CN101429630B - Novel austenite cold-heading stainless steel and its steel wire production method - Google Patents
Novel austenite cold-heading stainless steel and its steel wire production method Download PDFInfo
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Abstract
The invention relates to a novel austenitic cold heading stainless steel and a method for manufacturing a steel wire thereof. The stainless steel comprises the following chemical components in weight percentage: 15.0 to 16.0 percent of Cr, 8.0 to 10.0 percent of Mn, 3.0 to 4.0 percent of Ni, 2.0 to 4.0 percent of Al, less than or equal to 0.06 percent of C, less than or equal to 0.10 percent of N, less than or equal to 1.00 percent of Si, less than or equal to 0.035 percent of P, less than or equal to 0.015 percent of S, and the balance being Fe and inevitable impurities. The method for manufacturing the steel wire comprises the following steps: using a rotary cutting or scraping cutting method to strip off the surface layer with the thickness of between 0.1 and 0.15 millimeter of a stainless steel wire material; performing annealing treatment on the wire material at a temperature of between 800 and 900 DEG C; and performing the following treatments on the wire material: skin film treatment, drying, rough drawing, intermediate drawing, wire rolling, cleaning agent surface treatment, continuous furnace bright annealing, finished product drawing or surface film coating, and oxalate coating treatment. The austenitic cold heading stainless steel has a plurality of advantages of low yield ratio, high plasticity, good oxidation resistance, good low temperature resistance, good diamagnetism, intergranular corrosion resistance and the like, thus the austenitic cold heading stainless steel can partially substitute the prior Cr-Ni austenitic stainless steel such as 0Cr18Ni9.
Description
Technical field
The present invention relates to the manufacture method of a kind of cold-heading stainless steel and steel wire thereof, especially relate to the manufacture method of a kind of novel austenite cold-heading stainless steel and steel wire thereof.Described steel wire is mainly used in standardized component such as making bolt, screw, nut and rivet, belongs to the metal products technical field.
Background technology
After the develop rapidly and entry into the World Trade Organization along with China's modernization, the demand of stainless steel standard part sharply increases both at home and abroad in recent years.Carbon steel chromium plating or zinc-plated standardized component have almost all been replaced at household electrical appliance, indoor decoration, precision instrument industry stainless steel standard part, in the also lasting rising of the demand of industry stainless steel standard parts such as food, traffic, machinery, building.
Have again along with cold headers develop towards multi-work-station, maximization and high speed direction, the per minute operation is up to 400-600 time, the high speed cold-heading worsens its steel texturizing condition, simultaneously because the standardized component of the numerous and diverse section of manufacturing, deep trench etc., steel is proposed strict more technical requirements, the firstth, corrosion-resistant in empty G﹠W, non-corrosive; The secondth, the intensity of requirement steel is lower, plasticity is high; General requirement tensile strength is not more than 800MPa, and elongation is greater than 40%, and relative reduction in area is greater than 70%, and simultaneously, yield tensile ratio is less than 0.7.The 3rd is that cold heading performance is splendid, and the cold-work strengthening rate is low, and the cold-heading scrap rate is less than 3%; The 4th requires the surface of steel not allow to exist to using deleterious defective, the dimensional precision height, and tolerance of dimension is ± 0.01mm; The 5th is that requirement is inexpensive or the like.
A large amount of both at home and abroad at present Ni-Cr austenitic stainless steel manufacturer's standard parts that use are as trades mark such as MLOCr18Ni12, MLOCr18Ni9; According to the data introduction, have 60% to be used to produce stainless steel approximately in the global nickel output, nickel is more rare and expensive metal, belong to strategic materials, often stainless cost and price also often fluctuate with the ups and downs of nickel valency, and the nickel valency rises suddenly and sharply over nearly 2 years, almost turns over; In addition, chromium metal China also lacks very much, and price is also constantly soaring, so Ni-Cr stainless steel price is also along with soaring.Therefore, the continuous research and development of domestic and international in recent years metallurgical expert go out the new trade mark of a series of joint Ni austenitic stainless steels.
Summary of the invention
The objective of the invention is to do not reducing under the rustless property prerequisite of steel, substitute portion C r metal with Al, when carrying Mn and fall Ni, add the Cu metal, to control the content of elements such as C, N in addition, having is exactly when making cold-heading wire again, proposes new technique manufacturing method, makes the integrated performance index of steel reach the novel austenite cold-heading stainless steel of the technical matters requirement that the cold upsetting steel uses and the manufacture method of steel wire thereof.
