CN104651666B - PTC thermistor alloy wire and preparation method thereof - Google Patents
PTC thermistor alloy wire and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a PTC thermistor alloy wire and a preparation method thereof. The alloy wire comprises the following chemical components in percentage by weight: 64%-78 % of nickel, 0.1%-0.6% of silicon, 0.22%-0.30 % of manganese, 0.02%-0.04 % of yttrium, 0.04%-0.06 % of mixed rare earth, less than or equal to 0.05 % of carbon, less than or equal to 0.01% of sulfur, less than or equal to 0.001% of phosphorus, and the balance of iron; the average resistance temperature coefficient of the alloy wire at 0 DEG C-150DEG C is 4300*10＜-6＞/DEG C-4800*10＜-6＞/DEG C, the resistivity of the alloy wire is (0.19-0.27) +/-0.02mu ohm.m; and the PTC thermistor alloy wire is a PTC thermistor alloy wire with the resistance temperature coefficient of higher than 3000 *10＜-6＞/DEG C currently needed, thus meeting the requirement on the more sensitive temperature control of new electrical equipment and the like.
Description
The application is Application No. 201310031374.5, and the applying date is on January 28th, 2013, and invention and created name is
The divisional application of the application for a patent for invention of " PTC thermistor B alloy wire and preparation method thereof ".
Technical field
The present invention relates to a kind of B alloy wire, and in particular to a kind of semistor B alloy wire and its preparation side
Method.
Background technology
PTC (Positive Temperature Coefficient, positive temperature coefficient) critesistor is a kind of with temperature
The semiconductor resistor of degree sensitivity, when more than certain temperature (Curie temperature), its resistance value is with the rising of temperature
Almost it is in increasing for phase step type.PTC thermistor can, temperature excessive in current surge it is too high when circuit is shielded.
According to the difference of material, PTC thermistor include ceramic PTC critesistor, organic polymer PTC thermistor and
Metal PTC critesistor.
Ceramic PTC thermistor material is with BaTiO3Or SrTiO3Or PbTiO3For the sintered body of main component, wherein mixing
Entering the oxides such as micro Nb, Ta, Bi, Sb, Y, La carries out atomicity control and is allowed to semiconducting, generally by this semiconducting
BaTiO3Semiconductor porcelain is referred to as Deng material；Simultaneously also addition increases the oxidation of Mn, Fe, Cu, Cr of its positive temperature coefficient
Thing and play the additive of other effects, shaped using general ceramic process, high temperature sintering and make Barium metatitanate. etc. and its solid solution partly
Leading, so as to obtain the PTC thermistor material of positive characteristic.
Organic polymer PTC thermistor material is made up of macromolecular material addition conducting particles, and its ultimate principle is
A kind of balance of energy.Heat is produced when electric current flows through element, a produced heat part is dispersed in environment, one
Divide the temperature that increased macromolecular material.Under operating current, the heat of generation and the heat for distributing reach balanced balanced current can be with
Normal through.When super-high-current passes through, element produces substantial amounts of heat and can not timely distribute, and causes macromolecular material
Temperature rises, and when temperature reaches material crystalline melt temperature, macromolecular material gathers expansion, blocks molecular by conductive particle
Conductive path, causes resistance to rise rapidly, limits high current and passes through, so as to play overcurrent protection.
PTC thermistor B alloy wire is the core material of metal PTC thermistor element.As PTC thermistor alloy
It has medium resistivity, and big and positive temperature-coefficient of electrical resistance, its resistance value is linear with temperature, and resistance
Good stability.PTC thermistor B alloy wire is widely used in atmospheric temperature heater and various household electrics in Aeronautics and Astronautics device
Device element, it has temperature automatically controlled, Automatic Power Adjust, constant current, current limliting and improves many-sided function such as component life.Additionally,
PTC thermistor B alloy wire can be additionally used in making resistance thermometer and carry out thermometric.
The production of China's PTC thermistor B alloy wire just has started in last century the eighties, but the kind for producing at that time
Very single, temperature-coefficient of electrical resistance also can only achieve 3000 × 10-6/ DEG C or so.With the development of national economy, particularly reform
Since open, China joined WTO, PTC thermistor alloy has obtained extensive popularization and application.Metal PTC critesistor is in recent years
Extensively to replace ceramics and organic polymer critesistor, application also to extend.According to the preliminary statistics, at present only metal PTC is warm
There is every year nearly more than 100 tons of demand in quick electric resistance alloy silk, the whole nation, but current country's PTC thermistor B alloy wire does not form and is
Row product, single varieties, the temperature-coefficient of electrical resistance that user is badly in need of is higher than 3000 × 10-6/ DEG C also do not have.Due to emerging electric
Equipment needs the control of more smart temperature and the resistive element for adjusting, it is necessary to improve the temperature-coefficient of electrical resistance upper limit of resistance wire.
