected as too costly and a refocus on the delivery of a more practical solution to problem. The process flow from the SHYMAN plant was designed to operate at flows of up to 1 wt % of solids, with the potential product specification being 10wt% or higher. The downstream or post-processing plant had to be capable of processing 4.8 m3h-1 and had to be designed to sit within a footprint of around 85m2 on the site of the SHYMAN plant at Genesis Park in Nottingham.
From observation of the behaviour of different nanomaterials produced hydrothermally at both lab and pilot scale, particles produced fall into one of two categories: ‘unstable’- particles that settle out from a liquid after a short period, and ‘stable’ – particles that remain evenly dispersed within a liquid after a sustained period. Two separate strategies therefore evolved during planning for stable and unstable product streams. For the unstable materials with higher settling velocities, the most cost and energy efficient separation method is settling by gravity. In order to keep the process completely continuous, a number of large volume settling tanks were required. The SHYMAN post-processing plant consists of three polyethylene 6.9 m3 settling tanks for normal operation during settling, as well as a fourth tank of the same size for contingency and overflow. This sizing means each tank takes around 90 minutes to fill when the plant is running at maximum output. All settling tanks are cone-bottomed, allowing for easy emptying of solid materials. Once a tank is filled, a high level of separation should be achieved in approximately 1.5 hours before being manually emptied to the product tank & waste by the operator. Initially the concentrated nanomaterial sediment is emptied out of the tank under gravity, before the waste water in supernatant is emptied, also via gravity. The arrangement on the tank outlet incorporates an in-line sight glass next to a manual three way switching valve, giving the operator a clear visual representation of when the effluent switches from concentrated material (for product tank) to waste water (for waste water treatment), so they can direct the flow accordingly.
Without testing the large scale tanks, it is difficult to predict accurate levels of separation, as this is based almost entirely on the visual representation of the flow as seen by the operator, however based on tests at smaller scale and current practices used at pilot scale, a final product weight loading of 10% should be easily achievable via settling alone.
Because stable products have very slow settling velocities, an alternative method of separation was required. After an early feasibility study, it was decided that filtration is the most cost and energy efficient choice for separating ‘stable’ particles from water. The SHYMAN post-processing plant consists of a six hollow fibre filter system. The filters use tangential flow technology, where water permeates through the pores in the filter fibres when the stream is under pressure of around 2.1 Bar. Filters pores are 5kD (1nm) in diameter, therefore allow nanomaterials to remain in the retentate.
In order to maintain sufficient pressure, a pneumatically actuated pinch mechanism pressure control valve is fitted on the retentate outlets of the filters. This is controlled via a pressure transducer on the pump-side of the filter. The calculations required for this final design relates to total flow rates, and surface area of the filters themselves.
Following the recommendation of project partners and the local water authority’s guidelines (Severn Trent Water), the main objective for the water treatment system is to provide achieve a neutral pH level in the effluent water from what could be potentially very acidic (i.e. Aluminium Oxide Hydroxide, pH<1) or basic (i.e. Silicon (IV) dioxide, pH~11) process water. The SHYMAN plant waste water treatment system consists of 4 tanks all of 1m3 capacity. This includes 1 buffer tank, and a triple stirred-tank weir system. The weir system allows for 2 rounds of dosing with 32% HCL and/or 32% NaOH as required and a final pH check before the waste water can be sent to the drain. Using LTH MXD73 pH monitoring and dosing technology, this system ensures all effluent leaves the plant within the required pH window (6-9).
Initial recommendations during the early stages of the SHYMAN project included vacuum evaporation and NH3 stripping which have not been implemented within the water treatment system for practical and environmental reasons. However the ability for re-direction of supernatant for filtering (should suspended solids be high) has been designed into the plant.
The final product tank is a 6.9m3 cone-bottomed tank, exactly the same as the settling tanks. Its purpose is to store concentrated material that has been through the post-processing system, and should theoretically be ready to be transferred into an IBC container via P-410 and shipped, or be taken for further processing.
Overall this project has shown that it is possible to build a universal down-stream product-refining system for the hydrothermally synthesized nanomaterial process on the SHYMAN WP8 plant’s scale, with a small budget.
HIGHLIGHTS
• Online DLS monitoring system – allowing real-time measurement of the nanoproducts
• Real time waste water effluent treatment – allowing continuous plant operation
• The ability to increase weight loading from 1% to 10% in real time during operation – to formulate products continuously without stopping production
• Cost effective water processing – simple and continuous neutralisation system prior to disposal
6 CASE STUDIES
6.1 Healthcare
The aim of WP4 Case Study 1 was to investigate the potential of the nano-hydroxyapatite (nHA) manufactured using hydrothermal synthesis for healthcare applications. In particular, the focus of this case study was to use nHA in the manufacture of synthetic bone graft substitutes in paste and block form. Synthesis protocols were adjusted in order to produce nHA particles within the threshold level for pH, conductivity and endotoxins for paste formulation. Several samples of bone pastes from nHA platelets were produced and these were then taken forward for indirect and direct biocompatibility assays in vitro in Rat Bone Marrow cells. It was demonstrated that the cells cultured in direct contact with the SHYMAN pastes had a reduced biocompatibility when compared to the commercial control (ReproBone® novo). It is important to note that in vitro data does not always reflect the in vivo response. Whereas, cells cultured with in-direct contact (use of pre-conditioned media) showed a much improved biocompatibility. It can therefore be concluded that the pastes have demonstrated potential for use in bone repair although further investigation would be needed to take this product forward prior to commercial production.