The integrated performance index of above-mentioned steel is embodied in: intergranular corrosion resistance in rustless property, low yield strength ratio, high-ductility, high antioxidant, heat-resistant anti-fatigue, hot corrosion resistance, anti-low temperature (173 ℃) performance, diamagnetism (magnetic permeability mu≤1.2 under magneticstrength 18KA/m condition), anti-sulfuric acid or the reductant.
The object of the present invention is achieved like this: a kind of novel austenite cold-heading stainless steel, its chemical ingredients consists of (% weight ratio): Cr 14.0～17.0, and Mn 7.0～10.0, and Ni 1.5～5.5, Cu1.50～3.50, Al 1.0～4.0, C≤0.06, N≤0.12, Si≤1.00, P≤0.035, S≤0.015, surplus is Fe and unavoidable impurities.
The preferred chemical ingredients of novel austenite cold-heading stainless steel of the present invention is (a % weight ratio): Cr15.0～16.0, Mn 7.0～8.0, Ni 3.0～4.0, and Cu 2.0～3.00, and Al 1.0～2.0, C≤0.05, N≤0.10, Si≤1.00, P≤0.035, S≤0.015, surplus are Fe and unavoidable impurities; Or: Cr 14.0～15.0, and Mn 8.0～9.5, and Ni 2.0～3.0, and Cu 1.0～2.0, and Al 2.0～3.0, C≤0.04, N≤0.10, Si≤1.00, P≤0.035, S≤0.015, surplus is Fe and unavoidable impurities.
The present invention is a Cr-Mn-Ni-Cu-Al alloying constituent system, is that a kind of Ni of falling carries Mn, uses Al for Cr, adds Cu, control C, N again, and the theoretical foundation of design is as follows:
Alloying element is that people are in order to obtain the element with certain content range that tissues needed and various performance add in stainless steel.The principle that main alloy element of the present invention is determined is: carry Mn fall Ni, with Al for Cr, add Cu, control C, N etc., all the other alloying elements are normally used content range.
Nickel equivalent:
%+0.5 * Mn%+0.3 * the Cu% of nickel equivalent=Ni%+30 * (C+N).
Numeral before each element is equivalent to the multiple that nickel forms the austenite ability for this element forms the austenitizing ability.
1) Ni and Mn content determines
From Ni equivalent formula as seen, Ni is an important element in the austenitic stainless steel, it is to form austenitic first-selected element, because Ni is many-sided to stainless contribution, except forming the stable austenite, because Cr-Ni coexistence in the stainless steel, Ni can promote the passivation for stainless steel membrane stability, can significantly improve that stainless steel is moulded, toughness, can reduce stainless brittle transition temperature, have cold resistance and diamagnetism and features such as cold formability and weldability are favourable.But the Ni metal is rare and valency is high, and metallurgical for many years expert seeks the substitute element of Ni again, and the Mn alloying element is comparatively ideal substitute, as seen, is can substitute the 1%Ni element to form austenitic with 2%Mn from Ni equivalent formula.So Ni and Mn content range are defined as on average reducing about 4%Ni in the new trade mark of the present invention, it is suitable carrying about Mn8%, i.e. Ni1.5%-5.5%, Mn7.0%-10.0%.
2) Cu content determines
Copper can improve stainless rustless property and solidity to corrosion, and particularly the effect in reductants such as sulfuric acid is more obvious.Copper is stable and forms the austenitic alloy element, copper can significantly reduce stainless intensity and cold hardening tendency, improve the plasticity of steel, simultaneously stainless steel surface had germ resistance, but copper content is unsuitable too high, because Cu content increases in the steel, stainless thermoplasticity reduces, and is rational so Cu content range of the present invention is defined as 1.5-3.5%.
3) C and N content determines
As seen, C and N form two the strongest elements of austenite ability from the nickel equivalent formula, are 30 times of Ni; But in austenitic stainless steel, generally do not adopt C as forming austenitic element, because, increase along with C content in the steel, though can improve intensity, but the moulding of steel, toughness, solidity to corrosion, cold formability, weldability etc. will significantly reduce, it is generally acknowledged that its fraud is far longer than profit, so C content will reduce as far as possible, carbon content of the present invention is defined as≤the 0.06%th, suitable.
