CN1124359C - Fe-Ni series alloys for punching plane shadow mask and plane shadow mask using said alloy and colour cathode ray tube - Google Patents

Abstract

To develop an Fe-Ni based alloy for a press forming die perfect flat mask improved in strength (falling impact deformation resistance) and having low thermal expansibility. This Fe-Ni based alloy for a press forming die perfect flat mask maintaining low thermal expansibility, and whose proof stress and Young's modulus are improved as well has a composition containing 33 to 37% Ni and 0.001 to 0.1% Mn, voluntarily containing 0.01 to <2% Co and further containing one or more kinds selected from 0.01 to 0.8% Nb, 0.01 to 0.8% Ta and 0.01 to 0.8% Hf by 0.01 to 0.8% in total, and the balance Fe with inevitable impurities, in which, preferably, as the impurities, C is controlled to <=0.01%, Si to <=0.04%, P to <=0.01%, S to <=0.01% and N to <=0.005%. The flat mask and color cathode-ray tube use the same.

Description

The punching plane shadow mask is alloy and planar aperture mask that uses this alloy and color cathode ray tube with Fe-Ni

The present invention system is alloy and whole plane shadow mask and the color cathode ray tube that uses this alloy about a kind of impact briquetting whole plane shadow mask that need not hang up but make whole plane shape by punching press with Fe-Ni; Particularly usually to keep Fe-Ni by the interpolation unit of selecting particular types be the low heat expansion property that alloy has about a kind of, and make that improving, be more preferably the above-mentioned impact briquetting whole plane shadow mask that allows Ni segregation rate be low to moderate below 1.0% as the yield strength of the index of anti-drop impact deformability and Young's modulus is alloy and whole plane shadow mask and the color cathode ray tube that uses this alloy with Fe-Ni.Again, in the present invention, low heat expansion property means that 30～100 ℃ mean thermal expansion coefficients is 12 * 10 ^-7/ ℃ below, Ni segregation rate is low to mean that the measured value of analyzing the Ni segregation rate of gained with EPMA (Electron Prove Micro Analyzer) is below 1.0%.

Color cathode ray tube is that the phosphor body of the electron beam bump face glass inboard of getting by electron beam gun comes display frame.Coming the element of controlling electron beam direction with magnetic force is deflector coil.Near the face glass part, be provided with mechanism's (being called shadow mask) that picture element unit is separated so that electron beam clashes into the phosphor body of regulation.The shadow mask of colorful cathode ray tube can roughly be divided into: carry out stamping forming shadow mask (shadow mask) mode after the material for shadow mask etching and processing is become point-like or strip, and, be etched into behind the curtain shape on framework with bigger tension force its aperture grille of hanging up up and down (aperture grille) mode.Two modes respectively have its relative merits, are all market and adopt.

On the other hand, at the existing many trials of the exploitation of the smooth picture of display frame planarization.Big problem is how to make shadow mask and aperture grille near smooth one of during with the picture planarization of cathode tube.Though a difficult problem is separately respectively arranged, utilizes punching press to make the surface of shadow mask come difficultly (for example, [NIKKEI ELECTRONICS] 1999.7.26 (No.748) is 128 pages) than the mode of hanging up of aperture grille basically near smooth.

This be because, the tinsel drawing is made by shadow mask system, different with the mode of hanging up, it must keep shape by self conformal power; Basically, if not spherically just can't keep shape.On the other hand, the whole plane shadow mask is because will make the shadow mask almost flat, just with above-mentioned described contradiction.For head it off, except the intensity with shadow mask improves, have no other way.So-called herein " shadow mask intensity ", (for example, according to the intensity of tension test gained) meaning difference means that anticathode x ray tube integral body is impacted, and whether can cause the distortion of shadow mask after the cathode tube assembling with general metal strength.Particularly, be that cathode tube is fallen from certain height, whether the test shadow mask can be out of shape.Prevent the exploitation of the shadow mask of shock-produced deformation for this kind, the whole plane piping is belonged to necessary.

