1. Field of the Invention
This invention relates to austenite grain size control by preventing grain coarsening of austenite in upstream processing of niobium microalloyed steel in order to produce thicker gage products with excellent drop weight tear test (DWTT) toughness (as measured in accordance with API RP 5L3 (Apr. 1, 1996)). In current technological practice, there is no intentional control measure to prevent grain coarsening of austenite before entry to finish rolling. As a consequence, heavy rolling reductions are applied to coarse grained austenite during finish rolling in order to increase the surface to volume ratio by geometric means through heavily pancaked austenite. Heavy rolling reductions applied in the finishing mill, often approaching limits of mill loading, inevitably limit thickness of the final product. In order to improve the safety and efficiency of the transport of natural gas and oil through the pipe lines, there is a growing demand for thicker gage pipes, particularly for deep offshore projects.
This invention targets austenite grain size control upstream i.e., at high temperatures in order to produce thicker gage product. This invention utilizes the formation of nano-scale TiN—NbC composite precipitates to pin austenite grain boundaries and prevent them from coarsening at high temperatures (>980° C.) so that less rolling reduction and pancaking of austenite is required to obtain target properties of high strength and excellent toughness at low temperature as measured by ductile to brittle transition temperature and percentage shear in drop weight tear tests. There are additional benefits related to reduced texture related anisotropy of properties and improved ductile fracture arrestability of pipes in service resulting from less thermo-mechanical rolling reduction during finish rolling.
2. Description of Related Art
Although austenite grain size at the end of roughing is fine (<20 microns), significant grain coarsening of austenite occurs subsequent to the end of roughing, which must be prevented from occurring in order to produce a thicker gage product. If the austenite grain size is coarse, it is feasible to apply heavy rolling reductions to “pancake” the austenite and increase the surface to volume ratio of austenite, which increases the nucleation sites for ferrite upon transformation. To the extent that grain coarsening is controlled by a diffusion mechanism which is dependent on time and temperature, rapid thermal cooling should decrease the kinetics of diffusion for grain coarsening. However, it has not been found feasible to adequately cool the center of thick transfer bars to prevent grain coarsening. Nevertheless, accelerated cooling upstream is still beneficial to avoid rolling in the partial recrystallization regime and avoid depletion of solute niobium by excessive growth of niobium carbide precipitates upstream. Therefore, there is a need to develop alternative strategies to prevent grain coarsening. Although solute niobium retards grain coarsening by retarding boundary mobility, the magnitude of solute drag on boundary mobility is weak at high temperatures. As a consequence, even though most of the niobium is available as solute in conventional processing, it is not found to be effective in preventing grain coarsening. Thus, an object of the present invention is to prevent grain coarsening of austenite grains by metallurgical means, through pinning austenite grain boundaries by second phase particles using the Zener pinning mechanism. The use of TiN particles to pin austenite grain boundaries by the Zener pinning mechanism is well established and has been disclosed in prior patents (see, for example, U.S. Pat. No. 6,899,773; U.S. Pat. No. 6,183,573; and U.S. Pat. No. 5,900,075). While these patents identify conditions under which high number density of TiN precipitates can be promoted, the limiting austenite size achievable by TiN alone is typically 60 to 80 microns in the high temperature window of processing. NbC is sluggish to nucleate by itself and is aided by dislocations generated by deformation to promote strain induced nucleation of NbC, which is associated with large undercooling. Strain induced precipitation of NbC is used in controlled rolling of microalloying technology, where strain induced precipitation of NbC is used to pin austenite grain boundaries during thermo-mechanical controlled rolling during the low temperature window of processing. However, by promoting epitaxial growth of NbC on pre-existing TiN in accordance with the present invention, TiN—NbC composite precipitates are obtained with negligible undercooling in the high temperature window at the end of roughing. These nano-scale TiN—NbC composite precipitates are available to pin austenite grains at the end of roughing and limit austenite grain size to under about 30 microns on entry to finish rolling, which is essential to produce thicker gage in line pipe grades.
