SN 2011-01-0007

CORROSION RESISTANT NITROGEN ALLOYED STEELS WITH HIGH HARDNESS Odd Sandberg and Alf Sandberg Uddeholms AB, SE-683 85 Hagfors, Sweden

ABSTRACT A unique series of corrosion resistant nitrogen alloyed steels has been developed. By substituting most of the carbon content by nitrogen in martensitic Cr-V-Mo alloyed steels it has been possible to significantly increase corrosion resistance, close to that of austenitic stainless steels, and at the same time obtain a hardness level around 60 HRC. The elimination of hard phase particles of chromium carbide type, M7C3, and introduction of finely distributed hard phase particles of type MN results in high general wear resistance and low friction properties. The unique property combinations for these new high nitrogen alloyed steel grades have been possible to combine by using a special powder metallurgy process route. The paper presents the properties profile of the new high nitrogen alloyed steels as well as industrial application results. INTRODUCTION Increasing demands on tooling components often occur as more effective, robust and/or higher performing process systems are introduced. With higher process temperatures and stresses the tool components are subjected to more wear, erosion and/or corrosion. Food processing is nowadays subjected to rigorous measures to maintain clean and functional environments. Plastic processing incorporates more advanced polymers containing corrosive additives and wearing reinforcements involving both long processing times and high temperatures. The design of the plastic component is another aspect to consider as the part has to be easily ejected without being distorted or giving a high scrap rate it is thus advantageous that the adhesion force of the plastic part to the metal insert/mould is low. Due to low wear resistance and hardness austenitic or ferritic stainless steels of type AISI 316 and AISI 444 are not in common use in applications where wear and indentations are typical failure mechanisms, else frequent refurbishment actions as e.g. regrinding must be performed. However, the corrosion resistance of these low carbon alloys is very good as corrosion resistance is based on a thin passive layer consisting of a chromium rich oxide surface film. The effectiveness of this protective surface film is strengthened with increasing amounts of Cr, Mo and N in solid solution in the steel. In mild environments as water based non-chloride containing solutions chromium in solid solution of 12-13% is normally adequate to avoid the base metal to start dissolving and forming corrosion products. In more aggressive solutions as sea water, salt, acid or alkaline solutions found in food or plastic processing, there is a need of steels possessing higher alloy contents of chromium, molybdenum and/or nitrogen in solid solution in order to counteract severe corrosion damages.