Again, the whole plane pipe is required to have excellent protuberance (doming) characteristic.That is along with shadow mask becomes whole plane by sphere, the input angle of electron beam in 4 corners of shadow mask of emitting from electron beam gun just acutangulates.In other words, it means that shadow mask because of thermal expansion produces skew slightly, the electron beam miscontacting of screen just can take place cause having problems such as colour cast.Therefore, need exploitation ratio shadow mask in the past to have the more shadow mask of low-thermal-expansion.

But, hang up the big advantage of one of required framework to not using the mode of hanging up, form the impact briquetting whole plane shadow mask of whole plane, have not need to use, therefore by punching press, hope can solve the problem that is accompanied by whole planeization and comes on this kind impact briquetting whole plane shadow mask.

Using the Fe-Ni of low bulk in shadow mask is alloy (Fe-36%Ni:Invar alloy), but along with the whole planeization of picture, also requires better low thermal expansion characteristics and high strength as mentioned above.

Therefore, hope can be kept the thermal expansion equal or lower with the Fe-36%Ni:Invar alloy, and shadow mask intensity is improved.

On the other hand, Fe-Ni is that alloy is processed in the shadow mask, and the Ni segregation phenomena is arranged in the material, when this segregation is serious, then the etching character of Ni segregation place is different with other positions, just can't make electron beam pass through shadow mask itself equably, thereby streak (striated passes through fault) takes place.At this, streak means and is forming the electronics line by when the hole with etching on the shadow mask, difference of height is appearring with row inside, hole partly, the connected hole of Ni segregation portion, and make light from the inboard directive outside, when by the hole face side being done comprehensive observation by the electronics line, different with other parts with the light intensity that this Ni segregation portion connected hole row part is emitted, observations is a striated.Therefore, the existence of Ni segregation is promptly represented in the generation of streak.

Problem of the present invention, it has been color cathode ray tube progress from now in response to the whole plane type, develop the anti-drop impact deformability of sening as an envoy to and improve required intensity raising, and the impact briquetting whole plane shadow mask that Ni segregation rate is low, thermal expansion is little is an alloy with Fe-Ni.

The present inventor is in order to increase the shadow mask intensity that anti-drop impact deformability is improved, in order to understand why and carried out various experiments as the requirement of material for shadow mask, it found that the Young's modulus of material for shadow mask and yield strength have maximum influence power.Promptly find,,, the shadow mask distortion can not take place yet even in the Impact Test of whole plane cathode tube by yield strength and Young's modulus are increased to the material that is higher than in the past.And, can reach the element that the unprecedented brand-new material of low-thermal-expansion should add to exploitation and inquire into.

Found that,, reduce the Mn addition, add Co according to circumstances in right amount, and add Nb, Ta and Hf in right amount, can solve this problem effectively, thereby finish the present invention based on the Fe-Ni alloy.

On the other hand, the patent No.29020004 number (day for announcing: on March 19th, 1999; Open day: on April 10th, 1991) propose, in common crooked shadow mask, in order to prevent because volume etc. from the outside colour cast that influence caused that adds vibration (vibration due to the singing), should improve the vibration damping energy of shadow mask, thereby with 0.1～5% Nb and Ta solid solution in nickelalloy.In an embodiment, use the 36%Ni-Fe alloy as nickelalloy.But this document is object not as the present invention with the whole plane shadow mask, and will strengthen shock-resistant deformability is problem, therefore can not be as reference of the present invention.

Known if consider etching or the like, the content that then limits impurity can be more suitable.Especially think that the qualification meeting is of value to hot workability and etching with the content that Nb, Ta and Hf form the N of nitride.

As relevant application, the applicant has proposed the patent application No.2000-031661 that relevant Fe-Ni-2～8%Co is an alloy material, can be alloy material with more low-cost manufacturing Fe-Ni but the object of the present invention is to provide.

Therefore, the invention provides that (1) is a kind of can keep low heat expansion property and make yield strength and impact briquetting whole plane shadow mask that Young's modulus improves is an alloy with Fe-Ni, it is characterized in that, with quality percentage (%) be benchmark (below, represent with %), contain Ni:33～37% and Mn:0.001～0.1%; Consider Co:0.01～2% that adds; Also contain one or more elements that are selected from Nb:0.01～0.8%, Ta:0.01～0.8% and Hf:0.01～0.8%, add up to 0.01～0.8%; And surplus is Fe and unavoidable impurities.