In recent years, N is widely applied in austenite and duplex stainless steel, because N can significantly improve the intensity of steel by solution strengthening, contains the chromium element of q.s simultaneously in the steel, and N can improve the passivation ability of steel, improves corrosion resistance of austenitic stainless steels;
Surpass certain when a certain amount of when containing N amount in the steel, as surpassing at 0.15 o'clock at austenitic stainless steel N, the cold and hot working of steel and cold-forming reduce, and particularly unsuitable too high with steel N to cold-heading, it is rational should suitably being controlled at and being not more than 0.1%.
4) Cr content determines
Cr has the decision influence to the rustless property and the anti-spot corrosion of steel, increase along with Cr content in the stainless steel, not only in the anti-corrosion increase of oxidizing acid medium, and, stainless steel abilities such as anticorrosion stress-resistant, spot corrosion, crevice corrosion in chloride soln all there is raising, so the Cr element is indispensable important element at stainless steel, generally can not be less than 13%, it is suitable that Cr content range of the present invention is defined as 14-17%.
5) Al content determines
After adding elements such as AL and Cr in the steel, can improve the temperature that FeO occurs, as contain 1%Cr and can make FeO, FeO is occurred 800 ℃ of temperature if contain 1.1%Al 600 ℃ of appearance. than higher Cr, Al content the time, can make FeO in temperature appearance more than 800 ℃.Comprehensive Cr, the Al element of using can be brought into play bigger anti-oxidant usefulness, and steel has good resistance of oxidation, and resisting temperature drastic change ability is better, and heat-resistant anti-fatigue and resistance to high temperature corrosion performance are better than the 18-8Cr-Ni stainless steel simultaneously; In addition owing to there is the content of more Al in the steel, can make AUSTENITE GRAIN COARSENING, coarse grain steel wire tensile strength and yield strength reduce, elongation, relative reduction in area obviously increase, cold heading performance increases substantially, can bear bigger cold deformation and do not ftracture, this is the fundamental point that the present invention pursues, and the present invention determines that the Al content range is that 1-4% is suitable.
Indulge the above, novel austenite cold-heading stainless steel of the present invention, have low yield strength ratio, high-ductility, good in oxidation resistance, plurality of advantages such as cold resistance is good, diamagnetism is good, anti intercrystalline corrosion, therefore can partly substitute traditional Cr-Ni austenitic stainless steels such as OCr18Ni9.
Other has, and at being used for heat-resisting high antioxygen, heat-resistant anti-fatigue and the good standardized component of high temperature corrosion, can select Cr-Mn-Ni-Al series austenitic stainless steel for use, promptly removes the content that Cu increases Al, also can reach promising result.Under the high-temperature oxidation resistant situation, Al can be better for the Cu effect.Discover that according to metallurgical expert same the adding after 1%Cu or the Al, FeO formation temperature Al improves 200 ℃ than Cu in steel, oxidation-resistance obviously improves, in addition, and Al aboundresources, Cu resource-constrained.Its concrete composition (% weight ratio) composed as follows: Cr 15.0～16.0, and Mn 8.0～10.0, and Ni 3.0～4.0, and Al 2.0～4.0, C≤0.06, and N≤0.10, Si≤1.00, P≤0.035, S≤0.015, surplus is Fe and unavoidable impurities.
The manufacture method of austenite cold-heading stainless steel silk of the present invention, the processing step of described method is as follows:
Step 1, wire rod peeling
To the top layer that STAINLESS STEEL WIRE is peelled off certain depth with the method for rotary cut or scraping, the general degree of depth is 0.1-0.15mm, makes
5.5-10mm wire rod can be eliminated following defective:
1, the surface imperfection of wire rod, as crackle, fold, scab etc.;
2, the non-metallic inclusion on nearly surface.
The wire rod that removes surface imperfection can be used for making high-quality standardized component, and the cold-heading yield rate improves more than 5%.
Step 2, wire annealing
The wire rod that obtains after rotary cut or scraping is carried out 800-900 ℃ of anneal, and the shortcoming that mould is cut the peeling wire rod is that the surface can produce a kind of hardened layer, should not directly go drawing and need soften thermal treatment, could further drawing after eliminating stress.