SN 2011-01-0007

Hard, > 58 HRC, and wear resistant steels are found in more or less advanced variants exhibiting very varying corrosion properties. To target a properties profile consisting of high hardness, adequate ductility, high wear resistance and a favourable corrosion resistance both carbon, nitrogen, alloying elements and processing conditions must be carefully selected. Carbon and nitrogen has to be balanced in relation to the desired amount of carbide forming elements, Cr, Mo, W, V and Nb, resulting in wear resisting hard phases, which also controls the amount of Cr in solid solution affecting corrosion resistance. Besides this, a certain amount of carbon and/or nitrogen is necessary in solid solution to produce a hard martensitic matrix. Generally, to counteract any type of wear the hard phase should have a high hardness (M6C ~1500HV, M7C3 ~1700HV, MC/MN ~2800HV) and to promote ductility the hard phase particles should be small and evenly distributed in the matrix. AISI D2 (12%Cr-1,5%C) is a common tool steel grade in many applications and can be heat treated to 60 HRC. The carbide content of 14% M7C3 results in good wear resistance. Even if this grade nominally is alloyed with 12% Cr most of the Cr is ineffective from a corrosion resistant point of view as it is used for formation of carbides. In as-quenched condition only about 6% Cr is in solid solution, which is far below an acceptable level from a corrosion perspective. Also, as this grade normally is high temperature tempered chromium is further depleted from solid solution due to secondary hardening forming submicron chromium carbides. To protect against corrosion methods as Cr-plating or PVD surface coating are sometimes used. As long as the surface coating is intact and crack free corrosion can be avoided, but wear and stresses will in due time cause delamination and/or scratching of the surface layer resulting in corrosion attacks. A more suitable grade in applications requiring both corrosion and wear resistance is the 17%Cr-1,1%C grade of AISI 440C type. As for AISI D2 this grades is normally conventionally cast and contains an anisotropic carbide structure of M7C3 emerging from the solidification process. After hardening at 1050oC (1920oF) approximately 12,5% Cr is in solid solution resulting in fairly modest corrosion properties as the residual chromium content is tied up as M7C3. Tempering at high temperatures, ~500oC (~930oF) results in an intense precipitation hardening of chromium carbides resulting in a further reduction of chromium in the matrix. The abrasive wear resistance is enhanced by the presence of big solidification carbides, but is counteracted by the softness of the M7C3 carbide (1700HV). Also, ductility is low due to the anisotropic carbide microstructure encountered in both AISI D2 and AISI 440C. One concept to increase wear resistance is to add strong carbide forming elements as V (3-9%) or Nb (<4%) to promote the formation of MC carbides and at the same time utilize a high austenitizing temperature, 1150oC (2100oF) to partly dissolve M7C3 and eventually any M6C carbides. These grades are then normally produced via powder metallurgy (PM) resulting in a fine distribution of smaller hard phase particles, which at the same time improves ductility. Furthermore, by limiting the Cr-content to 14% even more MC carbides are formed at solidification resulting in about 50% MC carbides (1). However, still a high amount (40-90%) of the less desired M7C3 carbide is present in these high alloyed PM grades resulting in a maximum amount of Cr in solid solution of around 11-13%. A more viable concept to produce high hardness steels with very good wear and corrosion resistance is to exchange most of the carbon with nitrogen. This eliminates the presence of the less wear resistant M7C3 and M6C carbides resulting in the formation of one very stable hard phase particle of type MN. This nitride is hard and wear resistant. Thus, this new alloy system can achieve the same wear resistance with lower amount of hard phase particles than carbon based alloys due to the lack of softer hard phase particles. Alternatively, at the same hard phase fraction the new high nitrogen alloyed grades show improved wear resistance (2). Another feature of this alloy system is the presence of a dense distribution of hard phase particles with a high aspect ratio (height to width) with an ability to reduce cold welding or adhesion of the work material to the tool steel surface. This characteristic feature is the same as that found in non corrosion resistant low friction steel grades based on alloy systems with high amounts of vanadium and nitrogen (2, 3). In many applications even coated systems can be replaced by non-coated grades of this new alloy system due to their anti-galling and excellent corrosion properties. The use of an adapted thermodynamic database (4) has shown to be a valuable tool to develop these advanced nitrogen alloyed grades. To provide correct information to the database of chemical composition of the stable phases an analytical scanning electron microscopy has been used. The hard phase particles have been coarsened by

SN 2011-01-0007

long time annealing at high temperatures to be measurable and Fig. 1 illustrates the technique used to provide this information. The phase fractions of the stable phases at various temperatures have been determined by image analysis of microstructures of the heat treated samples.

C 0,5

N 18

V 42

Cr 36

Mo 0,5

Fe 3

Figure 1. Measured composition in weight percent of the MN phase of a high nitrogen Cr-V-Mo alloy after long time annealing at high temperature. In this paper two high nitrogen alloys are presented with an amount of hard phase particles varying from 9 up to 23 vol-% MN. Both grades exhibit an excellent corrosion resistance due to a high solid solution content of Cr, around 18%, N and Mo in the matrix. The corrosion properties of these high nitrogen alloyed grades are superior compared to all existing carbide rich corrosion resistant steels and also significantly improved even to high hardness matrix carbon and nitrogen alloyed grades with 13-15%Cr (2). Thus, the benchmark from a corrosion properties point of view for this new alloy family has moved from corrosion resistant tool steels to low carbon austenitic and ferritic stainless steel grades (5). These new high nitrogen alloyed grades are produced via powder metallurgy. Materials in bars or sheets are processed from HIP-capsules via forging or rolling. Besides the normal bar executions as flat and round dimensions the alloys are suitable also for HIP-clad processing especially against stainless base material, as no reduction of the corrosion resistance of the base material occurs in the HIP compound zone (6). In the following a summary is given of the properties of these novel high hardness and high nitrogen alloyed steels as well as showing the wide application range suitable for these alloys. RESULTS Material, microstructure and heat treatment The investigated steel grades all have a certain combination of corrosion and wear resistance and an ability to achieve a hardness after heat treatment in excess of 56 HRC. Table 1 and 2 show the chemical composition of the investigated steels, the solid solution content of Cr after austenitizing and quenching to room temperature, the PRE number as well as the amount and type of hard phase particles. Cr in solid solution and the PRE number are measures to indicate the resistance to general and pitting corrosion, respectively, where a high PRE number indicates a higher pitting corrosion resistance. The PRE number is the sum in weight percent of the following elements in solid solution Cr+3,3Mo+16N. It should be pointed out that at tempering at higher temperatures, ~450oC (~842oF) precipitation of chromium rich phases will start to reduce the amount of chromium in solid solution and thus also the PRE number. Table 2 shows the amount and type of hard phase particles present in the grades. The two high nitrogen alloyed development grades, Vanax 35 and Vanax 75, have approximately the same base chemistry consisting of 0,2%C, 2021%Cr, 1,3-2,5%Mo, but different alloy contents of V and N to form the desired amounts of hard phase particles of type MN. V and N contents in Vanax 35 and Vanax 75 are set to 2,8%V/1,9%N and 9,0%V/4,3%N , respectively. The amount of Cr in solid solution is for both grades around 18%, which is significantly higher than for any other tool steel grade available today. As reference materials three carbon based PM steel grades with a high amount of carbides have been included; Uddeholm Elmax (18%Cr-