Particularly,, add up to 0.01～0.5%, and make the low person of Ni segregation rate for good because of containing one or more elements that are selected from Nb:0.01～0.5%, Ta:0.01～0.5% and Hf:0.01～0.5%.

As impurity, its content is to be limited to C: Si≤0.01%: P≤0.04%: S≤0.01% :≤0.01% and N :≤0.005% for good.

Alloy of the present invention is characterised in that, is 120 in the Young's modulus of 900 ℃ of annealing after 30 minutes, 000N/mm ²More than; And, in 0.2% yield strength of 900 ℃ of annealing after 30 minutes at 300N/mm ²More than.

Again, recommendering folder invention heat treatment of alloy condition is to implement 5 minutes to 1 hour under 700 ℃～900 ℃ temperature.

Again, the invention provides (2) a kind of impact briquetting whole plane shadow mask, it is characterized in that adopting above-mentioned Fe-Ni is alloy, and (3) a kind of color cathode ray tube, it is characterized in that using this Fe-Ni is alloy system impact briquetting whole plane shadow mask.

The invention is characterized in, Fe-Ni for the low heat expansion property that has been reduced by the Mn addition is the alloy that reaches a certain low-thermal-expansion that alloy becomes, do not make under the big situation of its thermal expansivity change, as in order to the raising yield strength that promotes anti-drop impact deformability and the interpolation element of Young's modulus, add Co as one feels fit, an amount of Nb, Ta and/or the Hf of adding, again, it is preferable limiting various impurity element C, Si, P, S and N.The qualification reason of the composition element relevant with the present invention will be described as follows.

Fundamental element

The content of Ni:Ni is 33～37%, and preferred range is 34～36%, has been deleterious tissue such as martensite (martensite) is produced, and has reached low-thermal-expansion with the effect that multiplies each other with Co.

Co:Co also has the function of the yield strength of making raising when thermal expansion is reduced.Therefore, minimum addition is good with 0.1%, and still, addition is in case surpass more than 2%, because of and Ni content between equilibrium relationship can make the thermal expansion rising.And from manufacturing cost and magnetic properties aspect, it also is disadvantageous further improving Co content, is not a good method.Though Co is random composition, with regard to purpose of the present invention,, particularly be added to good with 0.5～1.8% scope with 0.01～2%.Be accompanied by the interpolation of Ni, the micro-Co of＜0.01% degree can sneak into as associated element.

Mn:Mn is used as reductor to be added, but along with its interpolation can make thermal expansivity increase, therefore, for the mean thermal expansion coefficients that reaches at 30～100 ℃ is 12 * 10 ^-7/ ℃ below, the interpolation scope is necessary for 0.001～0.1%, preferred range is 0.001～0.05%.

Add element

Nb, Ta, Hf: under the situation that thermal expansion is increased,, can obtain desired high-yield strength, further improve Young's modulus by bringing into play the effect that multiplies each other with the compound interpolation of Co (when being added).Addition is discontented with 0.01% to no effect, otherwise if surpass 0.8%, then can cause the increase of etching reduction and thermal expansion.Interpolation scope when not only adding separately is necessary for 0.01～0.8%, and these total content that add element also must be in 0.01～0.8% scope.

Again, the etching characteristic of the shadow mask when making alloy of the present invention must be noted the generation of Ni segregation, and known Nb, Ta, Hf are relevant with the generation of Ni segregation.

Though detailed mechanism is unclear, in a single day infer and add Nb, Ta, Hf, Fe-Ni is that the solidus temperature and the liquidus temperature of alloy just can change, just becoming during casting is easy to take place the Ni segregation.Again, the present inventor also finds that when the Ni segregation took place, Young's modulus just reduced.Inferring the reason of this reduction, is because Ni segregation when taking place, and Fe-Ni is that the crystal orientation of alloy changes, Young's modulus thereby change.Though the Ni segregation is not only relevant with the addition of Nb, Ta, Hf, also can be cast and the influence of forging condition, but, as long as Nb, Ta, Hf distinctly add scope 0.01～0.5%, add up to the words of addition in 0.01～0.5% scope, Ni segregation rate just can be below 1.0%, can be not that alloy-sample takes place because of the streak due to the Ni segregation with the Fe-Ni that does not add Nb, Ta, Hf just.Therefore, the interpolation scope of Nb, Ta, Hf is respectively 0.01～0.5%, and their total addition is 0.01～0.5.