A second healthcare related case study manufactured samples of Platinum (Pt), Silver (Ag) and Gold (Au) nanoparticles which were then structurally characterised. The most promising samples were taken forward for in vitro cell testing. Samples of stabilised Ag NPs were produced by PROM and were found to pass through a syringe filter, which indicates that the particles are stable and not aggregated. The filtering process also sterilises the sample to a degree, by removing impurities. This sample was carried forward for in vitro cytotoxicity tests in two human cell lines - healthy cells (Human dermal fibroblasts) and tumour cells (Human Pancreatic Carcinoma cells). It was found that the Ag NPs were not toxic to these cells under the conditions tested.
6.2 Printed Electronics
A range of different materials for various aspects of printed electronics were tested within this Case Study. Initial tests investigated the use of sulfide materials with the aim of increasing the efficiency of organic photovoltaics. Subsequent tests focussed on Indium Tin Oxide (ITO) for the application of transparent electrodes. Here, promising sheet resistance values were obtained but the haze of the coating was above the accepted threshold. This could certainly be improved with changes to the formulation of the ITO slurry. Final tests focussed on the use of Zirconium Dioxide (ZrO2) for use in transparent coatings with a high refractive index. Three samples of ZrO2 in PGMEA (at up to 20 wt% concentration) were coated onto glass substrates. It was found that all samples produced transparent and homogeneous coatings, indicating that no particle agglomeration had occurred. At this stage, the spectra obtained from UV-Vis spectroscopy showed no differences to uncoated glass, indicating the coatings had not densified or percolated enough so further optimisation work is required to either increase the weight loading or increase primary particle size.
6.3 Enhanced Polymers
Initial tested focussed on introducing nanomaterials into polyurethane foams prior to the foaming process by dispersing nanoparticles into polyols. It was found that, by using a silane capping agent on the NPs, dispersion of SiO2 particles into the polyol could be achieved up to 2000 ppm. Homogeneous foams were produced but no improved effects were found for the properties tested. Higher weight loadings might have been an answer. The focus then changed to nano enhanced polyols for coatings, adhesive and sealants. Here, SiO2 particles were introduced into alternative polyols (used for coatings rather than foams).
6.4 Optical Devices
This case study focussed on the potential use of nanomaterials with photoluminescent properties for use in car headlights. The aim in this study was to produce nanopowders which emitted visible light covering the entire white light spectrum, when excited with light in the UV range. Samples of Yttrium Aluminium Garnet (YAG), Cerium-doped YAG, Europium-doped ZrO2, Gadolinium-doped ZrO2, ZnO, and Copper-doped ZnO were produced and tested. The most promising result was found for Europium-doped ZrO2 particles, where emission in the visible light range was detected. Nevertheless, the emission intensity was still lower than that of commercial phosphors which probably relates to the particle size and the problems with obtaining high intensity emissions from nanoparticles. One solution might be through the sintering of the SHYMAN materials to create large clustered particles. Sintering is not an expensive or complex step so a route to market with these nanomaterials definitely exists but with some small post processing stages prior to use.
6.5 Coatings
This Case Study looked into the introduction inorganic nanomaterials into PVDF paints to increase the hydrophobicity, in order to produce self-cleaning coatings for architectural surfaces (e.g. bridges, building facades). Samples of hydroxyapatite, TiO2, SiO2, CeO2 and ZnO were manufactured and then incorporated both the treated and untreated particles into their paints. The paints were coated onto panels and tested for abrasion, adhesion, thermal stability and weathering. All samples met the requirements under the standard adhesion and abrasion tests (set out by the American Architectural Association, AAMA 2605) but the HA, TiO2 and CeO2 samples showed poor thermal stability. The most promising results were observed for surface-treated ZnO particles which were thermally stable and significantly improved the water contact angle of the paint, so were tested under weathering conditions. The weathering data showed no significant changes to the gloss or colour of the paint after 5000 hours of UV and humidity exposure (simulated in a weatherometer). SiO2 and TiO2 particles were also tested in a different PVDF paint formulations (water based rather than solvent based). The TiO2 particles showed yellowing in the paint but the SiO2 particles were shown to significantly improve the WCA of the paint even without any surface modification. A second coatings case study studies a wide range of nanomaterials, with the aim of improving the chemical or mechanical properties or automotive coatings. These have included SiO2, ZrO2, Ce-doped ZrO2, Fe2O3, BaTiO3 and hydroxyapatite. With the exception of SiO2, these materials were introduced with the aim of imparting anti-corrosion properties to the paint; unfortunately, it was found that, at the concentrations tested (up to 500 ppm), no differences in these properties were seen. Nano SiO2 was also introduced into the automotive clearcoats to increase the hardness and scratch resistance of the coating. Initial SiO2 samples were produced in methanol and xylene but these samples gelled before they could be tested. A formulation route was achieved through phase transfer of SiO2 particles into xylene. This material was successfully incorporated into a coating formulation without any particle sedimentation observed. Nevertheless, the haze of the resulting dispersion was too high (i.e. not transparent for a clearcoat) so could not be tested further. A final polymer based case study introduced nanomaterials into polypropylene (PP) to produce nanocomposites which have enhanced flame-retardancy or UV-resistance properties, for use in vehicle dashboards. PROM produced several samples of coated and uncoated Titanium Dioxide (TiO2), Zinc Oxide (ZnO), Aluminium Oxide Hydroxide (AlOOH) and Layered Double Hydroxides (LDHs), which were then compounded and tested. The most promising results for UV-resistance was found to result from a 2.5 weight loading of nano TiO2 in PP. For flame retardancy, when Mg-Al-CO3 LDHs were added into PP with a graft stabiliser at a concentration of 2.5 wt%, the burn rate improved by over 50 % compared to blank PP.