Step 3, epithelium are handled, oven dry
The employing film agent is right
Handle 5.5-10mm wire surface carries out epithelium, in the stoving oven oven dry, furnace temperature 100-150 ℃, the time is 0.5-1.0 hour then.
Step 4, rough or in draw, take-up
In the drawing of bull continuous drawing machine, first road adopts the big draft of 25%-30%, draft one by one successively decreases later on, be generally the 6-7 passage rough pull out or the 7-8 passage in after the drawing, take-up, condition of delivery are for gently drawing steel wire, steel wire is reserved the 6%-10% draft and gently is pulled to the trimmed size size before the finished product, and soft attitude steel wire is moved the trimmed size size to.
Step 5, clean-out system surface treatment, continuous oven clean annealing
According to user's needs, condition of delivery is soft attitude steel wire, adopts the clean-out system treat surface behind the unwrapping wire, washes, dries up, enters the continuous bright heat treatment furnace then, 1100 ± 10 ℃ of furnace temperature, and linear velocity 20m/ branch, after feeding ammonia decomposes in the pipe, 75%H
2, 25%N
2Mixed gas is protected stove, water-cooled, washing, oven dry;
Step 6, end product drawing or surface-coated film and oxalic acid coating are handled
After the soft attitude delivery steel wire bright heat treatment, warehouse-in is checked, weighs, packed to surface-coated film or oxalic acid coating after handling; Gently draw the delivery steel wire, carry out passing through again after pickling and surface-coated film or oxalic acid are coated with the inverted drawing of 6%-10% draft small deformation degree, check, weigh, pack warehouse-in again.
Above-mentioned technological process control has following 3 innovative points:
1, in order to improve the cold-heading yield rate, remove wire surface defective and nearly surface inclusion, wire surface is carried out the 0.1-0.15mm peeling handle, be first innovative point of technology controlling and process;
2, producing sclerosis and stress after eliminating the wire rod peeling, wire rod is carried out 800-900 ℃ of anneal, in order to drawing, is second innovative point of technology controlling and process;
3, bright temperature is brought up to 1100 ℃ ± 10 ℃ by general 1050 ℃, can make fully dissolvings such as alloy cpd AlN, gently pull into simultaneously the product steel wire and adopt little draft drawing below 10%, be beneficial to obtain less than 0.70 yield tensile ratio, improve plasticity index elongation and relative reduction in area, obtain splendid cold upsetting performance at last, satisfying customer requirements is the 3rd innovative point of technology controlling and process.
Embodiment
Embodiment 1:
Make chromium manganese ambrose alloy aluminium series austenite cold-heading stainless steel.Its chemical ingredients consists of (% weight ratio): Cr 14.0～17.0, and Mn 7.0～10.0, and Ni 1.5～5.5, and Cu 1.50～3.50, Al 1.0～4.0, C≤0.06, N≤0.12, Si≤1.00, P≤0.035, S≤0.015, surplus is Fe and unavoidable impurities.
Technical process:
Batching-electric arc furnace smelting-AOD stove is concise-ladle-tundish-continuous casting and direct rolling machine-solution treatment-take-up-pickling-bundling-packing-warehouse-in.