SN 2011-01-0007

3%V), AISI 618 (13%Cr-4%Mo) and 14Cr9V. Furthermore, three conventional produced high carbon high chromium grades are also included; AISI 440B (18%Cr-0,9%C), AISI 440C (17%Cr-1,1%C) and AISI D2 (12%Cr-1,5%C). In addition to the above grades having hard phase contents of 9 to 23 vol-% two martensitic matrix steels, 13Cr and 15Cr, are included. The latter grade is an ESR produced steel showing an improved corrosion resistance due to partial substitution of carbon by nitrogen compared to the conventional 13Cr steel. Table 1: Chemical composition and solid solution content of Cr in wt-%. Calculated by Thermo-Calc. PM=Powder metallurgy. IC=Ingot cast. CC=Continuous cast. ESR=Electro slag remelted. C N Cr Mo V Cr Steel Process TA PRE grade route weight-% Vanax 35 PM 1080oC (1975oF) 0,2 1,9 19,8 2,5 2,8 18,2 35 Vanax 75 PM 1080oC (1975oF) 0,2 4,3 21,2 1,3 9,0 18,0 30 o o Elmax PM 1080 C (1975 F) 1,7 0,1 18,0 1,0 3,0 12,0 15 14Cr9V PM 1180oC (2155oF) 2,3 0,09 14,4 1,1 8,6 11,4 14 AISI 618 PM 1050oC (1920oF) 1,1 0,03 13,3 4,2 0,19 9,8 20 o o AISI 440B IC 1050 C (1920 F) 0,9 0,03 18,0 1,1 0,05 13,6 17 AISI 440C IC 1050oC (1920oF) 1,1 0,04 17,0 0,6 0,05 12,6 15 o o AISI D2 IC 1020 C (1870 F) 1,5 0,01 12,0 0,9 0,8 6,4 8 15Cr ESR 1050oC (1920oF) 0,3 0,4 15,0 1,0 0,05 14,9 24 13Cr IC 1080oC (1975oF) 0,6 0,02 13,4 0,03 0,06 12,4 13 Table 2: Amount and type of hard phase particles. Calculated by Thermo-Calc. PM=Powder metallurgy. Hardness in heat treated condition. IC=Ingot cast. CC=Continuous cast. ESR=Electro slag remelted. MN MC M2N M6C M23C6 M7C3 Total Steel Process TA grade route Volume-% o o Vanax 35 PM 1080 C (1975 F) 9 9 Vanax 75 PM 1080oC (1975oF) 23 23 Elmax PM 1080oC (1975oF) 2 16 18 14Cr9V PM 1180oC (2155oF) 9 10 19 o o AISI 618 PM 1050 C (1920 F) 1 9 10 AISI 440B IC 1050oC (1920oF) 5 5 AISI 440C IC 1050oC (1920oF) 9 9 o o AISI D2 IC 1020 C (1870 F) 14 14 15Cr ESR 1050oC (1920oF) 1 1 o o 13Cr IC 1080 C (1975 F) 2 2 The microstructure and hardness in the hardened and tempered condition for the steels are shown in Fig. 2. All grades have a tempered martensitic matrix with various amount and type of hard phases. The size of the hard phase particles is around 50% bigger in carbon based PM steels compared with MN particles in the nitrogen alloyed PM grades. In absolute values an average size of the MN particles is around 0,7 m in the heat treated condition. The conventionally ingot manufactured grade, AISI D2 and AISI 440B/C, may have maximum carbide sizes up to 100-200 m depending of ingot size and hot working reduction. A hardness of 56-61 HRC is attainable using the heat treatment cycles specified in Fig. 2. By utilizing low temperature tempering, 180-250oC, an optimum corrosion resistance is obtained by maintaining maximum amount of chromium in solid solution. At high temperature tempering, ~500oC, corrosion resistance deteriorates significantly and add little gain to hardness. However, both the new high nitrogen alloyed grades can be tempered up to 450oC or even 500oC and still maintain good corrosion properties if product application conditions require a higher tempering temperature.