HIGHLIGHTS
• The SHYMAN process was shown to be highly flexible - creating new materials and new formulations for each case study
• A majority of the case studies were able to successfully create a commercially viable product - with all case studies providing a way forward for a materials in development
• A successful shift from bench to pilot to full scale manufacture for each target material – all materials have proved to be scalable
7 NEW MATERIALS DEVELOPMENT
The SHYMAN project also provided the opportunity to create new materials using continuous hydrothermal and solvothermal synthesis. The main objective of this activity was to increase the scope or potential impact of the process by increasing the scope of range of materials that were possible through the technology. The list below show materials been made (for the first time) using continuous hydrothermal/solvothermal routes.
I. Sulphides – including CdS, CuS, FeS2, PbS, Bi2S3, ZnS and MoS2
II. Metal Organic Frameworks – including ZIF8, MIL53, MIL101, HKUST-1, NOTT300 UiO-66.
III. Mixed metal oxides – BaTiO3, SrxBa1-xTiO3,
IV. Doped Metal Oxides - Co-TiO2, Ni-TiO2
V. Phosphates – including LiFePO4, LiMnPO4
VI. Layered double hydroxides – including Ca2Al-NO3, Mg3Al-C3O, Mg2Al-CO3, Co3-Al-CO3, Co3-Al-NO3, Hybrids, TiO2@Mg2Al-CO3, TiO2@Co2Al-CO3, Co3O4@Mg2Al-CO3
VII. Metals – including Ag, Pt, Pd, Au, Ni, Cu
7.1 Sulphides
As mentioned above, many different metal sulphides have been produced and in different morphologies from 2D hexagonal platelets to 3D tetrapods during the course of the project. This was achieved by altering the process flow setup to either allow both precursors (the metal and sulphur source) to mix before the reactor, or by preheating the sulphur source in the superheated downflow. With Cd++ and thiourea in the upflow into the reactor resulted in cadmium sulphide with a mixture of 11% cubic hawleyite and 89% hexagonal greenockite phase CdS,. The TEM images of this product reveal a mixture of rod and multipodal morphologies, with several clearly defined tetrapodal nanoparticles with 40 nm diameter cores and 100 nm long arms.
www.nottingham.ac.uk/~eczehl/SHYMANFR/SANDT.html
7.2 Metal Organic Frameworks
In recent years novel methods for synthesising MOFs have been reported such as microwaves, ultrasound, and mechanochemical synthesis which can benefit from reduced synthesis times and easier post-processing of products; however, none of these techniques have been adapted for the continuous production of MOFs. There are stil only a few reports for the continuous production of MOFs. A first article was published in 2012 (at the start of the SHYMAN project) showing the continuous synthesis of HKUST-1 and CPO-27(Ni). Since then Schoenecker et al. have reported a continuous process for the synthesis of UiO-66 using their patented reactor which uses batch technology with an integrated flow system to allow for the removal of products and introduction of reagents in situ.
Many groups have reported the hydrothermal synthesis and continuous synthesis of ZIF-8, but to the best of our knowledge, none have reported the continuous hydrothermal synthesis of ZIF-8. We used the SHYMAN reactor technology to synthesise HKUST-1 and CPO-27. We also used the continuous process for ZIF-8 in a purely hydrothermal system. This lab-scale process was shown to be capable of producing over 200 g per day of activated ZIF-8. Using the internal volume of the rig (55 mL), the space-time yield for this method was calculated to be 3,875 kg m-3 per day, which is a significant increase on values which have been reported for other process technologies. The SHYMAN pilot system was then used to demonstrate production at ~6 kg per day. Characterisation of the products synthesised using this technology showed that the materials have similar properties as batch-produced materials, making this a viable industrial method for producing ZIF-8. We have now published a review of the progress made by researchers across the world in using continuous reactors to produce MOFs, since its inception at the start of the SHYMAN project.
