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Sherardising
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Sherardising or Zinc thermal diffusion is a process of galvanization of ferrous metal surfaces, also called vapour galvanising and dry galvanizing. The process is named after British metallurgist Sherard Osborn Cowper-Coles (son of naval inventor Cowper Phipps Coles) who invented and patented the method c. 1900.[1][2][3][4] This process involves heating the steel parts up to 500 °C in a closed rotating drum that contains metallic zinc dust and possibly an inert filler, such as sand.[5] At temperatures above 300 °C, zinc evaporates and diffuses into the steel substrate forming diffusion bonded Zn-Fe-phases.
Sherardising is ideal for small parts and parts that require coating of inner surfaces, such as batches of small items. Part size is limited by drum size. It is reported that pipes up to 6 m in length for the oil industry are sherardised.[citation needed] If the metal surface is free of scale or oxides, no pretreatment is needed. The process is hydrogen-free, hence hydrogen embrittlement is prevented.
Application
[edit]During and shortly after World War I, German 5 pfennig and 10 pfennig coins were sherardised.
Standards
[edit]- ISO 17668:2016 (replaced BS EN 13811:2003): Sherardizing. Zinc diffusion coatings on ferrous products. Specification
- ISO 14713-3:2017: Zinc coatings. Guidelines and recommendations for the protection against corrosion of iron and steel in structures. Part 3. Sherardizing
See also
[edit]References
[edit]
Wikimedia Commons has media related to Galvanization.
- ^ US patent 701298, Sherard & Cowper-Coles, "Process of depositing metals on metallic surfaces and the product thereof", published 3 June 1902
- ^ "Original Patent (Google patents)".
- ^ Porter, Frank C. (1991). Zinc Handbook. CRC Press. ISBN 978-0-8247-8340-2.
- ^ Eric J. Mittemeijer; Marcel A. J. Somers; F. Natrup; W. Graf (21 November 2014). "20 - Sherardizing: corrosion protection of steels by zinc diffusion coatings". Thermochemical Surface Engineering of Steels: Improving Materials Performance. Elsevier Science. pp. 737–. ISBN 978-0-85709-652-4.
- ^ H. G. Arlt, "Finishes on the Metal Parts of Telephone Apparatus", Bell Laboratories Record, Volume 9(4), 175 (December 1932)
Sherardising
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History
Invention and Patenting
Sherard Osborn Cowper-Coles, a British metallurgist born in 1866, invented the sherardising process during his research in electro-metallurgy.[4] Working at his laboratory in London, Cowper-Coles discovered the method around 1900 through an accidental observation: iron and steel samples packed in zinc dust for annealing developed a uniform zinc coating upon heating.[5] This finding built on his prior expertise in electrolytic metal deposition, where he sought alternatives to overcome limitations like uneven coverage on complex shapes.[6] The initial motivation for sherardising was to produce a durable, rustproof zinc coating on iron and steel without relying on electrolytic or hot-dip galvanizing techniques, which were prone to inconsistencies and required conductive solutions or molten metal immersion.[7] Cowper-Coles aimed for a dry, vapor-based diffusion process that could apply a homogeneous, corrosion-resistant layer suitable for diverse industrial applications, leveraging thermal diffusion to alloy zinc directly into the metal surface.[6] Cowper-Coles secured the original British patent for the process in 1901, followed by the U.S. patent No. 701,298 on June 3, 1902, which detailed the method of heating metal articles in zinc dust within a closed receptacle to achieve vapor deposition.[7][6] The process was publicly demonstrated and began commercialization in Britain by 1904, marking the transition from laboratory innovation to practical use.[8]Early Adoption and Developments
Following its patenting in 1901 by British metallurgist Sherard Cowper-Coles, Sherardising saw its first commercial adoption in Britain during the early 1910s, primarily for coating small metal components such as screws, bolts, and fittings where precision was essential.[9] The process quickly proved advantageous over traditional hot-dip galvanizing, as it avoided dimensional changes and the need for recutting threads on intricate parts, enabling its use in engineering applications without compromising fit or function.[1] By 1910-1911, initial facilities were operational in the UK, marking the transition from experimental to industrial-scale production for rust-proofing ferrous items.[9] A notable early application occurred during and after World War I, when metal shortages prompted innovative uses of the process. In Germany, Sherardising was employed to coat iron 5 and 10 pfennig coins with zinc between 1915 and 1922, creating a rust-resistant cladding that allowed continued circulation of low-denomination currency despite the scarcity of precious metals. These coins, composed of iron cores sherardised with zinc, demonstrated the process's reliability in high-volume production, with many surviving examples remaining corrosion-free to this day.