binder jetting

Water Electrolysis for Hydrogen Production Facilitates Decarbonization

The thermal processing industry is a good example of how the on-site production of hydrogen by water electrolysis can be beneficial for many of its processes and for reducing the CO2 of its plants. In today’s Technical Tuesday, David Wolff, industrial sales director at Nel Hydrogen, discusses how, from plasma spray to metal AM binder jet to annealing at rolling mills, industries across medical, automotive, and beyond are looking to water electrolysis for hydrogen production.

This informative piece was first released in Heat Treat Today’s December 2024 Medical & Energy Heat Treat print edition.


Hydrogen atmospheres are widely used in high temperature thermal processing, including annealing, brazing, PM, MIM, and binder jet AM sintering, metal-to-glass sealing, and related processes such as thermal spray. Hydrogen helps heat treaters achieve acceptable product characteristics. It’s used as a very powerful reducing agent, and it actively cleans surfaces as compared to inert gas atmospheres which only displace oxygen.

Relative to hydrogen’s use in helping plants decarbonize, it’s a fact that major OEMs buying heat treating services and heat treated products are demanding that their suppliers report their decarbonization progress. To meet the needs, hydrogen generation is becoming ever more compelling to heat treaters to ensure hydrogen for atmosphere needs inside the plant, and to help minimize their carbon footprint.

The Clean Energy Supply Conundrum

Most U.S. heat treating facilities get their atmosphere components delivered by truck. The truck emits CO2 and the hydrogen on that truck is likely “gray” hydrogen made from natural gas. Hence, the carbon footprint from their hydrogen use is notable. Importantly, the electricity grid operators are actively seeking ways to enhance the business success of providers of low carbon electricity. The key issue with those providers — solar, wind, hydro, and nuclear — is that they cannot easily follow the ups and downs of demand. Instead, consumers get electricity from those resources when the wind is blowing, the sun is shining, or the river is high. In the case of nuclear plants, they preferentially run at near fixed output, day and night. They run continuously regardless of demand. As the grid demand is very low at night, they get very low prices for the electricity they generate. They only make money for 12 or so hours a day. That’s why a lot of nuclear plants are threatening shutting down for economic reasons.

Taking Advantage of Low Demand Period Energy Prices for Use During High Demand Hours

Consider this scenario: What if a client with electrolysis capacity to produce hydrogen, such as a heat treater, could buy electricity at lower nighttime prices to make the hydrogen it needs during the day shift for its various processes, perhaps even heating their furnaces? The clean energy provider would be pleased to have more income during its low demand, low price times. The heat treat plant is happy saving money buying decarbonized electricity at low demand prices to make clean hydrogen for its various thermal processes and to operate its furnaces. And, the heat treat company’s OEM clients demanding decarbonization are satisfied, too.

How To Get Started

The scenario described above is a practical and real one for the heat treat industry today. Nel Hydrogen recommends that a heat treat company begin with a plan. That plan may comprise several phases. It’s important to seek out a knowledgeable hydrogen partner in this endeavor to specify exactly what’s needed. For heat treat applications, users generally would want compact equipment, extreme hydrogen purity, load following, near-instant on and instant off, and sufficient hydrogen pressure that make it flexibly suited for a variety of thermal processes, and for hydrogen storage addition at a later time if desired.

Figure 1. Compact hydrogen generators using water electrolysis for thermal processing applications (Source: Nel Hydrogen)

Both batch and continuous processes can be served. Batch processes may benefit from a small amount of surge storage at the outset. By combining on-site hydrogen generation with a small amount of in process hydrogen surge storage if needed, on-site hydrogen generation can be used to meet the needs of batch processes such as batch furnaces and thermal spray. By carefully choosing generation rate and pressure, and surge storage vessel volume and pressure capacity, the combination of generation with surge storage can provide maximum process flexibility while minimizing the amount of hydrogen actually stored.

The presence of a small amount of hydrogen surge storage also protects clients’ parts in case of an electric interruption that stops hydrogen production. The surge storage hydrogen can protect the parts while they cool under a reducing atmosphere.

In practice, specific client priorities such as minimum hydrogen storage, or lowest system capital cost, or highest degree of expandability, or least amount of space occupied, can be met by choosing the specific hydrogen generator capacity and surge storage system employed for any particular production challenge.