As mentioned in the initial section, different MOFs have been produced in the last 3 years using the SHYMAN process but in addition to the MOF work, other work was undertaken to see if MOFs could be manufactured and activated in a single process. Activation remains one of the major hurdles to scale up and industrial take up. The use of ethanol, instead of diluting with more water, was necessary as the as-synthesised ZIF-8 forms a very stable suspension in pure water which cannot be centrifuged efficiently. The successful activation of all the ZIF-8 samples and the fact that the activation rig can be easily connected to the synthesis rig shows that this method is a viable technique for industrial production which could dramatically cut post-processing times. This report demonstrates the large-scale production of ZIF-8in a continuous hydrothermal system. More importantly this work shows a route to the one-step continuous synthesis and activation of these materials. The ability to activate the material in situ will reduce time and cost of full-scale production. This method represents a viable industrial method for the production of activated ZIF-8.
7.3 Doped Oxide Materials
Doping oxides (away from their pure form) can drastically alter properties such as particle size, crystal structure and UV absorbance properties. Some work was undertaken to see how the photocatalytic performance of TiO2 could be improved through doping. The crystallite diameter of pure anatase TiO2, as calculated using the Scherrer equation, is 15 nm. Doping TiO2 with cobalt or nickel resulted in sizes of ~ 6 nm. Surface area analysis of the samples showed all three samples to have typical Type IV isotherms with H2 type hysteresis loops indicative of mesoporous aggregates. The calculated BET surface area of the undoped anatase was 128 m2 g-1 while the smaller doped samples both showed surface areas of ~ 230 – 250 m2 g-1, consistent with the smaller particle sizes calculated from the XRD and observed by TEM.
The absorbance profile of the undoped titania was as expected, showing a sharp decrease in absorbance immediately below 400 nm, corresponding to the anatase band-edge, followed by a tail off in absorbance with increasing wavelength. The 1% cobalt doped sample showed a similar profile at low wavelengths; however it also exhibits additional absorbances across the 400 nm to 700 nm range, due to the d-d transitions of the cobalt ions. Similarly the 1% nickel doped sample showed gentler tail-off up to 540 nm and an additional absorbance at 720 nm arising from the characteristic 3A2g → 3T1g transition of octahedrally coordinated Ni(II). These materials were also tested for applicability as nanocatalysts for the photoreduction of a dye. The doped ceramics were shown to have a higher activity that the non-doped TiO2.
Barium Titanate was discovered in the early 1940s as a capacitor material to replace mica. The flexibility of the perovskite structure is such that a wide range of metal cations may be accommodated, particularly in the A position. With respect to barium titanate this allows significant variation in composition, with barium easily replaced by alternative M2+ ions. One of the most common substituents is strontium – a smaller Group 2 metal ion. The full phase diagram of Ba(1-x)SrxTiO3 from x = 0 to x = 1 is known. It has been shown that increasing strontium content stabilises the cubic phase (as mentioned above SrTiO3 itself adopts the cubic perovskite structure at room temperature). This substitution has the effect of altering the ferroelectric properties of the base BaTiO3, allowing fine tuning to suit the desired application. Elemental analysis by ICP shows that, in all cases, the total M2+:Ti ratio is significantly lower than desired, varying between 0.8 and 0.9. Given that presence of MCO3 species were observed in each material and removed in the washing step this lowered M2+ content is to be expected. It is also worth noting that the strontium is seemingly more prone to being incorporated into the perovskite structure than barium, with all mixed Ba(1-x)SrxTiO3 samples showing significantly higher higher Sr:Ba ratios than expected, suggesting that where both M2+ ions are available barium is more likely to form the carbonate and be removed. The pure SrTiO3 sample does still show a low Sr:Ti ratio of 0.81; however, which indicates that carbonate formation remains an issue for the generation of strontium titanate.
A final area for the new materials discovery was in battery materials, which lead to the development of lithium iron phosphate (LFP) and lithium manganese phosphate (LMP). Opportunities arose for collaboration with Tohoku University in Japan on batch synthesis and additives to assist particle formation (Jan 2014) and also Sungkyunkwan University on coin cell development and testing (April 2015) which meant that the SHYMAN materials could be fully evaluated. The use of additives such as citric acid, and ascorbic acid was found to improve and control particle size and shape during batch experiments and this was carried forward to continuous tests on the SHYMAN rig. The lithiation process was found to be a key controlling step in the production of LFP whereby residence time was the key to ensuring that all iron phosphate is converted to lithium iron phosphate.
These two factors (additives) and the use of a longer reactor were used to create LFP that was taken forwards for coin cell testing. The experiments demonstrated a clear correlation between increasing residence time (in the reactor) and performance. This linked to the findings around residence time and degree of lithiation. An optimal residence time was identified to create the best LFP and a rig was purpose built to produce this material. Coin cell tests are ongoing.