[10] This wartime necessity highlighted Sherardising's potential for mass application, contributing to its recognition as a practical alternative to wet galvanizing for items requiring uniform, adherent coatings.[1] Post-World War I, Sherardising expanded across Europe for industrial parts, with the first large-scale facilities established in the UK and Germany by the 1920s to meet growing demand in manufacturing sectors like fasteners and hardware.[10] In the UK, adoption surged for small components in engineering and construction, while German operations scaled up for similar uses following the coin production success. By the 1930s, developments focused on refining the process, including larger rotating drums to handle increased batch sizes and improved temperature controls around 300-420°C to optimize coating uniformity and reduce processing times to as little as 2.5 hours per cycle.[1] These enhancements lowered costs to approximately $0.035 per pound by 1935 and solidified Sherardising's role as a viable, dry alternative to wet methods, particularly for delicate or threaded items where hot-dipping posed risks of distortion.[1]Process
Preparation and Setup
Sherardising is applicable exclusively to ferrous metals, such as iron and steel articles, including structural steel, heat-treatable steel, and cast iron, due to the need for zinc-iron alloy formation during diffusion.[11][12] Prior to processing, parts must be thoroughly cleaned to remove contaminants like oil, grease, rust, scale, lacquers, wax, paint, or moulding sand from castings, ensuring optimal surface readiness for zinc vapor interaction.[11][12] Mechanical methods, such as grit or shot blasting, are preferred for surface preparation, while chemical options like alkaline degreasing or hydrochloric acid pickling may be used if followed by thorough rinsing and drying; no additional chemical pretreatment is required for mechanically prepared metallic blanks.[11][12][13] The primary equipment consists of a closed, slowly rotating drum or container, typically made of steel and housed within a furnace, with dimensions around 2,000 mm × 480 mm × 400 mm for standard batches, limiting it to small or complex items like fasteners and suitable for batch processing.[12][11] These drums are designed to withstand temperatures up to 500°C and rotate at approximately 4–5 revolutions per minute to promote even distribution of materials during setup.[11] Specialized setups can accommodate larger items, such as pipes up to 6 m in length, though most applications focus on compact, geometrically intricate components.[14] The zinc source is high-purity zinc dust or powder, with a minimum zinc content of 95% and particle sizes ranging from 5–40 μm on average, up to a maximum of 70 μm, to facilitate controlled evaporation. In modern variants, the zinc powder may be mixed with an activator such as ammonium chloride to promote diffusion.[11][15][3] It is typically mixed with inert fillers, such as silica sand or alumina (Al₂O₃), at ratios like 50:50 to prevent clumping and sintering while occupying less than 60% of the reaction space volume.[11][15][16] Safety measures emphasize an airtight, low-oxygen environment within the closed container to prevent oxidation and excessive zinc fume release, with oxygen levels controlled to ≤5 vol.% (ideally ≤0.01 vol.%) through evacuation or inert gas like nitrogen.[15] Initial pre-heating to 300–350°C is applied to initiate zinc evaporation without melting, typically maintaining temperatures 300–420°C overall to avoid exceeding zinc's melting point and minimize distortion risks.[15][11][12]Thermal Diffusion Procedure
The thermal diffusion procedure in Sherardising begins once the ferrous parts and zinc dust have been loaded into a sealed, rotating drum or container. The drum is then placed in a furnace and rotated at a speed of 4-5 revolutions per minute to ensure uniform exposure of the parts to the zinc vapor. Heating is applied gradually to the assembly, raising the temperature to between 300°C and 420°C over a controlled period, with the process duration typically ranging from 1 to 4 hours depending on the desired coating thickness (higher temperatures up to 450°C may be used in some variants).[11][17] At temperatures above approximately 300°C, the zinc dust undergoes sublimation, evaporating to form zinc vapor without melting in standard processes. This vapor diffuses into the steel surface through thermal activation in a solid-state reaction, creating a dry process that avoids the use of fluxes or liquid zinc. The diffusion occurs via atomic migration of zinc into the iron lattice, facilitated by the high temperature and vapor proximity to the substrate.[18][11][17] The reaction results in the formation of layered zinc-iron intermetallic alloys, establishing a metallurgical bond between the coating and the base metal. These layers include the outer zeta (ζ) phase (FeZn₁₃), and the inner delta (δ) phase (FeZn₇), with possible traces of deeper Γ phase, with composition gradients providing enhanced corrosion resistance. The thickness of these layers increases with exposure time and temperature, for example reaching 17 μm after 1 hour and up to 75 μm after 4 hours at 400°C.[11][18][19] Precise temperature ramp-up is essential to prevent uneven coating formation or thermal stresses in the parts. Upon completion, the drum is removed from the furnace and cooled in an inert atmosphere, such as nitrogen, to room temperature, thereby avoiding oxidation of the freshly formed zinc-iron layers.[11][17]Post-Processing and Coating Characteristics