Examples of Thermal Processors Producing Hydrogen On Site with Water Electrolysis

Decarbonization will be a near-future requirement as part of the global effort to evolve towards a cleaner, greener world. On-site hydrogen generation in industry makes great sense to align with those initiatives. Right now, the thermal processing industry is experiencing the benefits of producing hydrogen on site for its production processes, and the decarbonization demand will be easier to accommodate with that infrastructure in place.

Here are a few examples of companies performing a variety of thermal processes that have made the decision to use water electrolysis to produce hydrogen on site:

Plasma Spray of Cast Iron Cylinder Liners

One of the most compelling examples has been implemented by two different U.S. automakers to accommodate the increasing use of low-weight aluminum engine blocks in today’s high efficiency vehicles. Aluminum blocks must have a cast iron lining on the inside of the cylinder bore to maximize the durability of the engine. (Older readers may recall the notorious Chevy Vega that used an aluminum engine without a cast iron liner. The author’s wife had one Vega which burned through three engines!)

Figure 2. Plasma torch used to spray-apply metal coatings in additive manufacturing processes (Source: Shutterstock)

The traditional approach to provide a cast iron liner was to drive a sleeve into the aluminum engine block. However, a new technology has been commercialized by which the cast iron liner is spray-applied using a plasma torch. The torch uses hydrogen and argon gases to add energy and maintain the necessary low oxygen atmosphere. The plasma spray was a new addition to engine production facilities that had not previously been equipped with hydrogen supply and thus elected to generate their own to minimize delivered hydrogen and avoid the need for hydrogen inventory and extensive supply piping.

The electrolyzers recommended for plasma spray applications are compact and produce high purity hydrogen of better than UHP grade at 200+ psig pressure, with less hydrogen stored than would fill a party balloon bouquet. About the size of a washing machine or refrigerator, depending on the model, each unit is low maintenance, compact, quiet, and can be installed nearly anywhere in a facility.

Metal Additive Manufacturing (AM) Binder Jet

One of the most exciting approaches to metal AM is the technology called binder jet, which creates a near net shape part using polymer and wax binders to adhere metal powders. After the part is formed, the binders are chemically or thermally removed. Then the part is sintered to attain near net shape and full part density. Hydrogen is required for the sintering atmosphere to prevent oxidation of the part during the sintering process. Binder jet technology promises to provide for mass production of individually customized parts at high production rates and consequently lower costs than parts produced individually.

Figure 3. Binder jet metal AM parts sintered in a hydrogen atmosphere (Source: Shuttershock)

Many new metal AM production facilities are being established in factories that are not already equipped for the delivery, storage, and internal piping/distribution of hydrogen. As such, many have chosen instead to use zero inventory hydrogen made on site to minimize infrastructure investments. Electrolyzers for small-scale applications requiring up to 230 scf/hr of hydrogen gas at 99.999+ % purity are advised for metal AM. About the size of a large refrigerator, the units require minimal facility floor space, are easy to maintain, and can be installed in any non-classified space. Applications for AM include medical, electronics, industrial, and automotive components.

Annealing at Rolling Mills

Plate and strip metal are processed in rolling mills where the thickness of the metal is reduced by alternating “cold” rolling steps followed by intermediary hot annealing steps. Cold rolling makes the metal more brittle, so it is necessary to have an annealing step following each rolling step. The metal is alternately thinned and then softened for what could be several iterations. Hydrogen is required for the annealing steps to maintain metal surface quality while heated. Because of the periodic market disruptions in delivered hydrogen from plant outages or trucking interruptions, several rolling mills have chosen to generate hydrogen on site to augment or entirely replace their delivered hydrogen supply. The benefits that the plants experience are primarily focused on supply reliability. Of course, they are also eliminating the carbon footprint associated with truck delivery. In this case, the carbon footprint of the generated hydrogen is determined by the particular electricity generating mix that serves the plant site.

Most often at rolling mills, electrolyzers that produce up to 1,140 scf of hydrogen gas at 99.999+ % purity are best suited for the hydrogen requirement. These units replace the need for hydrogen tube trailers or liquid hydrogen storage. They can be installed in the mill or can be containerized outdoors, offering flexible siting and reduced operational safety risks compared to delivered hydrogen.

Figure 4. Steel rolls are heated in an annealing step to soften the metal during production. (Source: Istock)

On Track Towards Decarbonization

Described in the examples above, once the means to generate hydrogen is chosen at a thermal processing facility, the company can move further along the decarbonization journey. This may be to apply a strategy as outlined in the electricity scenario whereby the company takes advantage of low demand rates or institutes an alternative creative idea. Certainly, as more and more clients demand proof that suppliers are reducing their carbon footprint, more strategies will be developed and implemented to serve the thermal processing industry. Simply generating hydrogen on site removes the trucking emissions factor and is a beneficial and practical starting point.