SN 2011-01-0007

Vanax 35 - 9%MN - 59 HRC Vanax 75 - 23%MN - 61 HRC Elmax - 16%M7C3 + 2%MC - 59 HRC 1080C (1975F)/DC + 200C (392F)/2x2h 1080C (1975F)/DC + 200C (392F)/2x2h 1080C (1975F) + 200C (392F)/2x2h

14Cr9V - 10%M7C3 + 9%MC - 60 HRC 1180C (2155F) + 450C (842F)/2x2h

AISI 618 - 9%M7C3 + 1%M6C - 59 HRC 1050C (1920F) + 200C (392F)/2x2h

AISI D2 - 14%M7C3 - 60 HRC 1020C (1870F) + 200C (392F)/2x2h

AISI 440B - 5%M23C6 - 56 HRC 1050C (1920F) + 200C (392F)/2x2h

AISI 440C - 9%M7C3 - 58 HRC 1050C (1920F) + 200C (392F)/2x2h

40 m

13Cr - 2%M7C3 - 58 HRC 15Cr - 1%M2N - 58 HRC 1080C (1975F)/DC + 200C (392F)/2x2h 1050C (1920F)/DC + 200C (392F)/2x2h

Figure 2. Microstructure and hardness in hardened and tempered condition. DC=Deep cooling in liquid nitrogen (-196C; -320F) or dry ice (-40C; -40F to -80C; -112F). SEM.

SN 2011-01-0007

Performance comparison in selected applications The property profile of the steel is vital to recognize when selecting steel grades for specific application areas. Material properties of importance are related to aspects of corrosion, wear, adhesion and ductility. Manufacturing properties as machining, grinding and polishing in soft annealed or hardened condition as well as heat treatment conditions also has to be considered. In the following three application areas have been chosen to exemplify the potential performance increase that is attainable for the high nitrogen alloyed steels. The applications selected are processing of plastics, food and components in contact with biofuel. Plastic processing In plastic processing, as extrusion, the screw and cylinder are subjected to different failure mechanisms as metal to metal wear, abrasive and erosive wear, corrosive wear and adhesion depending on the plastics used and processing condition of the screw/cylinder system being exposed to different temperature, viscosity, contact pressure and relative speed of the plastic compound. Thus, the life time of the components is highly dependent on the corrosiveness and abrasiveness of the used polymers, fillers, lubricants, flame retardant and reinforcing products. A study has been made to investigate tribological wear and corrosion at the exit zone of the extruder (7). The test system consisted of two test platelets forming a rectangular gap, length 12 mm (0,47), width 10 mm (0,39), height 0,1 to 1,0 mm (0,004 to 0,04), mounted on the extruder outlet. A fixed amount, 20 to 50 kg (44 to 110 lbs), of the liquid polymer melt was extruded through the gap. Wear was determined as weight or volume loss as well as topographical change of the platelet geometry. Two different polymer resins of corrosive and abrasive nature were selected for the testing; PA 6/66 GF30 FR by EMS-Grivory and PVC GF30 by Polymer-Chemie. Both resins contained 30% glass fibres and the former also had flame retardant additives. The exit die temperature is close to the melting temperature corresponding to 315C (600F) and 210C (410F), resp. Vanax 75 was tested for two heat treatment conditions denoted 200C 61,5 HRC / 1080C (1975F)/30 min + DC + 200C (392F) /2x2h and 500C - 61 HRC / 1080C (1975F)/30 min + DC + 500C (932F)/2x2h. Grade 14Cr9V was tested in one condition: 60 HRC / 1180C (2155F )/30 min + 450C (842F)/2x2h. Two coating systems were included in the test programme: AISI D2 (58 HRC) + PVD Cr/CrN-multilayer and AISI D2 (58 HRC) + hard chrome. The result after extrusion of PA 6/66 GF30 FR shows an excellent performance for Vanax 75 both for low and high temperature tempered conditions and initially also of AISI D2 coated by CrN/Cr-multilayer. However, already extrusion of 20 kg (44 lbs) plastic resin resulted in excessive wear of the coating layer at inlet and outlet borders. It is assumed that the wear of the CrN/Cr-multilayered test platelets will increase significantly once the layer is entirely damaged. The carbon based PM grade 14Cr9V shows a magnitude higher wear loss. Thus, for this resin type the high nitrogen alloyed grade performs like a CrN/Crmultilayer coating, but with additional long-term stability. For PVC GF30, Vanax 75 shows the best performance in terms of wear resistance. AISI D2 + hard chrome initially perform like the Vanax grade, but in the end the entire layer is damaged and wear increases drastically. 14Cr9V shows the highest wear for PVC GF30 processing. Fig. 3 and 4 illustrates the above findings. Both corrosion and abrasive wear are limiting factors for the life time of tested steel grades.