Impurity

C: surpass 0.01% and just can form superfluous carbide, cause etching to worsen, therefore, content must be lower than 0.01%.Being good below 0.006%.

Si: though have deoxidation effect, surpass at 0.04% o'clock etching is worsened widely, therefore be decided to be below 0.04%.

P: excessive as if containing, just can become the reason that etching worsens, therefore be decided to be below 0.01%, be preferably below 0.005%.

S: in case surpass 0.01%,, also can to etching bad influence be arranged, so be limited on it below 0.01%, being good below 0.005% because of the sulfide inclusion thing becomes many except meeting hinders hot workability.

N: form compound with Nb, Ta, Hf, hot workability and etching are worsened, therefore be decided to be below 0.005%, being good below 0.003%.

For example,, just extend into wire after rolling, the edge shape in the etching and processing hole of point-like or strip is worsened because MnS and P segregation have ductility.For etching is worsened, the content that limits impurity is necessary.

The acquisition of material for shadow mask is after earlier the alloy material of required composition being founded with for example vacuum induction calciner (VIM stove), to be cast as ingot bar, after the forging, carry out hot rolling and cold rolling, afterwards, carry out clean annealing and cold rolling repeatedly, finally be cold-rolled to the specific thickness of 0.1～0.25mm at last.Afterwards, the plate that cuts into regulation is wide, makes material for shadow mask.Material for shadow mask after degreasing, at the two sided coatings photo-resist, toast out pattern and video picture after, carry out etching and punching processing, be cut into material for shadow mask unit one by one.

With the material for shadow mask unit in non-oxidizable ambiance, for example in the reductibility ambiance annealing (for example, in the hydrogen, 900 ℃ following 30 minutes), give its punching formation property.

After calibration processing, make it be shaped to the planar aperture mask form via punching press.

At last, after the whole plane shadow mask degreasing that impact briquetting is gone out, at atmosphere or CO/CO ₂Carry out melanism in the atmosphere surrounding atmosphere and handle, form black oxide film from the teeth outwards.

Impact briquetting of the present invention " whole plane shadow mask " has, and for example, the outside radius of curvature R is 100, more than the 000mm, and planeness: the intimate complete planar form that the maximum height of picture curved face part/active area diagonal-size=0.1% is following.

Impact briquetting whole plane shadow mask of the present invention is characterised in that, maintains 12 * 10 at 30～100 ℃ of mean thermal expansion coefficientses ^-7/ ℃ below, after the annealing of giving above-mentioned press formability, Young's modulus is 120,000N/mm ²More than, 0.2% yield strength is 300N/mm ²More than.As long as Young's modulus is 120,000N/mm ²More than and 0.2% yield strength be 300N/mm ²More than, in aforesaid cathode tube shatter test, even the whole plane cathode tube can not produce the shadow mask distortion yet.

Impact briquetting whole plane shadow mask of the present invention can be realized Young's modulus: 130, and 000N/mm ²More than, 0.2% yield strength: 330N/mm ²More than; Further can realize Young's modulus: 140,000N//mm ²More than, 0.2% yield strength: 350N/mm simultaneously ²More than.

Again, about etching characteristic, as long as Ni segregation rate is below 1.0%, just cord defects can not take place, but as long as surpass 1.0%, according to the form in the hole of shadow mask and the difference of etching condition, streak might take place.At this, Ni segregation rate is defined as follows.

ΔNi＝C _x-C _o

Δ Ni:Ni segregation rate (%)

C _x: the Ni concentration (%) of striped portion

C _o: near the Ni concentration (%) the striped portion

Embodiment 1

It shown in the table 1 the employed alloy composition of embodiment and comparative example.