One additional finding was the improvement in capacity with increasing crystallinity and carbon-coating. This suggests that the new materials (with an increased residence time) with an additional formulation step to allow in situ carbon-coating may allow the direct and scalable synthesis of high performance lithium iron phosphate nanopowders.
HIGHLIGHTS
• An increase in the portfolio of materials - including sulphides and metals
• Work on the mechanisms of LFP and LMP formation - and subsequent performance testing of materials
• Expansion of the portfolio of MOFs – and development of online activation of the MOFs
• Pilot scale and full scale production of new materials- all developed initially at bench scale
• Demonstration of the doped metal oxide nanomaterials - as UV photocatalysts and battery materials
Potential Impact:
IMPACT ASSESSMENT
The main aims of the SHYMAN project were to;
A. Scale up the continuous hydrothermal process – the output has increased 1000x from the pilot reactor scale.
B. Reduce the carbon footprint – LCA has shown the process to be highly sustainable compared with alternative technology
C. Reduce processing costs - the process can now operate and produce a 10wt% solution continuously and manufacture at approximately 5 euros per kilo
D. Create new materials – the materials portfolio has increased to include, metals, metal sulphides, metal organic frameworks and hybrid nanomaterials.
E. Increase efficiency of application - decreasing the need for excess nanomaterials with high dispersion rates
F. Improve nano-manufacturing safety – toxicology results are excellent, product formulation has been established to allow liquid dispersions to be maintained during processing, thus avoiding the need for handling of any dry powders.
The SHYMAN has achieved all these aims during the course of the project as highlighted in the S and T section.
www.nottingham.ac.uk/~eczehl/SHYMANFR/IMPACT
SOCIO ECONOMIC IMPACT
The ambition was to extend a proven platform technology (at bench scale) in the form of continuous hydrothermal synthesis and scale the process to industrial scale. This scale would have to be a minimum of 100 tons per annum to demonstrate industrial relevance. In reality the project has been able to push a high value low volume process into the industrial region (nominally low value and low quality) by creating a high quality lower value proposition. The plant will never compete with the nano-TiO2 pigments market, at €2 per kg, but it does increase the ‘reach’ well beyond the anticipated €30-50 per kg market.
A more interesting quantitative economic analysis, is the impact on cost of production from the bench scale system (that was available at the start of the SHYMAN project) compared to the development and optimisation of the pilot scale, the pilot+ scale and the final full scale SHYMAN plant. The production costs for each scale of the SHYMAN technology has been approximated and shows the net improvement in techno-economic ‘reach’ for production vs the over commoditised pigments sector. The SHYMAN process enabled us to increase the scale of production 1000x beyond the state of the art (pilot) and 50,000x beyond the original bench scale production.
The impact on the market made possible by the SHYMAN project, will be seen over the next 3-5 years as commercial production begins. Commercial operation was clearly not possible during the lifetime of the project, but the ability of the process to manufacture materials that are relevant to diverse market sectors now provides a significant opportunity. The production of metals, metal oxides, sulphides, phosphates, hydroxides, carbonates, metal organic frameworks all prove that the process is a platform technology. Promethean Particles has estimated a 2 fold increase in staff in the next 18 months as a result of the SHYMAN project. The use of case studies has also shone a spotlight on the opportunities in markets that include: healthcare – through diagnostics and bone materials; printed electronics – through conductives, semi-conductives and high refractive index materials; polymers – through flame retardant, scratch proof materials; photonics – through luminescent materials; coatings and lubricants – through UV resistant and superhydrophobic materials.
Nano enabled markets are still rapidly increasing; In coatings the current global smart coatings market ($363 million) is expected to grow at almost a 50% Compound Annual Growth Rate. It is therefore expected that this market will reach almost $3 billion by 2018, and $6 billion by 2020. Two of the sectors where superhydrophobic coatings can be applied, self-cleaning and anti-corrosion, are expected to reach $1.4 billion and $449 million, respectively, by 2018. The global market for printed and thin film electronics was estimated at around $9.5 billion in 2012 (42.5% of that will be predominately organic electronics - such as OLED display modules). By 2022 the market will be worth an estimated $63 billion, with 45% printed and 33% on flexible substrates. In 2009 the global battery market was estimated at $47.5 billion and predicted to rise to $74 billion by 2015. This predicted growth was attributed to the high demand for secondary or rechargeable batteries. Lithium-ion batteries account for the largest market share of the secondary battery market with an estimated 37.9%. This figure is expected to increase into 2020 as new improved environmentally friendly lithium-ion batteries with decreasing costs replace older technologies which have maximised their potential. In relation to healthcare the global market for synthetic bone graft substitutes is expanding and is expected to rise from $2.1 billion in 2013 to approximately $2.7 billion by 2021. This is due to an increase in procedures due to the aging population and a shift to the use of synthetic materials over autograft (the patient’s own bone). Cancer treatment and nano-enhanced diagnostics, where the value of the products enhanced with nanoparticles will almost equal the oncology market estimation for that period, has been estimated to reach €117-147 billion by 2018. In nano-enhanced polymer systems such as flame retardant polymers the market is still developing and demand is growing; global demand for conventional flame retardants is projected to expand 4.6 percent per year through to 2018 to 2.8 million metric tons, valued at £4.5 billion (Freedonia, 2015). The world-total LED revenue will be saturated soon and may even start decreasing as a result of a significant increase of LED efficiency, long life-time of the devices and price-drop.