About the Author:

David Wolff
Eastern Regional Sales Manager
Nel Hydrogen

David Wolff has 45 years of project engineering, industrial gas generation and application engineering, marketing and sales experience. He has been at Nel Hydrogen for over 25 years as a sales and marketing leader for hydrogen generation technologies.

For more information: Nel Hydrogen at sales@nelhydrogen.com. 



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The Role of Heat Treat in Binder Jetting AM for Metals

OC

Additive manufacturing (AM) at a commercial scale began about 30 years ago and has expanded well beyond its original scope. As AM becomes increasingly prominent across different industries, heat treaters need to know how to handle AM parts in their shops. Learn about the history of binder jetting AM, the alloys used in this technology that require heat treatment, and what heat treaters should expect for the future.

Read why Animesh Bose of Desktop Metal thinks that binder jetting AM is only going to be used more and more in several heat treating sectors.

This article first appeared in Heat Treat Today’s December 2022 Annual Medical and Energy print edition.


Binder Jetting of Metals: Origins

Animesh Bose
Vice President of Research & Development
Desktop Metal
Source: LinkedIn

Additive manufacturing (AM) at a commercial scale began about 30 years ago and has expanded well beyond its original scope. At the beginning, rapid prototyping (RP) was the name for the burgeoning technology; it emerged in the 1990s to bridge the gap between the need for quickly produced prototypes for manufacturers, not just plastic replicas. Rapid tooling (RT) of metal tooling parts joined RP R&D at this time as the research frontier for materials engineers. The current name for these technologies stands at “additive manufacturing,” or AM, though the popular terminology is simply “3D printing.”

Polymers

Developments in polymer AM also advanced rapidly with both extrusion-based technology as well as through advancements in Digital Light Processing of photopolymers. Stratasys Ltd., an American-Israeli manufacturer of 3D printers, software, and materials for polymer additive manufacturing as well as 3D-printed parts on-demand, began using a material extrusion-based process with their FFF (fused filament fabrication) technology to print parts, patented in 1989. This worked by feeding coils of polymeric materials though a printer, which would extrude the material through a small, heated chamber where the material would pass through a small orifice to extrude – or print – in a three dimensional design. This method allowed for very fine, hair-like material to print in a precise X ,Y, and Z motion, building layer by layer. Vat polymerization was another polymer AM technology that gained traction and involved photopolymer processing. Both technologies are currently used for polymeric materials. Interestingly, both processes have been adapted and are being used for metal 3D printing.

Metal AM

In 1993, an MIT engineering professor named Emanuel “Ely” M. Sachs – a man who could be considered the father of metal binder jetting technique – along with his colleagues from MIT patented the process of laying fluent, porous materials in layers between 50- to 100-micron thickness to form 3D parts. They were able to do this by spraying an organic binder on each layer of material where they wanted to increase the height of the part to produce a bonded layer in the selected area. This layering is repeated several times before the unbonded powder is removed immediately or after further processing.

One of the biggest advancements in metal AM happened in 2014 when GE Aviation combined multiple parts into one huge, complex design using a laser-based additive manufacturing method called direct metal laser melting. The end result was an airplane fuel nozzle made of 20 parts for the LEAP™ engine. All of AM came into the limelight, and direct metal laser melting – a melt-based technology – just took off.

But there were limitations to this laser process, the main one being cost and special powder requirements to layer and melt to form the part. The process was also technologically intensive and not fast enough for high volume production (as would be necessary for automotive or consumer good-type application).

Binder Jetting Technology

Binder jetting that had been developing in the early 2000s started to gain traction as a non-melt-based process for high volume mass production. Instead of melting the powder material, a binder is used to adhere the powder metal layers where needed. This method of printing results in a more uniform final part microstructure compared to the melt-based processes. ExOne, a binder jet 3D printing company, pursued the binder jetting technology using a license from MIT. In 2015, Desktop Metal was formed, and they focused on high volume mass production by binder jet using their Single Pass Jetting (SPJ™) technology. As binder jet gained traction, other companies entered the market (HP, GE, and Digital Metal). Desktop Metal recently acquired ExOne and efforts at developing standards for the technology are in full swing.