SN 2011-01-0007

70 Mass loss after 30 kg PA GF30 FR 60 50 Mass loss (mg) 40 30 20 10 0 14Cr9V D2+PVD-CrN/Cr Vanax 75 200C Vanax 75 500C 20 kg PA GF30 FR

a)
14

Mass loss after 50 kg PVC GF30

12 10 Mass loss (mg) 8 6 4 2 0 14Cr9V D2+Hard chrome Vanax 75 200C

b)
Figure 3. Wear of tested platelets at processing of a) PA 6/66 GF30 FR and b) PVC GF30.

Figure 4. Wear of PVD multilayer CrN/Cr of AISI D2 after 20 kg extruded polymer resin of PA 6/66 GF30 FR.

SN 2011-01-0007

In injection moulding applications where a high surface quality is required, as for optical parts, sticking may appear between the plastic component and the steel mould surface. Strong adhesive forces can lead to difficulties at component ejection, but also to a deteriorated surface finish of the plastic part. In a recent investigation (8) Vanax 75 were compared to a non corrosion resistant high nitrogen alloy grade, Vancron 40 and an improved AISI 420 variant. The injection moulding tools were fabricated and polished to a mirror like surface. The experiments gave considerably lower ejection forces for both Vanax 75 and Vancron 40 when compared to the improved AISI 420 variant when injection moulding polycarbonate test discs, as shown in Fig. 5. Also, when injection moulding COC (Cyclic Olefin Copolymers) significant differences were found in the sticking tendency; 6 and 17 injection cycles were documented until sticking occurred for AISI 420 improved and Vanax 75, respectively. The mechanism is still not clear, but a difference in the adhesive layer thickness at the metal surfaces may be one explanation. The low content of non-metallic inclusions and the structure of small nitride precipitates give good conditions to perform high gloss polishing of both Vanax 35 and Vanax 75.