SHYMAN has indeed had an impact on the SMEs within the consortium, from two significant aspects: Internally, the access to the network of excellence of the main partners in the project allowed these small companies to be in direct contact with the most advanced developments and knowledge in the field; the potential gains -both tangible and intangible- could not be expected by the sum of all the individuals partners activity. Externally, partnering such a relevant consortium has added value to all 7 SME’s. Each SME has been able to promote their involvement in the project this increasing the confidence any third party could request for our capability of managing complex projects. Both aspects are really difficult to achieve for a spin-off company with no track record as an organization. Also, in essence participating in this project has placed many of the SMEs on the map of European nanotechnology research.
Before the SHYMAN project started, there was only one global competitor using hydrothermal synthesis called Hanhwa. This Korean company developed a 600 ton per year plant for LFP production, for battery applications. The plant (seemingly) was only able to manufacture LFP and the markets became highly competitive over the last four years with Chinese manufacturers dominating the market, either for cost or quality reasons. This plant is no longer in operation. If the SHYMAN plant proves to have an output of over 1000 tons per year, then it will remain the world’s largest continuous hydrothermal plant for many years to come. As such, the SHYMAN project has placed an EU consortium at the forefront of world nanomanufacturing and given the technology sufficient traction to create considerable global interest. This has generated EU jobs in an emerging market place where new IP generation (around the process and products) now form a strong platform for global manufacturing. The SHYMAN project has enabled the technology to be scaled to an industrially meaningful level whilst demonstrating that it is a low cost, high quality alternative to existing nanomanufacturing processes. As a result, the SHYMAN project has guaranteed EU jobs and not just income for EU companies.
WIDER SOCIETAL IMPACTS
As mentioned above, the scope or reach of the technology means that many materials and products can be made using nanomaterials from the SHYMAN plant. The diversity of market sectors that have direct societal implications, from cancer therapies to sunscreens and enhanced fabrics to flexible electronics. All these market sectors impact on society on a daily basis. The most significant impact of the SHYMAN project is probably the creation of a new industrial scale plant that can create high quality nanomaterials using a highly sustainable process i.e. using water as a solvent, high levels of recycling ad with very efficient heat recovery. All of these aspects make the process and the plant environmentally sound for a society that desperately needs to ‘do more but use less’.
Fortunately nanotechnology hasn’t been identified by the general public as the next ‘GMO scare story’ i.e. something that creates an irrational fear that overshadows any net benefit. As mentioned previously the wider societal impact is measured by a positive attitude towards nanotechnology as a potential means of achieving more effective products, processes in a more sustainable society. A positive public perception of the benefits of nanotechnology can only be achieved through better education about nanotechnology, and the measures that are taken to ensure that nanotechnology is safe and sustainable. The SHYMAN project has allowed many promotional videos, public lectures (to adults and children), blogs and tweets to promote nanotechnology. The videos have had over 250,000 hits during the lifetime of the SHYMAN project predominantly from the general public.
Through attendance at many conferences, tradeshows, the publication of conference and journal articles and student participation (through interns, design projects, R&D projects) the SHYMAN project has have a significant impact on the academic community This should be regarded as seminal work that forms the foundations on which further progress can be made i.e. it is probably true to say that continuous hydrothermal synthesis is still in its infancy with the potential to move from first generation nanomaterials to second generation (more complex, hybrid, multifunctional) production.
The use of the case studies within the SHYMAN project has been an effective means to assess and create impact within the business community. Each case study has allowed key nano-enabled markets to be evaluated and a plan of action to be established. The creation of the plant itself has created considerable interest and curiosity outside the project within the business community. The end of the project will see more engagement with these potential end-users.
MAIN DISSEMINATION ACTIVITIES
Partners have attended around 30 conferences during the course of the project and around 50 papers have been presented on the technology, the scale up developments, the products from continuous hydrothermal synthesis, the life cycle assessment of the process and examples of where LCA has shown the SHYMAN process to be highly sustainable. Many of these presentations were given as invited, keynote or plenary lectures. Around 15 new animations and videos were created to explain the technology and how continuous hydrothermal synthesis works. Academic partners have been successfully publishing journal articles and writing conference proceedings (with acknowledgement to the SHYMAN funding). This has resulted in around 20 journal publications with as many again in preparation for submission in the next 12 months.