Table 1

	Alloy No.	Ni	Mn	C	Si	P	S	N	Co	Nb	Ta	Hf
													Example of the present invention	1	36.1	0.01	0.004	0.01	0.002	0.001	0.0025	＜0.01	0.31	0.001	＜0.001
2	35.8	0.08	0.003	0.01	0.002	0.001	0.0027	＜0.01	0.35	＜0.001	＜0.001
												3		34.1	0.03	0.003	0.01	0.003	0.001	0.0030	1.55	0.29	＜0.001	＜0.001
4	34.5	0.03	0.004	＜0.01	0.002	0.001	0.0027	0.90	0.26	＜0.001	＜0.001
												5		35.8	0.04	0.003	0.02	0.003	0.002	0.0019	＜0.01	＜0.001	0.32	＜0.001
6	36.1	0.02	0.005	＜0.01	0.002	0.001	0.0020	＜0.01	＜0.001	＜0.001	0.27
												7		35.7	0.02	0.004	0.01	0.003	0.001	0.0032	0.80	0.21	0.12	＜0.001
8	35.5	0.05	0.003	＜0.01	0.002	0.002	0.0018	＜0.01	0.18	0.12	0.10
												9		36.0	0.05	0.003	0.01	0.002	0.003	0.0022	＜0.01	＜0.001	0.20	0.25
10	34.4	0.02	0.003	0.01	0.002	0.001	0.003	1.40	0.13	0.14	0.13
												11		34.4	0.02	0.004	0.01	0.002	0.020	0.0030	1.65	0.29	＜0.001	＜0.001
12	35.4	0.03	0.018	0.01	0.002	0.002	0.0022	0.90	＜0.001	0.35	＜0.001
												13		34.6	0.04	0.003	0.11	0.003	0.002	0.0035	1.55	＜0.001	＜0.001	0.45
14	36.2	0.03	0.004	＜0.01	0.020	0.001	0.0040	＜0.01	0.37	0.15	＜0.001
												15		35.9	0.02	0.003	＜0.01	0.003	0.003	0.0072	0.90	0.30	＜0.001	0.20
Comparative example	16	36.0	0.32	0.003	0.01	0.003	0.002	0.0025	＜0.01	0.31	0.17														0.15
												17	35.7	0.03	0.004	0.01	0.002	0.003	0.0032	3.35	0.29	＜0.001	＜0.001
	18	35.5	0.03	0.004	＜0.01	0.002	0.002	0.0037	0.001	＜0.001	＜0.001													＜0.001
												19	32.1	0.03	0.003	＜0.01	0.003	0.001	0.0029	＜0.01	0.35	0.15	＜0.001
	20	38.9	0.05	0.003	0.01	0.002	0.001	0.0033	＜0.01	＜0.001	0.35													＜0.001
												21	36.3	0.03	0.004	0.01	0.002	0.002	0.0029	＜0.01	0.40	0.70	＜0.001
	22	35.9	0.02	0.002	＜0.01	0.003	0.002	0.0036	1.50	0.29	0.35													0.40

The alloy of 10 kilograms of these compositions is founded with vacuum induction calciner (VIM stove).Found the back forge down at 1200 ℃, then under 1200 ℃, be rolled into 3mm thick after, repetitiousness carries out cold rolling and clean annealing, work is into about the thick cold rolling material of 0.12mm.Afterwards, the plate that cuts into regulation is wide as material for shadow mask, and this material is annealed in the reductibility ambiance (in the hydrogen 900 ℃ * 30 minutes) gives press formability.

Material after this annealing is carried out Elongation test, when measuring tensile strength and 0.2% yield strength, carry out the flexural resonance method, at room temperature measure Young's modulus according to " JIS R1605 ".

This method system is in the mode of the flexural vibration that can gain freedom, suspention line with drive-side and detector side comes the trapeze test sheet, and the top and bottom of test film are applied motivating force from vibrator, see through detector and produce peak swing, and the node of measuring vibration decides the resonance vibration number one time, according to fixed formula, calculate the dynamic elasticity rate by the quality and the size of resonance vibration number, test film.Moreover, the mean thermal expansion coefficients between measuring 30～100 ℃, and for the surface with 60 ℃ of the pressure sprays of 0.3MPa, the ferric chloride in aqueous solution of 45 degree Beaume (Be), observe the state of etching face.