Figure 5. Ejection force integrals (ejection energy) versus number of shots at injection moulding for AISI 420 improved, 50 HRC, (green triangles), Vancron 40, 60 HRC, (blue dots) and Vanax 75, 60 HRC, (red diamonds) at processing polycarbonate discs (right part of picture) at 120oC (248oF) tool temperature and residence time 45 minutes. Biofuel engine components Work is ongoing worldwide to complement existing petroleum based fossil fuels with renewable biomass sources for energy production. Pyrolysis is one route in converting biomass to liquid products to be used in energy production. The future perspective is to use the liquids directly in diesel engines to generate electric energy. However, the pyrolysis oil is very corrosive as it is acidic (pH of 2-3,5), contains up to 40% water and also is erosive as it contains solid particles of tar and alkali (9). The injection nozzle system is a vulnerable component due to its tight tolerances and can be damaged if it is subjected to excessive wear, erosion, fatigue and/or corrosion. A study has been performed to evaluate the corrosive effects on steel samples from a pyrolysis oil with pH=2,6 and 40% water content (10). Four steel grades were immersed under non stirred conditions for seven days in pyrolysis oil of 20oC (68oF) to 130oC (266oF) in temperature. The steel grades tested were Vanax 35, Vanax 75, Uddeholm Elmax and AISI O1 (1%C-0,6%Cr steel). A standard heat treatment was performed according to data given in Fig. 2 for the three former grades and for AISI O1 the heat treatment was chosen to give a hardness of 60 HRC (850C (1562F )/30 min + 200C (392F) /2x2h. Additionally,

SN 2011-01-0007

the effect of the tempering temperature was studied for the two high nitrogen alloyed grades utilizing the same hardening procedure, but tempering between 200C (392F)/2x2h and 500C (932F)/2x2h, which resulted in hardnesses between 59-62 HRC. The results, based on weight loss of the samples and expressed as corrosion rate in mm/year, are presented in Fig. 6 and 7.
10000
1080C (1975F ) / 30 min + DC + 200-500C (392-932F)/2x2h

9000

Vanax 35
8000
7475 Corrosion rate (mm / year)

7000 6000 5000 4000 3000 2000

41 3253

1000 0 20
2 2,3 2,7 85

746

3,6

70

95

500 450 Tempering 400 temperature 200 (oC)

Biofuel temperature (oC)

130

Figure 6. Corrosion rate for Vanax 35 tempered between 200C (392oF) and 500C (932oF) after exposure in pyrolysis oil at 20C (68F) to 130C(266F) for 7days (10).

14000 12603 12000 10000 8000 6000 4000 2000 0 2,3 3,8 3641 11881

Corrosion rate (mm / year)

3253

Vanax 35 200C

Vanax 35 500C

Vanax 75 200C

Vanax 75 500C
o

Elmax 200C

AISI O1 200C

Biofuel temperature ( C)

Figure 7. Corrosion rate for the investigated grades tempered at 200C (392oF) or 500C (932oF) after exposure in pyrolysis oil at 70C (158F) for 7 days (10).

SN 2011-01-0007

Both the high nitrogen alloyed grades showed very similar results and Fig. 6 illustrates the results for Vanax 35. For tempering temperatures up to 400C (752oF) very low corrosion rates appear as the material is in a passive state. Even at a tempering temperature of 450C (842F) fairly low corrosion rates are valid, but at higher tempering temperatures as 500C(932F) a faster corrosion rate does occur, which is more accentuated with increasing biofuel test temperatures. Even so, the corrosion rate for the nitrogen alloyed grades is still significantly better after high temperature tempering, 500C(932F), than after low temperature tempering, 200C(392F) of the two reference grades, see Fig. 7. The corrosion type is pitting corrosion for the two high nitrogen alloyed grades when tempered above 450C (842F) versus general corrosion for Elmax and AISI O1 (10). Food processing Food safety and productivity are important aspects to consider in food processing. A suitable selection of tool materials can in certain parts of the process chain give rise to lower production costs, simplified maintenance and less adverse impact on food quality. The new generation of nitrogen alloyed steels exemplifies a concept where excellent corrosion resistance is combined with high hardness, good wear resistance and adequate ductility. This opens for new solutions in automated food processing where minimum downtime is crucial for operating success. The high hardness and good wear properties involve less frequent tool resharpening but, most of all, the tools survive the aggressive disinfection solutions of acidic, pH=2, and alkaline, pH=12, types for long times meaning replacement and adjustment of tools can be postponed, Fig. 8 and 9 (11).

Figure 8. Circular knife used in the food processing industry for loosening heart plucks of pigs, where Vanax 75 shows extended performance over the conventional grade (13Cr). 200x4 mm (7,8x0,16).
Company: Danish Meat Research Institute Tool component: Knife Work material: Tool dimension: Procedure: Pig tail 300 x 57 x 12 mm Rinsing in warm water in end of working day followed by immersion in acid solution, pH 2, and next day in a basic, pH 12, desinfection solution.