After the thermal diffusion procedure, the sealed drum containing the treated parts and zinc mixture is allowed to cool slowly to room temperature, typically in a closed chamber or separate cooling station, to prevent oxidation and ensure uniform coating stabilization.[11] This controlled cooling phase, often lasting several hours, maintains the integrity of the diffusion-formed alloy layers. Once cooled, the parts are unloaded from the drum, and excess zinc dust or inert filler is removed through mechanical methods such as screening, tumbling, or sieving to clean the coated surfaces without damaging the diffusion bond.[11][1] The resulting Sherardised coating consists of a uniform zinc-iron alloy layer, typically 15-150 microns thick, exhibiting a composition gradient that transitions from a zinc-rich outer phase (approximately 90-94% zinc in the ζ-FeZn₁₃ phase) to more iron-rich inner phases (such as δ-FeZn₇ with 87-92% zinc and traces of Γ phase near the substrate).[20] This multilayer structure forms through solid-state diffusion, providing strong metallurgical adhesion to the ferrous base without distinct interfaces or delamination risks. Hardness within the coating varies by phase and depth, generally ranging from 150-250 HV in the outer layers to higher values (up to 400-500 HV) in the inner iron-enriched regions, enhancing wear resistance.[13][20] Coating thickness is primarily controlled by process parameters including diffusion time, temperature (typically 350-450°C), and zinc vapor concentration, following diffusion kinetics where thickness approximates , with as the effective diffusion coefficient (approximately m²/s at 400°C), as exposure time, and as a proportionality constant dependent on alloy phase formation.[22][23] Longer exposure times yield thicker coatings, for example, increasing from about 15-20 µm after 1 hour to over 75 µm after 4 hours at 400°C, allowing precise tailoring to application needs per standards like ISO 17668.[11][16] The surface finish of the Sherardised coating is characteristically smooth and matte gray, free from drips, runs, or lumps due to the dry vapor-phase process, which conforms uniformly to complex geometries including threads and holes without requiring post-machining.[13][20] This finish provides a low-friction, aesthetically consistent appearance suitable for threaded fasteners and intricate parts, with surface roughness (Ra) typically decreasing from around 6 µm to 4.5 µm as coating thickness increases, improving wettability for subsequent treatments if needed.[11]Applications
General Uses
Sherardising is widely applied to fasteners and hardware components, such as screws, bolts, nuts, and washers, particularly in construction and machinery where uniform corrosion protection across threaded surfaces and intricate details is essential. This process ensures even zinc diffusion without buildup that could impair functionality, making it suitable for items requiring precise fit and long-term durability in exposed environments.[24] The coating method excels for small, intricate parts like chains, clips, springs, and wire goods, which often feature complex geometries that challenge other galvanizing techniques. By tumbling parts in a zinc-rich atmosphere, Sherardising achieves complete coverage without distortion or dimensional changes, preserving the mechanical integrity of delicate components used in assemblies ranging from consumer products to industrial tools.[16][24] For internal surfaces, Sherardising coats pipes, tubes, and hollow sections effectively, providing corrosion resistance in fluid-handling systems where moisture or chemicals pose risks. The vapor-based diffusion penetrates hard-to-reach interiors without requiring disassembly, ideal for underground pipelines, valves, and structural tubing that demand protection on both exterior and interior walls.[25][24] Decorative applications include historical items like iron coins coated in the 1920s, many of which remain rust-free today, demonstrating the process's enduring protective qualities. In modern contexts, it enhances architectural fittings such as gate furniture, door hardware, hinges, and window components, offering a matte zinc finish that combines aesthetic appeal with robust corrosion resistance for exterior and interior ironmongery.[10][26]Specific Industries