The content of the invention
The technical problem to be solved is to provide a kind of PTC thermistor B alloy wire and preparation method thereof.
The technical scheme for realizing the object of the invention is a kind of PTC thermistor B alloy wire, the chemical composition of the B alloy wire
And its weight/mass percentage composition is：Nickel 45%～82.0%, silicon 0.1%～0.6%, manganese 0.22%～0.35%, yttrium 0.02%～
0.04%th, mischmetal 0.04%～0.06%, carbon is less than or equal to less than or equal to 0.05%, sulfur less than or equal to 0.01%, phosphorus
0.001%, balance of ferrum.
The mean temperature coefficient of resistance of 0 DEG C of above-mentioned B alloy wire～150 DEG C is 2500 × 10-6/ DEG C～5000 × 10-6/
℃；The resistivity of B alloy wire is (0.17～0.43) ± 0.02 μ Ω m.
When above-mentioned B alloy wire chemical composition and its weight/mass percentage composition be nickel 64%～82.0%, silicon 0.1%～
0.6%th, manganese 0.22%～0.35%, yttrium 0.02%～0.04%, mischmetal 0.04%～0.06%, carbon are less than or equal to
0.05%th, sulfur less than or equal to 0.01%, phosphorus less than or equal to 0.001%, balance of ferrum when, 0 DEG C～150 DEG C of B alloy wire average
Temperature-coefficient of electrical resistance is 4300 × 10-6/ DEG C～5000 × 10-6/ DEG C, the resistivity of B alloy wire is (0.17～0.29) ± 0.02 μ
Ω·m。
When above-mentioned B alloy wire chemical composition and its weight/mass percentage composition be nickel 49%～65%, silicon 0.1%～0.25%,
Manganese 0.22%～0.35%, yttrium 0.02%～0.04%, mischmetal 0.04%～0.06%, carbon are less than or equal to 0.05%, sulfur
Less than or equal to 0.01%, phosphorus less than or equal to 0.001%, balance of ferrum when, 0 DEG C～150 DEG C of B alloy wire of average resistance temperature
Coefficient is 3000 × 10-6/ DEG C～4300 × 10-6/ DEG C, the resistivity of B alloy wire is (0.27～0.40) ± 0.02 μ Ω m.
When in the chemical composition of B alloy wire also include aluminum；The chemical composition and its weight/mass percentage composition of above-mentioned B alloy wire is nickel
45%～49%, silicon 0.2%～0.3%, manganese 0.30%～0.35%, yttrium 0.02%～0.04%, mischmetal 0.04%～
0.06%th, aluminum 0.4%～0.5%, carbon less than or equal to 0.05%, sulfur less than or equal to 0.01%, phosphorus less than or equal to 0.001%, it is remaining
Measure for ferrum when, 0 DEG C～150 DEG C of B alloy wire of mean temperature coefficient of resistance is 2500 × 10-6/ DEG C～3000 × 10-6/ DEG C, close
The resistivity of spun gold is (0.40～0.43) ± 0.02 μ Ω m.
As preferred, further above-mentioned PTC thermistor B alloy wire can be divided into into 6 according to mean temperature coefficient of resistance
Group, so as to obtain the PTC thermistor B alloy wire of 6 kinds, meets respectively different use occasions.
When the chemical composition and its weight/mass percentage composition of B alloy wire are：Nickel 78%～82%, silicon 0.28%～0.60%, manganese
0.30%～0.35%, yttrium 0.02%～0.04%, mischmetal 0.04%～0.06%, carbon are little less than or equal to 0.05%, sulfur
In equal to 0.01%, phosphorus less than or equal to 0.001%, balance of ferrum when, 0 DEG C～150 DEG C of B alloy wire of average resistance temperature system
Number is 4800 × 10-6/ DEG C～5000 × 10-6/ DEG C, the resistivity of B alloy wire is (0.17～0.19) ± 0.02 μ Ω m.Meet
The mean temperature coefficient of resistance of the PTC thermistor B alloy wire of mentioned component and content is very high, and highest can be to 5000 × 10-6/
DEG C, the vacancy of high temperature coefficient of resistance in PTC thermistor B alloy wire has been filled up, and B alloy wire is easy to be processed into filament, closes
The intensity and corrosion resistance of spun gold is preferable.