Accordingly, it is an object of the invention to reduce the need for large rolling reductions and heavy pancaking during finish rolling in order to obtain increased gages of finished product.
It is another object of the invention to produce uniform fine austenite grain size before pancaking and apply less pancaking to produce thicker gage product, which exhibits homogeneous properties without anisotropy due to unfavorable crystallographic texture development.
It is yet another object of the invention to obtain consistently low ductile to brittle transition temperature (DBTT) and good drop weight tear test (DWTT) performance. DWTT properties are empirically correlated with thickness of pancaked austenite grain. By refining the austenite grain size, less pancaking is required to meet target DWTT properties.
It has now been discovered that the addition of niobium to titanium-bearing super-martensitic stainless steel refines the austenite grain size due to the formation of titanium-niobium bearing composite precipitates. This led to the present invention's development of nano-scale precipitation engineering of TiN—NbC composite precipitates to prevent austenite grains from coarsening. According to the present invention, TiN precipitates, which are formed just after solidification in the continuous cast slab, are used to control the inter-particle spacing, while NbC precipitates growing on pre-existing TiN particles are used to control the size of the precipitates, both size and spacing of TiN—NbC composite precipitates are the key to pinning austenite grains of the required size to prevent them from coarsening. The driving force for grain coarsening is capillary force, which can be determined from the equation: capillary force=2 γ/R, where R is the radius of curvature of the grain boundary and y is the surface energy of the boundary.
The driving force for grain coarsening tends to decrease as the grain size increases. In accordance with the present invention, a 30 micron grain size is targeted instead of the conventional 60 microns. This driving force for boundary movement is counteracted if particles pin the boundary. The pinning force increases with the number density and size of the particles. Thus, the driving force for grain coarsening when the target grain size is 30 microns can be determined from the number density of particles [TiN], which sets up the interparticle spacing that can be measured, e.g., 200 nm. But the particle size of TiN is too small, about 15 nm. The limiting austenite grain size is 90 microns, which is rather coarse. By growing NbC, TiN—NbC composites can be formed, which are now large, about 25 nm. The limiting austenite grain size is 32 microns, which is close to target. By growing to 30 nm, as can be seen from Table 1 below, the limiting austenite grain size is decreased to 22 microns. It should be noted that the number density and the volume fraction of precipitates are controlled by the thermodynamics and kinetics of precipitation which, in turn, depend upon the chemical composition and processing parameters of the steel.
The validity of the mechanism underpinning the technology of nano-scale precipitation engineering for austenite grain size control in upstream processing is demonstrated by experimental results on line pipe grades processed under plate rolling and hot strip rolling conditions. The present invention provides a platform for austenite grain size control in upstream processing of austenite of niobium microalloyed steels to which downstream processing and final properties of the product are related.
A process for controlling austenite grain size in austenite processing through nano-scale precipitation engineering of TiN—NbC composites to produce thicker gage product of niobium microalloyed steel comprises controlling the base chemical composition of a steel product to include about 0.003-0.004 wt % nitrogen, 0.012-0.015 wt % titanium, 0.03-0.07 wt % carbon, and 0.07-0.15 wt % nobium; lowering the temperature of roughening to end the roughening operation in the temperature range of from about 980° C. to 1030° C.; retaining greater than about 0.03% niobium in solution in the matrix by rapid cooling of the product to enter the finish rolling operation below the temperature of no recrystallization, with an austenite grain size of about 30 microns; and applying reduced rolling reduction in the finish rolling operation. Lowering the temperature of roughening prevents grain refined austenite from coarsening above about 30 microns by formation of TiN—NbC composite precipitates. Applying reduced rolling reduction in the finish rolling operation acts to pancake the fine austenite grain size of about 30 microns to obtain a sufficient surface to volume ratio to produce thicker gage resulting steel product.