In the oil and gas sector, Sherardising is employed to coat long pipes up to 3.7 meters in length and various fittings, providing robust corrosion resistance in harsh environments such as offshore platforms and pipelines exposed to aggressive chemicals and moisture.[27][28] This application ensures the longevity of critical infrastructure components like threaded joints ranging from M8 to M80, where the coating's uniformity and resistance to hydrogen embrittlement support reliable performance under high-pressure conditions.[29] Within the automotive and aerospace industries, Sherardising protects precision components such as brackets and connectors, which must withstand vibration, temperature fluctuations, and corrosive elements without material embrittlement.[28][30] In automotive applications, it safeguards fasteners and small structural parts against road salts and exhaust fumes, enhancing vehicle durability.[28] For aerospace, the process improves load-bearing capacity, service life, and safety in components like engine mounts and airframe fittings, where even minor corrosion can lead to catastrophic failures, as evidenced by historical incidents including the 1998 Aloha Airlines Boeing 737 roof failure.[30] Sherardising finds extensive use in marine and offshore settings to coat anchors, rigging elements, and deck hardware, offering superior protection against saltwater exposure and mechanical wear in demanding maritime conditions.[31][32] These coatings ensure that steel fabrications and castings, such as swivel hoist rings and seawall anchors, maintain integrity in subsea and wave-impacted environments, reducing maintenance needs and extending operational lifespans.[33][34] In the electrical industry, Sherardising is applied to conduit fittings and grounding rods, balancing electrical conductivity with environmental protection to prevent failures in outdoor or humid installations.[28][31] This zinc diffusion layer on steel components like enclosures and threaded connectors resists corrosion from soil moisture or atmospheric pollutants while preserving the material's mechanical properties, making it suitable for grounding systems that require reliable earth connections.[28][35]Advantages and Disadvantages
Key Benefits
Sherardising provides superior corrosion resistance through the formation of a zinc-iron alloy layer that acts as both a sacrificial anode and a barrier, protecting the underlying steel from oxidation even if the coating is damaged. This metallurgical bond ensures long-term durability, with service life estimates exceeding 20 years for a 35 µm coating in urban environments (corrosivity category C3), depending on thickness and exposure. Unlike organic paints, which offer only superficial barrier protection prone to cracking and peeling, the diffused alloy layer integrates directly into the substrate, preventing underfilm corrosion and enhancing overall longevity.[18][13][11] The process delivers exceptional uniformity and precision in coating application, achieving consistent thicknesses of 10–110 µm across all surfaces, including threads, holes, recesses, and internal cavities of complex geometries. This even diffusion eliminates the buildup, drips, or inconsistencies common in liquid immersion methods like hot-dip galvanizing, ensuring no distortion or interference with mating parts. As a result, Sherardising is particularly advantageous for precision-engineered components requiring tight tolerances and functional integrity post-coating.[18][14] A key benefit of Sherardising is the effective avoidance of hydrogen embrittlement. Although preparatory acid pickling may introduce hydrogen, the dry, vapor-phase diffusion at 320–500°C bakes it out, eliminating risks associated with wet methods and preserving the material's ductility and tensile properties, making it ideal for critical applications in fasteners, springs, and structural elements where embrittlement could lead to brittle failure.[18][14] Dimensional stability is maintained throughout the Sherardising process, with no measurable change in part size, warping, or stress relief that could affect close-tolerance assemblies. The solid-state diffusion mechanism ensures the original geometry and fit of components remain unaltered, unlike wet processes that may cause expansion or contraction due to immersion or hydrogen absorption. This characteristic supports its use in high-precision industries without requiring post-coating machining.[18][36]Principal Limitations
One principal limitation of the Sherardising process is its restriction to small batch sizes due to the dimensions of the rotating drums used, which typically have diameters of 24 to 30 inches (approximately 0.6 to 0.76 meters), limiting the maximum part size to around 300 mm in length or diameter.[1][37] This constraint makes Sherardising unsuitable for coating large structures, such as bridges or extensive steel frameworks, where alternative methods like hot-dip galvanizing are preferred for scalability.[38] The process also involves extended processing times of 2 to 6 hours per batch, plus additional setup and cooling periods, which can extend to 6-8 hours overall, resulting in lower production efficiency compared to continuous methods.[16] Furthermore, the batch-oriented nature and specialized equipment lead to higher operational costs and energy consumption than hot-dip galvanizing, rendering Sherardising economical primarily for low-volume production of small components rather than high-throughput applications.[39][40] Temperature control during the diffusion phase, conducted at 300-500°C, poses a risk of distortion or warping in thin or complex ferrous parts if heating is not perfectly uniform, necessitating precise furnace management.[24] Additionally, Sherardising is limited to ferrous metals, such as iron and steel, as the zinc diffusion mechanism does not effectively bond with non-ferrous substrates.[14][16] Coating thickness in Sherardising is generally constrained to 10-110 microns, with achieving thicknesses beyond 100 microns requiring multiple treatment cycles, which further increases time and cost.[18] Variability can also arise from inadequate control of zinc dust distribution within the drum, potentially leading to uneven diffusion or residual contamination if post-processing is insufficient.[12]Standards and Comparisons