When the chemical composition and its weight/mass percentage composition of B alloy wire are：Nickel 64%～78%, silicon 0.1%～0.60%, manganese
0.22%～0.30%, yttrium 0.02%～0.04%, mischmetal 0.04%～0.06%, carbon are little less than or equal to 0.05%, sulfur
In equal to 0.01%, phosphorus less than or equal to 0.001%, balance of ferrum when, 0 DEG C～150 DEG C of B alloy wire of average resistance temperature system
Number is 4300 × 10-6/ DEG C～4800 × 10-6/ DEG C, the resistivity of B alloy wire is (0.19～0.27) ± 0.02 μ Ω m.Meet
The mean temperature coefficient of resistance of the PTC thermistor B alloy wire of mentioned component and content is higher, it is adaptable to need above-mentioned resistance temperature
The occasion of degree coefficient range.And B alloy wire is easy to be processed into filament, the intensity and corrosion resistance of B alloy wire is preferable.
When the chemical composition and its weight/mass percentage composition of B alloy wire are：Nickel 53%～65%, silicon 0.1%～0.60%, manganese
0.22%～0.30%, yttrium 0.02%～0.04%, mischmetal 0.04%～0.06%, carbon are little less than or equal to 0.05%, sulfur
In equal to 0.01%, phosphorus less than or equal to 0.001%, balance of ferrum when, 0 DEG C～150 DEG C of B alloy wire of average resistance temperature system
Number is 4000 × 10-6/ DEG C～4300 × 10-6/ DEG C, the resistivity of B alloy wire is (0.27～0.36) ± 0.02 μ Ω m.Meet
The PTC thermistor B alloy wire of mentioned component and content is applicable to the occasion of above-mentioned temperature-coefficient of electrical resistance scope.And close
Spun gold is easy to be processed into filament, and the intensity and corrosion resistance of B alloy wire is preferable.
When the chemical composition and its weight/mass percentage composition of B alloy wire are：Nickel 49%～53%, silicon 0.1%～0.25%, manganese
0.22%～0.35%, yttrium 0.02%～0.04%, mischmetal 0.04%～0.06%, carbon are little less than or equal to 0.05%, sulfur
In equal to 0.01%, phosphorus less than or equal to 0.001%, balance of ferrum when, 0 DEG C～150 DEG C of B alloy wire of average resistance temperature system
Number is 3000 × 10-6/ DEG C～4000 × 10-6/ DEG C, the resistivity of B alloy wire is (0.36～0.40) ± 0.02 μ Ω m.Meet
The PTC thermistor B alloy wire of mentioned component and content is applicable to the occasion of above-mentioned temperature-coefficient of electrical resistance scope.And close
Spun gold is easy to be processed into filament, and the intensity and corrosion resistance of B alloy wire is preferable.
When the chemical composition and its weight/mass percentage composition of B alloy wire are：Nickel 45%～49%, silicon 0.1%～0.25%, manganese
0.22%～0.35%, yttrium 0.02%～0.04%, mischmetal 0.04%～0.06%, aluminum 0.4%～0.5%, carbon are less than
Equal to 0.05%, sulfur less than or equal to 0.01%, phosphorus less than or equal to 0.001%, balance of ferrum when, 0 DEG C～150 DEG C of B alloy wire
Mean temperature coefficient of resistance is 2500 × 10-6/ DEG C～3000 × 10-6/ DEG C, the resistivity of B alloy wire be (0.40～0.43) ±
0.02μΩ·m.The PTC thermistor B alloy wire for meeting mentioned component and content is applicable to above-mentioned temperature-coefficient of electrical resistance model
The occasion enclosed.And B alloy wire is easy to be processed into filament, the intensity and corrosion resistance of B alloy wire is preferable.