1) batching
Cleaning steel scrap+Cr and Ni scrap metal+and slag making materials such as copper scrap+lime etc.; (also available high carbon ferro-chrome and high-carbon ferronickel etc.);
2) electric-arc furnace steelmaking
After batch materials added electric arc furnace successively, the energising heat fused, chemical examination C, Si, Mn, P, S, Cr, Ni, Cu adjust various chemical ingredientss again according to result of laboratory test, and slag making after furnace temperature reaches 1650 ℃, is skimmed, is tapped;
3) AOD refining furnace
After first furnace molten steel gone into stove, by in stove, being blown into Ar (N
2)+O
2Mixed gas, converting process are divided into oxidation period, reduction period, concise phase;
Mainly be that C falls in task oxidation period, and terminal point is skimmed below 0.03%;
Reduction period: add an amount of slag former, lime+CaF
2And Fe-Si, CaSi or Al powder etc., make reducing slag, basicity is 2.0～2.2, makes Cr, Mn element reduction, general Cr, Mn element recovery rate reach about 95%; Take off S simultaneously, take off S after skimming and lead and reach 70%;
The concise phase:, Cr, Mn, Al composition are adjusted, (because of Cu, the not oxidation substantially of Ni element according to result of laboratory test, recovery rate is generally more than 97%) adjust the back composition and reach target value, after liquid steel temperature is controlled at 1700 ± 10 ℃, skims, tap, ladle molten steel can change tundish over to and carry out continuous casting;
4) continuous casting
Molten steel passes through middle water containing opening---crystallizer---throwing, about speed 3M/ divided, the square billet specification was generally 150mm * 150mm;
5) tandem rolling
After square billet is checked, defective is removed, enter the process furnace heating after the reconditioning again, the insulation soaking, furnace temperature reaches 1200 ℃～1250 ℃ open rollings of coming out of the stove, generally by roughing mill-middle milling train-finishing mill-Laying head-shrend (1050 ℃～1100 ℃), after the solution treatment, take-up, pickling, bundling, weighing, check, packing, warehouse-in.
6) the finished product gauge or diameter of wire is
5.5～15mm, every dish heavily is about 1t～2t.
Embodiment 2:
Make chromium manganese ambrose alloy aluminium series austenite cold-heading stainless steel.Its chemical ingredients consists of (% weight ratio): Cr 15.0～16.0, and Mn 7.0～8.0, and Ni 3.0～4.0, and Cu 2.0～3.00, Al 1.0～2.0, C≤0.05, N≤0.10, Si≤1.00, P≤0.035, S≤0.015, surplus is Fe and unavoidable impurities.
Technical process: with example 1.
Embodiment 3: make chromium manganese ambrose alloy aluminium series austenite cold-heading stainless steel.Its chemical ingredients consists of (% weight ratio): Cr 14.0～15.0, and Mn 8.0～9.5, and Ni 2.0～3.0, and Cu 1.0～2.0, Al 2.0～3.0, C≤0.04, N≤0.10, Si≤1.00, P≤0.035, S≤0.015, surplus is Fe and unavoidable impurities.
Technical process: with example 1.
Embodiment 4: make chromium manganese nickel aluminium series austenite cold-heading stainless steel.Its chemical ingredients consists of (% weight ratio): Cr 15.0～16.0, and Mn 8.0～10.0, and Ni 3.0～4.0, and Al 2.0～4.0, C≤0.06, and N≤0.10, Si≤1.00, P≤0.035, S≤0.015, surplus is Fe and unavoidable impurities.
Technical process: with example 1.
Embodiment 5:
Make chromium manganese ambrose alloy aluminium series austenite cold-heading stainless steel silk.Processing step is as follows:
Step 1, wire rod peeling
To the top layer that STAINLESS STEEL WIRE is peelled off certain depth with the method for rotary cut or scraping, the general degree of depth is 0.1-0.15mm, makes
5.5-10mm wire rod.
Step 2, wire annealing
The wire rod that obtains after rotary cut or scraping is carried out 800-900 ℃ of anneal.
Step 3, epithelium are handled, oven dry
The employing film agent is right
Handle 5.5-10mm wire surface carries out epithelium, in the stoving oven oven dry, furnace temperature 100-150 ℃, the time is 0.5-1.0 hour then.
Step 4, rough or in draw, take-up
In the drawing of bull continuous drawing machine, first road adopts the big draft of 25%-30%, draft one by one successively decreases later on, be generally the 6-7 passage rough pull out or the 7-8 passage in after the drawing, take-up, condition of delivery are for gently drawing steel wire, steel wire is reserved 10% draft and gently is pulled to the trimmed size size before the finished product, and soft attitude steel wire is moved the trimmed size size to.
Step 5, clean-out system surface treatment, continuous oven clean annealing
According to user's needs, condition of delivery is soft attitude steel wire, adopts the clean-out system treat surface behind the unwrapping wire, washes, dries up, enters the continuous bright heat treatment furnace then, 1100 ± 10 ℃ of furnace temperature, and linear velocity 20m/ branch, after feeding ammonia decomposes in the pipe, 75%H
2, 25%N
2Mixed gas is protected stove, water-cooled, washing, oven dry;
After step 6, end product drawing or surface-coated film and oxalic acid coating were handled soft attitude delivery steel wire bright heat treatment, warehouse-in is checked, weighs, packed to surface-coated film or oxalic acid coating after handling; Gently draw the delivery steel wire, carry out pickling and surface-coated film or oxalic acid be coated with after again through the inverted drawing of 10% draft small deformation degree, check, weigh, pack warehouse-in again.