The grain size can be controlled in the range of about 20-40 microns at entry to the finish rolling operation. TiN precipitates can be in the range of about 10-20 nm and the inter-particle spacing can be about 200-300 nm. Thermodynamic potential for precipitation of NbC can occur towards the end of the roughing operation at temperatures ranging from about 980° C. to about 1030° C. TiN—NbC composites can be in the size range of about 20-50 nm. The process can include applying accelerated cooling upstream between the end of the roughing operation and the start of finish rolling to avoid depletion of solute niobium from the matrix to less than about 0.03 wt percent. Accelerated cooling of the product can be applied to avoid rolling in the partial recrystallization regime. The process can include controlling nitrogen at or below about 40 ppm and making a titanium addition to meet the stoichiometric requirement to combine with all nitrogen to form high number density of TiN precipitate in about the 10-20 nm size range. The process can include processing the steel product by conventional plate rolling, conventional hot strip rolling, steckel mill rolling, and/or near net shape processing. The steel product can be line pipe steel, infra-structure steel, and/or supermartensitic stainless steel. The crystallographic texture-related anisotropic properties of the resulting steel product can be minimized. The process can include substituting titanium partially or fully in the base chemistry with a member of the group consisting of Zr, Hf, Ta, W, V, Cr, Mo, Al and mixtures thereof, each with high affinity for nitrogen to form nano-scale precipitates on which NbC can grow epitaxially to give composite precipitates.
The process also can include partially substituting niobium in the base chemistry with other microalloying elements with high affinity for carbon selected from the group consisting of Zr, Hf, Ta, W, V, Cr, Mo and mixtures thereof, each to give composite precipitates. The process also can include substituting solute niobium on entry to finish rolling with other elements, which exhibit solute drag comparable to niobium. Still further, the process can include rapidly cooling the steel product to enter finish rolling at a temperature at or below about 920° C. The rolling reduction can be reduced substantially by more than about 15%. The steel product can exhibit a gage thickness of about 17-30 mm.
The steel without niobium addition but with titanium exhibits an austenite grain size of 80 microns, which shows that titanium addition alone is not effective in refining austenite grain size. But with the addition of 0.1 wt percent niobium, the austenite grain size is significantly decreased to 35 microns. The white lines in
The area occupied by particles on the boundary must be recreated before the boundary moves, and this is the energy preventing grain coarsening and is referred to as Zener drag. Solute atoms piling up at the interface exert a drag force on boundary mobility, which is referred to as solute drag. Solute drag of niobium is less pronounced in the high temperature window. Zener drag is increased as the interparticle distance is reduced and the particle size becomes bigger for a given volume fraction of precipitate, which is determined by the thermodynamic potential for precipitation for a given steel composition. TiN and TiN—NbC precipitates occur on a nano-scale and therefore engineering the size and dispersion of nano-scale precipitates is termed “engineering nano-scale precipitates for pinning grain boundaries.”
The breakthrough in austenite grain size control upstream arose out of observations in super-martensitic stainless steel, where a titanium addition by itself did not produce a fine austenite grain size. But when combined with niobium additions, a fine austenite grain size was obtained. This was caused by TiN—NbC composite precipitates, formed by NbC growing on pre-existing TiN. The number density of precipitates was controlled by the TiN. By increasing the size of the precipitates by growth of NbC on pre-existing TiN, it is possible to increase the pinning pressure of precipitates to arrest austenite grain boundary movement at the required austenite grain size. This discovery underlies the present invention of nano-scale precipitation engineering. The austenite grain size is controlled by inter-particle spacing of TiN precipitates and the size of the precipitates, each of which can be independently controlled by design of the base steel composition. A high number density of TiN is promoted when the precipitation occurs in the matrix at low temperature, which calls for lowering the nitrogen content and adding titanium to the stoichiometric requirement to form TiN, providing one atom of titanium for every one atom of nitrogen. By lowering nitrogen to less than 40 ppm and adding titanium to the stoichiometric requirement of about 0.014 wt percent, the inter-particle spacing was found to be around 200 nm and the TiN precipitate size was found to be in the 10-15 nm range. The Zener pinning pressure on the boundary is relatively small, capable of arresting austenite grains of about 80 microns from coarsening. The pinning pressure can be increased by growing NbC precipitates on TiN, thereby increasing the size of the composite precipitates of TiN—NbC. This requires lowering the temperature window of roughing so that the thermodynamic potential for growth of NbC on pre-existing TiN is obtained to form TiN—NbC composites. By increasing the particle size while retaining the same inter-particle spacing, the pinning pressure is increased to arrest the finer austenite grains from coarsening. By increasing the size of precipitates to 30 nm with an interparticle spacing of 220 nm, the Zener pinning pressure is increased to prevent austenite grain size of 30 microns from coarsening.