Heat Treating of AM Metals

Stainless Steels

There are two popular types of stainless steel for AM. The first is 17-4 PH, a precipitation-hardened stainless steel, which I like to call an “all purpose” stainless steel. When heat treated, one can achieve varying levels of strength, hardness, and elongation; and since it’s stainless steel it has a reasonable corrosion resistance. The aging treatments are already well-established – for example, H900, H1100, etc. The other popular grade is 316L, a non-heat treatable grade used in the food industry among others. Now, most stainless steels have chromium and nickel in decent amounts, so companies have developed a grade which is called “nickel-free stainless steel” for applications where people might be allergic to nickel. This class of alloy is also heat treatable. There are many more stainless steel grades that are being developed by the binder jet process.

Low Alloy Steels

Many low alloy steels are used in AM. For example, 4140 and 4340 have various, small amounts of alloying elements. These low alloy steels also need to be heat treated.

Tool Steels

Again, most tool steels are heat treatable. One of the most popular grades is H13; it is a tool steel that is heat treatable and can achieve fairly high hardness. It’s used for dies and other types of tooling.

Then, there is a category of tool steels known as A2 and D2; those are steels in which the strength can be changed through heat treatment.

Metal Alloys with Binder Jetting

There are also non-steel alloys that are used in binder jetting and require heat treatment. One example is nickel-based alloys, which fall in the broad category of super alloys. With some of these alloys, a heat treater would solutionize the part by taking it to a high temperature (950-1000°C), hold it for 60 minutes, and then quench in water, high pressure gas, or (in some instances) in air. The part then undergoes an aging treatment for several hours, depending on part thickness.

Additionally, there is a class of copper alloys with small amounts of zirconium and chromium that is heat treatable. These alloys have lower thermal and electrical conductivity compared to pure copper but have an advantage of higher strength and hardness over pure copper, which is very soft and malleable. For example, in applications that require additional strength and hardness compared to copper, the copper zirconium-chromium-based alloys may be appropriate since their strength and hardness can be increased by heat treatment.

This is just an introduction to the many alloys that have been used in binder jetting that need heat treatment.

Future of Binder Jet and Heat Treat

While heat treaters know about AM in the medical and aerospace industries, AM will likely gain more traction in the automotive industry. Presently, these are relatively small parts, but you will begin to see larger components coming from AM; one of the things to be aware of is that AM can create organic shapes, including all kinds of twisted and complex metal geometries. To ensure that these organic shapes do not distort or droop, larger parts must be well-supported. The development of a software known as Live Sinter™ by Desktop Metal offers the possibility of negatively distorting a complex shaped part (in the green state) so that after sintering, the part shrinks and distorts to eventually provide the desired complex shape at the end. This allows for the possibility of sintering parts either with minimal or without any support structures.

Heat treaters can also anticipate high volume AM production. This is one of the major focuses for binder jet engineers – to reduce costs for most automotive parts – as it will make AM very appealing to this cost-conscious industry.

Finally, optimizing sintering processes and related equipment for AM parts will result in meeting the production demands of the industry, and this will lead to AM parts being seen in heat treat shops more regularly. It would not be a stretch to consider (since there are heat treatments where gas atmosphere quenching at high pressures is possible), that the complete heat treatment cycle may be performed in the same furnace.

About the Author: Animesh Bose is the vice president of Research & Development at Desktop Metal, where he is responsible for building out the company’s palette of materials that can be used to print quality parts. He has been involved in the area of powder metallurgy and particulate materials (PM) for more than thirty years.

For more information: Contact Animesh at animeshbose53@gmail.com


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Sintering and Binder Jetting With Vacuum Furnaces

Source: TAV Vacuum Furnaces

Ever heard of binder jetting (BJT)? It's an evolving technology that is quickly catching up to metal injection molding (MIM). Compared to MIM, BJT has a lower cost per part rate, produces larger parts, and, because BJT is a cold process, it does not introduce residual stress inside the part.

Even though BJT is a cold process, sintering is a key step in BJT. Read this best of the web article to learn the ins-and-outs of sintering with binder jetting.

An excerpt:

"Vacuum sintering furnaces are usually the go-to choice for sintering of [binder jetting] parts, thanks to the ability to provide bright and shiny sintered parts, the tight process parameters control and the possibility to work with different debinding and sintering atmospheres."

Read more at "Binder Jetting and Vacuum Furnaces: Everything You Need To Know"


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