Steel Hardness Heat treatment Cuts/regrind Failure mechanism Note

AISI D2 60 HRC 1020oC/30 min + 200oC/2x2h 14 000 / 14 days Corrosion after cleaning procedure Not any longer approved from a health concern as a result from a veterinary verdict

Vanax 75 61 HRC 1080oC/30 min + DC + 200oC/2x2h > 400 000 / once As new 800 cuts per day

Figure 9. Flat knives used in the food processing industry for cutting pig tails, where Vanax 75 meets present health regulations.

SN 2011-01-0007

As the knife edge will be in contact with both soft and hard substrates as meat and bone it is essential the cutting edge stays sharp without being blunt due to wear, plastic deformation or micro chipping. Thus, the knife cutting edge must be properly balanced in alloy constituents for the selected application. Knife steels with lower hardness <54-55 HRC are suitable where severe impact stresses do occur and less importance is focussed on wear resistance. On the other hand if less bending and impact stresses are occurring as in robust and stable cutting machines a significantly better indentation and wear resistance may be found in knife steels with higher hardness and an increasing hard phase amount. Fig. 10 exemplifies the effect of an improved wear resistance of the high nitrogen alloyed grade resulting in an extended tool life between regrinds in case of a hole cutting knife for pig ham production, and thus an significantly improved cutting cost.

Company:

Danish Meat Research Institute

Tool component: Hole cutting knife Work material: Tool dimension: Pig ham 62 / 60 x 177 mm

Steel Hardness Heat treatment Tool life / regrinds Failure mechanism Cutting cost / pig Note

13% Cr

AISI 440B

Vanax 75

56 HRC 57 HRC 61 HRC 1050oC/30 min + 1050oC/30 min + 1080oC/30 min + o o 200 C/2x2h 200 C/2x2h DC + 200oC/2x2h 16 000 cuts / 8 40 000 cuts / 10 180 000 cuts / 15 Wear Wear Wear 0,23 DKK 0,12 DKK 0,05 DKK Stand still cost is not incl. in cutting cost

Figure 10. Hole cutting knife used in the food processing industry for cutting pig ham, where Vanax 75 shows the lowest cutting cost due to its better wear resistance. DISCUSSION Corrosion control in aqueous solutions In the food industry both the ingredients as e.g. mustard and ketchup are aggressive from a corrosion point of view, but even more the disinfection solutions of acidic and alkaline nature are most harmful and different remedies as passivation and chrome plating are put into service to extend the operation time of the cutting tools. However, these methods are short term based as wear will penetrate the thin passive layer or coating leaving the base metal open for wear and accelerated corrosion. Another actual application is biofuel production. The biofuel are more or less aggressive depending on its content of water, wear debris and electrochemical reactivity. It is expected that in many applications a search for new materials are a must to counteract the shorter life time of critical components due to increasing wear and corrosion problems. Cyclic polarization measurements performed in diluted chloride solutions can be used to rank materials in terms of their resistance to localized corrosion, i.e. from a passive state there is a break through of the passive layer and localized corrosion is initiated. The corrosion resistance for a number of steels has been compared versus tempering temperature, Fig. 11, and confirms the excellent corrosion resistance of Vanax 35 and Vanax 75 compared to carbon based high hardness and wear resisting grades with a high content of hard phase of M7C3 and MC carbides. Also, even compared to nitrogen alloyed matrix steels with 15%Cr both the high nitrogen alloyed grades have a significantly better corrosion resistance. The extended solid solution content of chromium, molybdenum and nitrogen all contributes to an improved pitting corrosion resistance for these new grades.

SN 2011-01-0007

400

392F Vanax 35 Vanax 75

752F

932F

300
15Cr

Break down potential (mV)

200

100

0
13Cr
Break down potential in 0,1 M NaCl (0,35%Cl-), pH=7 and 20oC. Initiation of pitting corrosion is delayed with higher break down potential.