Partners from the SHYMAN project have published more than 25 papers across a diverse set of disciplines and many as joint publications, with many more in the pipeline (so to speak). These include Reactor Design and Simulation; New Materials Discovery; Characterisation and metrology; Life Cycle Analysis;
The SHYMAN website (www.shyman.eu) has had over 10,000 visits during the 4 years and the videos posted on the video diary page (mainly accessed via YouTube links) have had over 250,000 views. The Project coordinator gave several radio interviews on nanotechnology and it’s significant in society. PR produced a private data basing site for the SHYMAN project to store the details of all metrology data for all the samples produced by all the partners. He also produced a public facing website that has had over 140,000 hits for scientists seeking to use his XRD interpretation program.
VLCI presented some of their WP3 work at the European coating congress, gaining a lot of interest. The audience was around 100 people, including people from Evonik (they have the nano-TiO2 on the market and was benchmarked). Exploitation potential for VLCI has also been furthered through contact with Lubrizol, the supplier of the stabilizer for the new nano-TiO2 used in the WP3/4 case study with Repsol.
During the course of the project we estimate that over 1000 students (chemists and chemical engineers) have engaged with the SHYMAN project through workshops, lectures, and design tasks relating to the design of the full scale process. One of the early design challenges for the chemical engineers was a preliminary heat and mass balance of the SHYMAN process at the same flow and production rates for making nano ceramics. A week long summer school was run in May 2014 at the University of Valladolid attended by 31 participants from 9 countries. 18 lecturers from 6 different countries attended and presented at the summer school. Some attendees actually went on to take up positions as interns, placement students and were involved in the SHYMAN project directly as researchers.
EXPLOITATION OF THE RESULTS
The most significant exploitable result from the SHYMAN project is the full scale plant in addition to some successful case studies. PROM has been involved with the build and operation of the full-scale plant. It is now fully operational with significant exploitation potential in the plant which will be used to manufacture large quantities of nanomaterials for consortium partners and external users. Furthermore, the research and development work being conducted at PROM at bench and pilot scales can be disseminated to the wider scientific community to publicise PROM’s capabilities. PROM has a full commercial plan to exploit the outcomes of the SHYMAN project by using the data generated during the project in sales and marketing activities; using technical progress to inform new product lines and using the full scale plant as a commercial manufacturing facility.
Connected to the point above, the tangible potential gain is the possibility to promote current products and applications inside the consortium and to identify new opportunities to exploit. Thanks to the diversity of the partner's activity in the project, unexpected areas of applications have arisen including, new lubricants, flame retardant materials and metal organic frameworks. Additionally, possible collaborations for new projects to be exploited together with other SMEs in the consortium can be explored for complementary know-how that we would not have considered without the close and durable communication that partnering facilitates. A H2020 project around the production and use of nanoporous materials was submitted 18 months ago (called SPONGE) which proposed 6 new pilot line production facilities, all enabled by the SHYMAN plant and PROM. The project was highly rated and considered ‘fundable’ but did not proceed. Many of the SHYMAN partners were part of this proposal.
Exploitation of any information on nano safety protocols, which arise from SHYMAN, or in collaboration with the FP7 project NanoMILE and H2020 NanoFase, will come through the European Commission and hopefully used to inform governing bodies particularly in the field of nanosafety and nanotoxicology. There is increasing interest from industry in the SHYMAN plant and associated technology and as policy makers include many industrial partners e.g. the BASF Dialogforum events, it is hoped that further exposure will be possible. The XRD ‘translator’ and database system from PR will hopefully be able to highlight (to EC policy makers) that experimental data created using taxpayers money should be made public, in the same way as open access journals.
With Ceramisys there is potential to exploit the use of nano-hydroxyapatite particles in pastes and porous blocks however at present they have not yet been proven to provide added benefit over the current products manufactured by Ceramisys. In addition, the in vivo data required to verify any significant benefit was not proposed as part of the SHYMAN project. If, at the close of the project, it is decided that there is sufficient potential for the new materials CERA would have the expertise in regulatory approvals and commercialisation of medical devices to take products to market, however, this would be a lengthy process (approximately 2-4 years post project) as additional studies (including in-vivo studies) would need to be carried out. One of the main benefits of the CERA case study would be that PROM have made improvements to their HA manufacturing process, in particular in water quality and post-processing, in order to achieve a suitable medical grade product for implantable devices. This will allow PROM to approach medical device manufacturers in a number of clinical areas to exploit the high quality nano-hydroxyapatite slurries.
At present, TopGaN is moving towards pilot line construction, what then would lead to the formation of a factory. Such a factory would be essential for mass-manufacturing of white-lamps. In parallel, TopGaN is applying for the EU Project (ECSEL) leading a consortium of lighting manufacturers (including the big company Valeo). This Project (WhiteGaN) has a goal to make a feasibility study if solid-state lighting can be based on LDs, instead of LEDs. If both (large LD factory construction and showing an advantage of LDs over LEDs) plans are realized (2017-18), TopGaN would need a large scale supplier of the luminophore for the white-lamps. Promethean Particles could be such a supplier in future, however, still some further research is necessary to get luminophore luminosity at least as good as it is for the commercial products from the Far East.