The results are shown in table 2.

Table 2

	Alloy Nb	Tensile strength N/mm 2	0.2% yield strength N/mm 2	Young's modulus N/mm 2	Mean thermal expansion coefficients (30～100 ℃ of measurement ranges) * 10 -7/℃	The etching face state
							Example of the present invention	1	485	332	133000	9.5	○
2	494	338	134000	9.8	○
						3		497	340	135000	8.6	○
4	490	335	134000	8.9	○
						5		480	330	132000	9.7	○
6	475	330	133000	9.5	○
						7		500	345	136000	9.2	○
8	505	340	139000	9.9	○
						9		510	350	140000	10.2	○
10	528	365	145000	11.2	○
						11		490	330	132000	9.2	△
12	530	370	143000	8.8	△
						13		495	340	139000	10.0	△
14	500	340	140000	10.4	△
						15		525	368	142000	10.9	△
Comparative example	16	540	378	146000	15.2								○
						17	520	348	141000	13.9	○
	18	430	279	115000	8.0							○
						19	496	336	133000	28.0	○
	20	480	325	134000	35.5							○
						21	555	380	145000	14.4	×
	22	565	388	145000	15.6							×

* 1 mensuration * 2 zero: good △ according to vibratory drilling method: slightly inferior, but use go up no problem *: the etched mark that small concavo-convex and foreign matter is arranged

What alloy No.1 of the present invention～10 surpassed thermal expansivity allows level (12 * 10 ^-7/ ℃), can fully realize Young's modulus 120,000N/mm as target ²More than, 0.2 yield strength 300N/mm ²More than, alloy No.9～10 particularly, it has realized Young's modulus 140,000N/mm simultaneously ²More than and 0.2% yield strength 350N/mm ²More than.Mn and impurity also in specialized range, demonstrate good etching face state.

Again, alloy No.11 of the present invention～15, because its impurity element S, C, Si, P, N surpass the impurity regulation level of claim 3 respectively, so the state of etching face is slightly inferior, but still in the scope of no use problem.Its 0.2% yield strength, Young's modulus and mean thermal expansion coefficients system satisfy target value of the present invention.

With respect to this, alloy No.16 is because containing of Mn surpasses 0.1%, so the mean thermal expansion coefficients height.Alloy No.17 because the content of Co surpasses 2.0%, and Ni content between inadequate balance, its mean thermal expansion coefficients height.Do not add the then non-constant of strength characteristics of the alloy No.18 of Nb, Ta, Hf.Alloy No.19～20 because Ni content not in 33～37% scope, so mean thermal expansion coefficients is very high.Alloy No.21 is because the content of Nb and Ta surpasses 0.8%, No.22 is because the total content of Nb, Ta, Hf surpasses 0.8%, the also bad result of state of demonstration mean thermal expansion coefficients height and etching face.

Again, about Ni segregation rate, be that material section is made mirror ultrafinish, be impregnated in after carrying out etching in 30 seconds in the ferric chloride in aqueous solution of 45 degree Beaume of water dilution tenfold, observe resulting segregation line.No.21 in the table 2 can be observed the most serious line of analysing.The Ni segregation rate of measuring this segregation line portion with EPMA is 0.98%.

Embodiment 2

Carry out the investigation of real machine level.Found the alloy of forming shown in the 6000kg table 3 with vacuum induction calciner (VIM stove); Found that forge down at 1200 ℃ the back, then to be rolled into 3mm under 1200 ℃ thick, cool off repeatedly then and clean annealing, work is into about the thick cold rolling material of 0.12mm.Afterwards, the plate that cuts into regulation is wide as material for shadow mask, and this material is annealed in the reductibility ambiance (in the hydrogen 825 ℃ * 15 minutes) gives press formability.

Annealing conditions 825 ℃ * 15 minutes was to obtain higher yield strength, thereby carried out under the temperature lower than embodiment.