Embodiment 6:
Make chromium manganese nickel aluminium series austenite cold-heading stainless steel silk.Processing step is with example 5.
Attached: every the key technical indexes requirement of finished product steel wire
According to GB/T4232-93 cold upsetting Stainless Steel Wire national standard or JISG4315-2000 Japan cold-heading stainless steel silk standard-required, the key technical indexes is as follows:
1) dimensions and permissible variation
Steel wire diameter: d=0.8-14.0mm
Permissible variation should meet 10 grades or 9 grades, 8 grades regulations of table 2 among the GB/T342.
2) condition of delivery
Carrying out the surface-coated film behind soft attitude (R) clean annealing handles;
Gently draw the drawing of carrying out carrying out behind the surface-coated film small deformation behind (Q) clean annealing.
3) mechanical property
4) surface quality
The smooth cleaning of Steel Wire Surface must not have using deleterious defective.
5) cold upsetting performance
Steel wire should carry out the cold upsetting test, and cold upsetting is to original sample height 1/2nd, and specimen surface must not have crackle and breach.
6) particular requirement
According to customer requirements, the austenite steel wire can be done Huey test, and test method is by the both sides of supply and demand agreement.
Claims (2)
1. austenite cold-heading stainless steel, it is characterized in that described stainless chemical component weight per-cent consists of: Cr15.0～16.0%, Mn8.0～10.0%, Ni3.0～4.0%, Al2.0～4.0%, C≤0.06%, N≤0.10%, Si≤1.00%, P≤0.035%, S≤0.015%, surplus are Fe and unavoidable impurities.
2. the manufacture method of an austenite cold-heading stainless steel silk, it is characterized in that: the chemical component weight per-cent of described Stainless Steel Wire consists of: Cr15.0～16.0%, Mn8.0～10.0%, Ni3.0～4.0%, Al2.0～4.0%, C≤0.06%, N≤0.10%, Si≤1.00%, P≤0.035%, S≤0.015%, surplus are Fe and unavoidable impurities, and the processing step of described method is as follows:
Step 1, wire rod peeling
STAINLESS STEEL WIRE is peelled off the top layer that the degree of depth is 0.1-0.15mm with the method for rotary cut or scraping, make
Wire rod,
Step 2, wire annealing
The wire rod that obtains after rotary cut or scraping is carried out 800-900 ℃ of anneal,
Step 3, epithelium are handled, oven dry
The employing film agent is right
Wire surface carries out epithelium to be handled, and in the stoving oven oven dry, furnace temperature 100-150 ℃, the time is 0.5-1.0 hour then,
Step 4, rough or in draw, take-up
The big draft of 25%-30% is adopted in drawing on the bull continuous drawing machine, first road, the draft that successively decreases one by one later on, through the 6-7 passage rough pull out or the 7-8 passage in after the drawing, take-up,
Steel wire is reserved 10% draft and gently is pulled to the trimmed size size before the finished product, makes condition of delivery for gently drawing steel wire, or directly moves the trimmed size size to, and making condition of delivery is soft attitude steel wire,
Step 5, clean-out system surface treatment, continuous oven clean annealing
At the described condition of delivery of step 4 is soft attitude steel wire, adopts the clean-out system treat surface behind the unwrapping wire, washes, dries up, enters the continuous bright heat treatment furnace then, 1100 ± 10 ℃ of furnace temperature, and linear velocity 20m/ branch, after feeding ammonia decomposes in the pipe, 75%H
2, 25%N
2Mixed gas is protected stove, water-cooled, washing, oven dry;
Step 6, end product drawing or surface-coated film and oxalic acid coating are handled
At the described condition of delivery of step 5 is soft attitude steel wire, and to the steel wire bright heat treatment, surface-coated film or oxalic acid coating are handled; For gently drawing the delivery steel wire, carry out passing through again after pickling and surface-coated film or oxalic acid coating are handled the inverted drawing of 6%-10% draft at the described condition of delivery of step 4.
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