The concept of nano-scale precipitation engineering to arrest grain coarsening is illustrated in the schematic diagram given in
Nitrogen is controlled to promote the formation of TiN precipitates at lower temperatures. The resulting finely-dispersed nano-precipitates of TiN then act as scaffolds for the epitaxial formation of NbC, thereby raising the volume fraction of dispersed composite precipitates by a factor of about 3X. This is sufficient to hold the austenite grain size to about 30 micrometer size in low nitrogen steel compared to 60 microns for higher nitrogen steel. The advantage here lies in the reduced austenite grain size, permitting the application of a reduced rolling reduction during final processing and the consequent ability to produce thicker gages of higher strength material (X-70, X-80, X-90, X-100) compared with high nitrogen steel, which requires heavy rolling reduction that limits final gage of the product.
By comparison,
The technology of nano-scale precipitation engineering of TiN—NbC composites involves two microstructural parameters. The first is the interparticle spacing. The second is the particle size. This invention is based on the discovery that TiN—NbC composites offer a window of opportunity to control interparticle spacing through optimum TiN distribution and the size of the particle by epitaxial growth of NbC on pre-existing TiN particles. The first step is to engineer a high number density and uniform dispersion of TiN particles. This is done by promoting nucleation of TiN in austenite at lower temperatures through control of the base steel chemical composition. Since the precipitates occur on a nano-scale, it is essential to characterize the precipitates by transmission electron microscope. The well-known carbon replica technique is used in this work to extract the precipitates occurring in benchmarked steels.
Steel-A with the highest nitrogen content of 0.0075 wt. percent exhibits a large mean inter-particle spacing of about 550 nm compared with Steels-B and C with a low N content of 35-40 ppm, which exhibit a mean inter-particle spacing of about 220 nm. Steel-D with intermediate nitrogen content of 55 ppm exhibits an intermediate interparticle spacing of about 400 nm. Clearly, the inter-particle spacing of 220 nm can be achieved by lowering nitrogen content to or below 40 ppm and adding titanium to the stoichiometric requirement to tie up all the nitrogen. The precipitate size of TiN—NbC of the highest nitrogen Steel-A is 83 nm, which gives Zener limiting austenite size of 62 microns. By comparison, Steel-B and Steel-C with low nitrogen give Zener limiting austenite grain size of about 27 microns.
In conventional processing of conventional nitrogen-bearing niobium microalloyed steel (0.005-0.008 wt. percent nitrogen), roughing is carried out where there is no thermodynamic potential for precipitation of NbC. The loss of niobium by excessive growth of NbC on pre-existing TiN particles is reduced by minimizing the time of processing in the mill. In the case of nano-scale precipitation engineering of TiN—NbC composites with finer inter-particle spacing, it is even more critical to prevent depletion of solute niobium in the matrix by accelerated cooling upstream between the end of roughing and the start of finish rolling. It is essential to control the finish rolling entry temperature below the temperature of no recrystallization in order to avoid rolling in the partial recrystallization regime, which requires accelerated cooling. Thus, accelerated cooling is required to prevent depletion of solute niobium by precipitate growth, subsequent to pinning the austenite grains of the required size in higher grade line pipe steel.