Table 3

Alloy No.	C	N	Si	Mn	P	S	Ni	Co	Nb	Ta	Hf
												23	0.003	0.0019	0.02	0.02	0.002	0.002	35.9	＜0.01	0.45	＜0.001	＜0.001
24	0.003	0.0023	＜0.01	0.02	0.003	0.002	36.3	＜0.01	＜0.001	＜0.001	0.29
												25	0.003	0.0012	0.01	0.01	0.003	0.002	36.2	＜0.01	0.10	0.11	0.12
26	0.002	0.0011	0.02	0.05	0.002	0.003	35.0	0.92	0.12	＜0.001	＜0.001
												27	0.002	0.0023	0.01	0.04	0.004	0.001	35.9	＜0.01	0.001	0.09	＜0.001
28	0.003	0.0011	0.02	0.04	0.004	0.003	35.9	0.07	0.05	0.06	0.04
												29	0.003	0.0025	0.02	0.02	0.003	0.02	35.8	＜0.01	0.30	＜0.001	＜0.001
30	0.003	0.0034	0.01	0.02	0.003	0.001	36.0	＜0.01	＜0.001	＜0.001	＜0.001
												31	0.003	0.0009	＜0.01	0.02	0.004	0.003	35.8	＜0.01	0.58	＜0.001	＜0.001
32	0.003	0.0024	0.01	0.02	0.003	0.003	36.3	0.03	＜0.001	0.59	＜0.001
												33	0.002	0.0032	＜0.01	0.02	0.003	0.003	35.5	0.23	＜0.001	0.20	0.39
34	0.004	0.0019	＜0.01	0.02	0.003	0.002	35.8	＜0.01	0.21	0.24	0.22

The same with embodiment 1, material after this annealing is measured its tensile strength, 0.2% yield strength, Young's modulus and mean thermal expansion coefficients, carry out the investigation of etching (having or not of the etched mark that foreign matter caused) and Ni segregation, also further confirm whether striate generation.

About the Ni segregation, the same with embodiment 1, with the segregation line of microscopic examination material section, each selected 3 have significantly segregation line person in each material, respectively it are measured Ni segregation rate with EPMA, and the maximum value in these 3 measurement results is showed.

As for having or not of streak, tie up on the material and to form one side and have after 80 μ m diameters, another side have the just round erosion resistance shadow mask of 180 μ m diameters, 60 ℃, the ferric chloride in aqueous solution of 45 degree Beaume are carried out etching with the pressure spray of 0.3MPa on its surface, confirm the generation of streak.

It the results are shown in table 4.

Table 4

Alloy Nb	Tensile strength N/mm 2	0.2% yield strength N/mm 2	Young's modulus N/mm 2	30～100 ℃ of mean thermal expansion coefficients * 10 -7/℃	Ni segregation rate %	The etching face state
								Having or not of streak	The etched mark that foreign matter caused
						23	512			353	141800	11.3	0.91	Do not have	Do not have
24	502	341	145300	10.1	0.78			Do not have	Do not have
						25	504			345	142200	11.0	0.82	Do not have	Do not have
26	478	322	137200	9.4	0.72			Do not have	Do not have
						27	480			325	136300	9.8	0.69	Do not have	Do not have
28	482	327	136700	8.8	0.71			Do not have	Do not have
						29	498			343	143800	10.2	0.77	Do not have	Have
30	458	275	116500	8.0	0.62			Do not have	Do not have
						31	515			358	134800	12.1	1.08	Have	Do not have
32	513	355	134500	12.1	1.10			Have	Do not have
						33	508			361	132300	11.9	1.15	Have	Do not have
34	519	357	131400	12.4	1.25			Have	Do not have

^*1 mensuration according to vibratory drilling method

^*Maximum value in 23 measured values

Alloy No.23～29, what not only surpass mean thermal expansion coefficients allows level 12 * 10 ^-7/ ℃, as the Young's modulus of target also at 130000N/mm ²More than, yield strength is also at 300N/mm ²More than, moreover Ni segregation rate is to realize good etching resistance below 1%, and do not produce streak.Particularly the total content of Nb, Ta, Hf can realize that at the No.23,24,25 and 29 of 0.2～0.5% scope Young's modulus is at 140000N/mm ²More than, 0.2% yield strength is 330N/mm ²More than, and Ni segregation rate is below 1%.