International Standards
Sherardizing practices are regulated by international standards to ensure reliable corrosion protection and consistent coating quality on ferrous products. The key global norm is ISO 17668:2016, which outlines specifications for zinc diffusion coatings applied through the sherardizing process, including requirements for coating uniformity, appearance, and minimum thickness across six classes.[41] Complementary guidelines appear in ISO 14713-3:2017, which addresses design principles for sherardized articles to optimize corrosion resistance in various structural applications, emphasizing factors like substrate preparation and environmental exposure.[42] Coating thickness requirements are classified to match duty levels, with minimum local thicknesses ranging from 10 μm for Class 10 to 75 μm for Class 75, with higher thicknesses possible if required, determined primarily by process duration and zinc concentration.[41] Adherence and thickness are verified using non-destructive magnetic induction methods for ferromagnetic substrates or microscopic cross-section analysis for precision.[43] Quality assurance protocols mandate high-purity zinc powder exceeding 99% to minimize impurities that could affect diffusion, alongside continuous temperature logging (typically 380–500°C) to maintain process stability and prevent defects. Post-coating evaluations include adhesion tests such as the bend test (per ISO 14713 series) to confirm bonding integrity and accelerated salt spray exposure (ISO 9227) to assess durability, ensuring coatings meet performance thresholds without flaking or cracking.[42] Regionally, the United States employs ASTM A1059/A1059M-24 for zinc alloy thermo-diffusion coatings on steel fasteners, aligning with sherardizing by specifying similar diffusion parameters, thickness classes (15–200 μm), and testing for embrittlement resistance.[44] In the European Union, sherardized products adhere to RoHS Directive 2011/65/EU, as the zinc-iron alloy layers contain no restricted hazardous substances like lead or cadmium above permissible limits.[45]Comparison to Other Zinc Coatings
Sherardising, a thermal diffusion process using zinc vapor, differs fundamentally from hot-dip galvanizing, which involves immersing steel in molten zinc at approximately 450°C. This dry, vapor-based method avoids the need for fluxing agents and molten metal handling, resulting in no residues or drips that can occur in hot-dip processes.[18][25] The coatings produced by Sherardising are smoother and thinner, typically ranging from 15 to 150 μm, compared to the rougher, thicker layers (50–200 μm) from hot-dip galvanizing. This thinner alloy layer—composed of zinc-iron intermetallics like gamma and delta phases—provides a more uniform finish suitable for small or complex parts, such as screws and threaded components, where hot-dip's excess zinc buildup could distort geometry. However, Sherardising is less scalable for large structures due to its batch-oriented nature in rotary furnaces.[18][25][46][47] In contrast to electroplating, which deposits a pure zinc layer via electrochemical means in aqueous solutions, Sherardising creates a metallurgical bond through atomic diffusion at 320–500°C, yielding superior adhesion without the risk of hydrogen embrittlement that can brittle high-strength steels in electroplating. While electroplating allows for precise, thin coatings (often <20 μm) at ambient temperatures, Sherardising's higher process heat ensures a more robust, alloyed barrier but limits its use to heat-tolerant substrates.[18][25][48] Compared to mechanical plating, a cold peening process that embeds zinc particles onto the surface without alloying, Sherardising forms a diffused zinc-iron layer that offers enhanced corrosion resistance through sacrificial and barrier protection. Mechanical plating provides a rougher, non-alloyed coating suitable for high-volume production, but Sherardising excels in uniformity and durability for intricate shapes, albeit at a slower pace and higher cost for bulk applications.[18][49] Overall, Sherardising is optimal for precision engineering components requiring uniform, residue-free protection, whereas hot-dip galvanizing remains preferred for expansive outdoor structures like bridges due to its thicker, cost-effective coverage.[25][46]References
- https://www.[mdpi](/page/MDPI).com/1996-1944/12/9/1400