Table 6 is extracted from Kozazu's diagram in
The principal differences in the processing of higher niobium steels between the prior technology without austenite grain size control upstream and the technology of the present invention based on austenite grain size control are examined in further detail and their consequence on product in terms of gage thickness and properties are highlighted in the following examples.
Steel-A is representative of prior technological practice, where a higher nitrogen content of 75 ppm gives coarse TiN particles with large inter-particle spacing of 550 nm. Roughing is carried out in the temperature window where there is no thermodynamic potential for precipitation of niobium carbide. Thus, the austenite grain size entering finish rolling is 60-80 microns. This then requires heavy pancaking below the temperature of no recrystallization. Thus, the final gage is generally limited to 16 mm. Typical property results obtained from 10 mm gage are reproduced below in Table 7:
Steel-E has a lower nitrogen content (40 ppm) with titanium and niobium addition comparable to Steel-A. The low nitrogen and stoichiometric addition of titanium to combine with nitrogen to form TiN has produced a high number density of TiN with a mean interparticle spacing of 220 nm. This steel was processed under two distinctly different conditions. The first set of conditions was where the rough rolling window was similar to Steel-A, that is where there is no thermodynamic potential for NbC precipitation to occur. Under these conditions, TiN particles alone are not able to develop pinning pressure adequate to pin a fine austenite grain size. Thus, the resulting coarse austenite grain size warrants heavy rolling reduction, which is not possible to achieve in 22 mm gage thickness. As a consequence, the final product fails as percentage shear area in the DWTT specimen is lowered to 55 percent at −15° C. (See Table 8).
Steel-E was also processed under a second set of conditions, where thermodynamic potential occurs for growth of NbC on pre-existing particles at the end of rough rolling. In this case, NbC grows on pre-existing TiN to increase the particle size so that the pinning pressure is increased to prevent austenite grain coarsening above 30 microns.
Once austenite grain size is refined at the entry to finish rolling, less rolling reduction is required in finish rolling in accordance with Kozazu's diagram in
22 mm thick gage —X80 Plate: (nitrogen 0.004, titanium 0.016, carbon 0.05, niobium 0.1)
Effect of processing temperature window on low nitrogen and high niobium steel.
Effect of rough rolling in the temperature window with and without thermodynamic potential for precipitation of NbC.
Steel-D presents a case, where nitrogen content is at an intermediate level of about 55 ppm and therefore the mean inter-particle distance is 390 nm. Though the temperature of finish rolling promoted growth of NbC on pre-existing TiN, the TiN—NbC composite did not have adequate pinning pressure to arrest austenite grains finer than 59 microns, see Table 9. This is partly due to low niobium content, i.e. 0.067 wt. percent. Thus, the strip rolled to 20 mm gage thickness exhibited 100 percent shear only at −10° C. and above, see Table 10a and 10b.
Steel-D: 20 mm thick gage X80 Strip
High nitrogen and lower niobium with rough rolling in the temperature regime where there is thermodynamic potential for precipitation of NbC.
In-depth characterization of Steel-C has confirmed that the interparticle spacing of TiN is 220 nm. Steel-C represents low nitrogen content, with optimized addition of titanium to promote high number density and uniform dispersion of TiN with an inter-particle spacing of 220 nm. The end of roughing is in the temperature window where thermodynamic potential for precipitation of NbC occurs.
TEM-EELS characterization of TiN—NbC precipitates shown in
Steel-C: 16.4 mm thick gage X90 Strip.
Low nitrogen and higher niobium with rough rolling in the temperature regime where there is thermodynamic potential for precipitation of NbC.