With respect to this, No.30 because the total content of Nb, Ta, Hf less than 0.01%, its Young's modulus and 0.2% yield strength are all low.

No.31～34 a total content because of its Nb, Ta, Hf surpasses 0.5%, and the unallowed high Ni segregation rate of embodiment occurred, and streak has also taken place.Again, the Young's modulus of these alloys is 130000～140000N/mm ²Though, on target, but still be that 0.2～0.5% No.23,24,25 and 29 is for low than the total content of Nb, Ta, Hf.

Therefore, particularly prevent on the purposes of Ni segregation in attention, should want can be easily or positively prevent the Ni segregation, though Nb, Ta, Hf content and total content thereof separately is controlled at below 0.5% in this suggestion, but, also can be by accurately managing the generation that the manufacturing processed that comprises casting and forging condition etc. prevented or reduced this streak.

More than, the Mn content that will contain in the Fe-Ni alloy of suitable Ni concentration is controlled at lower concentration, and it is complied with requiredly contain a spot of Co and reach low-thermal-expansion, reach insufficient yield strength by adding an amount of Nb, Ta and/or Hf simultaneously, thereby Young's modulus is also improved in the lump.Moreover, recognize that these elements also can not make thermal expansion character worsen, and can realize optimal performance as the effective material for shadow mask of whole plane.

Can prevent the deterioration of etching by the content that qualification comprises the impurity element of N etc. again.

Also handle for Ni segregation problem again.

Thereby, on from now on plane-type colour cathode-ray tube is handled, can obtain there is not colour cast, can not be out of shape when using, low-cost good impact briquetting whole plane shadow mask.

Claims (8)

1. an impact briquetting whole plane shadow mask is an alloy with Fe-Ni, and it keeps low heat expansion property and yield strength and Young's modulus to improve; It is characterized in that, in quality percentage (%), composed as follows; Ni:33～37% and Mn:0.001～0.1%; Consider Co:0.01～2% that adds; Be selected from Nb:0.01～0.8%, Ta:0.01～0.8%, and one or more elements of Hf:0.01～0.8%, adding up to content is 0.01～0.8%; And surplus is Fe and unavoidable impurities.

2. impact briquetting whole plane shadow mask as claimed in claim 1 is an alloy with Fe-Ni, it is characterized in that, and is in quality percentage (%), composed as follows: Ni:33～37% and Mn:0.001～0.1%; Consider Co:0.01～2% that adds; Be selected from Nb:0.01～0.5%, Ta:0.01～0.5%, and one or more elements of Hf:0.01～0.5%, adding up to content is 0.01～0.5%; And surplus is Fe and unavoidable impurities.

3. impact briquetting whole plane shadow mask is an alloy with Fe-Ni as claimed in claim 1 or 2, wherein, aspect impurity, is defined as C: Si≤0.01%: P≤0.04%: S≤0.01% :≤0.01% and N :≤0.005%.

4. impact briquetting whole plane shadow mask is an alloy with Fe-Ni as claimed in claim 1 or 2, wherein, is 120 in the Young's modulus of 900 ℃ of annealing after 30 minutes, 000N/mm ²More than.

5. impact briquetting whole plane shadow mask is an alloy with Fe-Ni as claimed in claim 1 or 2, wherein, is 300N/mm in 0.2% yield strength of 900 ℃ of annealing after 30 minutes ²More than.

6. being alloy as impact briquetting whole plane shadow mask as described in the claim 3 with Fe-Ni, wherein, is 300N/mm in 0.2% yield strength of 900 ℃ of annealing after 30 minutes ²More than.

7. stamping forming whole plane shadow mask, it is characterized in that using the described Fe-Ni of one of claim 1-6 is alloy.

8. a color cathode ray tube is characterized in that, using the described Fe-Ni of claim 7 is alloy system impact briquetting whole plane shadow mask.

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