Pielaszek research may expand its database services and characterisation tools to become an EU platform. It was already proposed to be used by Eu JRC in Ispra and discussions are underway with EC officials towards establishing a database for experimental data gained during EC-funded projects. It is unfortunate that the vast majority of experimental evidence is wasted, except for a small fraction that is used in scientific papers. We think experimental data obtained from public money should be made available back to the public, after IP concerns are resolved. Sample DataStore is a possible solution here (it may handle IP relations), so it’s possible that the scale of exploitation may appear much larger than expected.
The main objective of the Shyman project was the development and operation of a full scale nanoparticle reactor for industrial exploitation alongside several case studies with end user partners. This plant is going to be crucial for the future needs of any partner requiring large quantities of our nanomaterials, so most partners in WP4 are the same time collaborators and future users of the foreground of the project. Promethean will assess the use of foreground developed on the manufacturing process in line with commercial priorities. Case study partners who have developed foreground IP on particular materials may well wish to exploit their results by commissioning commercial manufacture of those materials using PROMs facilities including the large scale manufacturing facility at the end of the project.
PROM’s main role in SHYMAN has been the production of nanomaterials for case study partners (in WP4) to test. As such, the main users or stakeholders have been the case study partners themselves, or partners analysing and characterising the materials, so has not required the involvement of groups outside the consortium in this respect. Dissemination of the work and results through journal papers or presentations and trade shows have drawn the attention of other potential users in the future; in this scenario, they’re involvement will be considered and the whole Consortium will be informed. Other stakeholders such as policy makers, regulators and trade associations are being kept informed as the project develops through informal networks and meetings. In addition PROM have interacted more formally with the wider community as outlined below. Dissemination of the project outcomes to the general public has largely been the responsibility of UNOTT; however, PROM have actively participated in the production of a number of YouTube videos designed for a lay audience
TopGaN is just one of potential users of nanopowder luminophores produced by Promethean Particles. The others are LED manufacturers include Osram, Nichia, Cree, Lumileds, Samsung, etc. This market is now being evaluated and will be presented in Deliverable 4.7. IHPP is already collaborating with a company to use ZnO nanoparticles as an antibacterial agent. Success in the development of such fabrics would require scale up of production. This would be through SHYMAN partners and PROM in particular. ENDOR is also partnering a Tempus project (http://www.wimb.fink.rs/) to disseminate nanotechnology through university degree students in three Balkan countries, granted by the European Union. In their presentations the SHYMAN project has been used as an example of how academia and industry collaboration can lead to the technology transfer of know-how into society.
In addition to SHYMAN, PROM is a Consortium partner of the FP7 project NanoMILE. Co-ordinated by The University of Birmingham, NanoMILE is focussing on the interactions of nanomaterials with living systems and the environment. In particular, NanoMILE assesses any adverse effects on living organisms or the environment when they’re exposed to a range of doses of nanomaterials. From this, the pathways and mechanisms can also be studied. PROM has bridged a link between the two projects, by sending nanomaterial samples and waste water samples produced for SHYMAN to partners in NanoMILE for analysis. Any toxicity data generated from this can then be fed back into SHYMAN, to better understand how the nanomaterials should be handled, treated and disposed of. This work has also led to broader interaction with the NanoSafety cluster and through these projects PROM is an active partner in the NanoFASE consortium (H2020; project kick off Sep 2015) looking at the environmental fate of nanomaterials. TopGaN submitted the WhiteGaN proposal (and is starting work with UK companies (Optocap, CST) the Eurostar project GaNbar, which will develop highly efficient laser diode arrays (bars) which could be used for producing white-light emitters.
UNOTT, PROM and CERA are all now working in a Medical Devices Network called The Centre for Innovative Manufacturing in Medical Devices researchers and develops advanced design and manufacturing methods for the Class III, musculoskeletal medical device sector. (www.mede-innovation.ac.uk). This project has allowed information and know-how from the SHYMAN project to be exploited through the development of new formulation hydroxyapatite products that are bio-resorbable or 3D printable.
List of Websites:
www.shyman.eu is the public facing website to promote the project during the 4 years. This site has also been secured for the next 2 years in order to continue to act as a source of information for any interested viewer.
It provides a public facing site with a number of webpages to inform and educate.
· Home page – an introduction to SHYMAN project, highlighting the benefits of the technology. Funding sources are clearly marked and the link to the coordinators homepage.
· The Project – this explains the purpose of the project, the technologies involved and the partners. The specific areas for the wp4 case studies are also discussed.
· SHYMAN Process – this explains the concepts and principles of continuous hydrothermal synthesis and the possibilities
· Our Partners – this page explains who the partners in the SHYMAN project are, and a link to their own website.
· Nanotechnology – this page gives some useful links for viewers who are interested in learning more about nanotechnology and the concepts of ultrafine materials for industrial applications.
· Video Diary – this is a live page that allows users to see how the project has developed during the four years from bench scale innovations to pilot scale trials to full scale operation and breakthrough. We have had over 250000 hits on the various videos linked to this page via YouTube.