There are different mill designs available for compact strip processing. Nano-scale precipitate engineering of TiN—NbC composites offers a generic platform for preventing austenite grain coarsening by controlling interparticle distance by TiN, and particle size by NbC growing on the pre-existing TiN. In near net shape processing, in some cases, the transfer bar is reheated for the purpose of temperature homogenization, then the austenite grains inevitably coarsen in the absence of second phase particles. The technology of nano-scale precipitation engineering offers a sound basis for pinning austenite grain boundary with TiN—NbC composite precipitates at the end of roughing, and also during reheating. This process can be combined with accelerated cooling to prevent depletion of solute niobium by excessive growth of NbC, over and above the composite particle size required to prevent grain coarsening of austenite of a specific grain size. Trials of nano-scale precipitation engineering in a mill with two roughing stands and accelerated cooling at 4° C./s have given uniformity of microstructure, which is beneficial in achieving consistent strength and fracture properties.
The application of nano-scale TiN—NbC composite precipitation engineering offers a generic platform for austenite grain size control in upstream processing. A potential application to in-line strip rolling involving three roughing stands to produce X-80 grade strip of 15 mm gage is illustrated in
The foregoing examples distinguish the principal differences in processing higher niobium steels between the prior art without intentional austenite grain size control upstream and the present invention based on austenite grain size control and the consequences thereof on product in terms of gage thickness and properties. The salient points are summarized in Table 12.
According to the present invention, the process steps for controlling austenite grain size upstream before entry to finish rolling to produce thicker gage product are given below:
(i) Lower the nitrogen content in the base chemistry to 30-40 ppm and add titanium to the stoichiometric requirement (0.012-0.015 wt percent titanium) to combine with all nitrogen to form in austenite high number density of TiN precipitates in the size range of 10-20 nm with an interparticle spacing of 200-300 nm, before the start of roughing;
(ii) Refine austenite grain size by static recrystallization in rough rolling to a target grain size of 10-30 microns but preferably 10-20 microns at the end of roughing;
(iii) Adjust carbon content in the range of about 0.03 to 0.07 wt percent but preferably 0.04-0.05 wt percent and niobium in the range of about 0.07 to 0.15 but preferably 0.09 to 0.1 wt percent so that thermodynamic potential for growth of NbC on pre-existing TiN to form TiN—NbC composites occurs towards the end of roughing, i.e., between 980°-1030° C.;
(iv) Target TiN—NbC composites to grow to 25-50 nm but preferably 25-30 nm so that pinning pressure from TiN—NbC composites of 25-50 nm with an interparticle spacing of 200-300 nm can pin austenite of 30 microns grain size in the transfer bars;
(v) Apply rapid cooling between the end of roughing and the start of finish rolling so that (i) the temperature of the transfer bar on entry to finish rolling is below 920° C., the temperature of no recrystallization and (ii) adequate solute niobium >0.03 wt percent, but preferably 0.04 to 0.05 wt percent is retained for strain accumulation during finish rolling and transformation hardening on subsequent accelerated cooling; and
(vi) Control fine austenite grain of about 30 micron size in the transfer bar to enable thicker strip (17-30 mm) to be produced with less pancaking in finish rolling compared with heavy pancaking in coarse austenite grain size of about 60 microns in conventional thermo-mechanical rolling of higher niobium grades that results in thinner gage.
The foregoing examples are given to demonstrate how nano-scale precipitation engineering of TiN—NbC composite precipitates can be used for austenite grain size control in upstream processing of austenite to derive benefits in (i) producing thicker gage product (>17 mm) with excellent strength and fracture toughness at low temperature as measured by DBTT and DWTT, (ii) obtaining more uniform microstructures, and (iii) minimizing unfavorable crystallographic texture related problems. These examples are for illustrative purposes only and the invention is not intended to be limited to any of the specific examples. However, it will be understood by those skilled in the art that modifications and changes may be made to the present invention to combine other elements having a high affinity for nitrogen and carbon similar to titanium and niobium without departing from their scope of controlling particle interspacing and size independently to bring about adequate pinning pressure on the austenite boundary and prevent austenite grain coarsening upstream.