-100

-200
AISI D2, AISI 440B, AISI 440C, AISI 618, 14Cr9V, Elmax

-300

-400 150 200 250 300 350 400 450 500 550

Tempering temperature, 2x2h (C)

Figure 11. Pitting corrosion resistance in 0,1 M NaCl measured as break down potential at electrochemical polarization testing showing the superior corrosion resistance of the two high nitrogen alloyed grades. Application Areas for High Nitrogen Alloyed Tool Steel Grades The new generation of high nitrogen steels has a unique properties concept, which is of importance for many applications, and consists of: Excellent corrosion resistance Low friction properties High hardness High wear resistance Good ductility Good machinability and grindability

An excellent corrosion resistance has before not been possible to combine with all the above mentioned properties. Applications in need of material with high indentation resistance, high hardness, good wear resistance and excellent corrosion resistance in e.g. water based chloride solutions, acidic or alkaline solutions may find interesting property combinations in the new nitrogen alloy system represented of Vanax 35 and Vanax 75. Such applications may be knives, sliding / rolling machine elements and valves in corrosive environments. Plastic moulding where mould release, wear resistance and corrosion aspects are of importance is another important application area.

SN 2011-01-0007

CONCLUSIONS A new generation of high nitrogen PM alloys with an excellent corrosion resistance in combination with high hardness, low friction properties and high wear resistance has been developed. Besides the normal bar executions as flat and round dimensions the alloys are suitable also for HIP-clad processing especially against a stainless base material as no reduction of the corrosion resistance of the base material occurs. Applications are found in various machine and engineering processes as well in food processing. Plastic moulding and special cold work applications are other suitable areas for these grades. This is due to the presence of a well distributed low friction phase of MN type in a martensitic matrix with a high content of Cr, Mo and N in solid solution. Tool making and heat treatment are according to standard procedures. When the tool needs refurbishment this can rapidly be performed in-house by conventional machining procedures saving cost and lead-time. Also, compared to surface coated grades similar or even a better performance have been found in various applications for this new generation of steels. REFERENCES 1. M.K. Sawford, J.J. Eckenrod, A. Kajinic and A.L. Wojcieszynski, Corrosion and Wear Resistance of PM Martensitic Stainless Tool Steels for use in Food Processing Environments, Proceedings of the 8th International Tooling Conference, compiled by P. Beiss, C. Broeckmann, S. Franke, and B. Keysselitz. Aachen, 2009, pp. 201-212. 2. O. Sandberg and A. Sandberg, Corrosion and Wear Resistant Nitrogen Alloyed Steels, Proceedings of Dansk Metallurgisk Selskabs Vintermte, Gothenburg, 2010, p. 165-182. ISBN 87-87535-40-8 3. O. Sandberg, Advanced Nitrogen Alloyed Steels - Properties and Application Experiences, Proceedings of the 8th International Tooling Conference, compiled by P. Beiss, C. Broeckmann, S. Franke, and B. Keysselitz. Aachen, 2009, pp. 357-367. 4. K. Frisk, G. Lindvall, N. Olsson, O. Sandberg, and I. Siller. Alloy Design of Tool Steels using Thermodynamic Calculations, Proceedings of the 8th International Tooling Conference, compiled by P. Beiss, C. Broeckmann, S. Franke, and B. Keysselitz. Aachen, 2009, pp. 727-736 5. O. Sandberg and A. Sandberg, Martensitic Nitrogen Alloyed Steels with Excellent Corrosion and Wear Resistance, Proceedings of Stainless Steel World America 2010 Conference, Houston 2010. 6. G. Lindwall, J. Flyg, K. Frisk and O. Sandberg,Experimental and Theoretical Investgations of Hot Isostatically Pressed-Produced Stainless Steel/High Alloy Tool Steel Compound Materials, Met. & Mat. Trans. A, Dec. 2010. 7. Deutsches Kunststoff Institut, Darmstadt. Contract work 10T088V0, 2010. 8. Deutsches Kunststoff Institut, Darmstadt. Contract work A08T077, 2009. 9. C. Bertoli, J. DAlessio, N. Del Giacomo, M. Lazzaso, P. Massoli and V. Moccia, Running Light duty DI Diesel Engines with Wood Pyrolysis Oil , SAE paper 2000-01-2975. 10. A. R. Gholi. The effects of tempering on corrosion properties of martensitic stainless steel and tool steel in pyrolysis oil. Swerea KIMAB. Diploma work 2011. 11. J. Carsten, Danish Meat Research Institute, http://danishmeat.eu/DMRI/Forsideelementer/Forsidenyt /New_steel.aspx