When the chemical composition and its weight/mass percentage composition of B alloy wire are：Nickel 45%, silicon 0.25%, manganese 0.35%, yttrium
0.03%th, mischmetal 0.05%, aluminum 0.45%, carbon are less than or equal to less than or equal to 0.05%, sulfur less than or equal to 0.01%, phosphorus
0.001%th, during balance of ferrum, 0 DEG C～150 DEG C of B alloy wire of mean temperature coefficient of resistance is 2500 × 10-6/ DEG C, B alloy wire
Resistivity be 0.43 ± 0.02 μ Ω m.The PTC thermistor B alloy wire for meeting mentioned component and content is applicable to
State the occasion of temperature-coefficient of electrical resistance scope.And B alloy wire is easy to be processed into filament, the intensity and corrosion resistance of B alloy wire is preferable.
The preparation method of above-mentioned PTC thermistor B alloy wire is comprised the following steps：
1. the preparation of raw material.
2. vacuum melting：In nickel that 1. step is prepared, the crucible of ferrum input vacuum melting furnace, remaining trace element material
Each it is placed in hopper and waits to put into；Verifying vacuum drying oven and heating makes to start the trace element in loading hopper after nickel, ferrum fine melt；Charging
Finish rear refine；Calm after refine, then powered cast, pouring temperature is 1130 DEG C～1170 DEG C；It is cold with stove after being poured
But, destroy and come out of the stove after vacuum.
3. forge hot is carried out to the spindle of gained after step 2. vacuum melting；Alloy heating-up temperature is 1010 DEG C～1050 DEG C,
Temperature retention time 30～40 minutes, hot stove total 90～120 minutes heat time heating times.
4. hot rolling, by step 3. gained square forging stock be rolled into diameter 7mm～8.8mm wire rods.
5. anneal, the wire rod obtained by step 4. hot rolling is annealed.
6. the wire rod after 5. annealing to step carries out successively wire drawing and annealing, reciprocal three times, divides 3 times by 7mm～8.8mm disks
Bar wire drawing is to required B alloy wire diameter.
7. finished product detection packaging is dispatched from the factory.
Above-mentioned steps 2. vacuum melting when, the charging sequence of the trace element in hopper be followed successively by silicon, manganese, mischmetal,
Yttrium.
Well formula tempering furnace is adopted when 6. above-mentioned steps anneal for the first time, silk base first rinses dry with suds greasy dirt before annealing
It is net and dry；The furnace bottom of well formula tempering furnace places Linesless charcoal.
The present invention has positive effect：(1) PTC thermistor B alloy wire of the invention is by matching somebody with somebody that change is wherein constituted
Than content, 0 DEG C～150 DEG C of mean temperature coefficient of resistance is 2500 × 10-6/ DEG C～5000 × 10-6/℃；Except existing market
Upper existing mean temperature coefficient of resistance is 2500 × 10-6/ DEG C～3000 × 10-6/ DEG C PTC thermistor B alloy wire outside, also
It is higher than 3000 × 10 including the current temperature-coefficient of electrical resistance being badly in need of-6/ DEG C PTC thermistor B alloy wire, and average resistance temperature
Coefficient highest can be to 5000 × 10-6/ DEG C, meet more smart temperature control of emerging electrical equipment etc. and require.
(2) PTC thermistor B alloy wire of the invention includes metallic yttrium.The performance of B alloy wire is particularly resistance temperature system
What number was mainly determined by alloying component；In PTC thermistor B alloy wire temperature-rise period when in use, by outside air or Jie
The impact of matter, can produce Oxidation in alloy surface, so that the composition of alloy changes, affect the performance of alloy.
Add in nickel-base alloy after metallic yttrium, metallic yttrium is oxidized in alloy internal priority during intensification, form fine and close diffusion trapping layer,
Prevent the severe oxidation of alloy key component, it is ensured that the stability of B alloy wire and the service life under Elevated Temperature Conditions
It is long.
In addition, in fusion process, metallic yttrium can generate dystectic oxide with the nonmetallic inclusion such as oxygen, nitrogen and on
It is floating, play a part of to purify alloy.
(3) present invention adds mischmetal in the course of processing of PTC thermistor B alloy wire, it is to avoid metallic nickel is closed
Sulfur corrosion in golden raw material, increased B alloy wire service life in a heated condition.
Specific embodiment
(embodiment 1, PTC thermistor B alloy wire)
The chemical composition of the PTC thermistor B alloy wire of the present embodiment is respectively by weight percentage：Nickel (Ni)
78.0%th, silicon (Si) 0.6%, manganese (Mn) 0.3%, yttrium (Y) 0.02%～0.04% (being 0.03% in the present embodiment), mixing are dilute
Soil 0.04%～0.06% (in the present embodiment be 0.05%), carbon (C) less than or equal to 0.05%, sulfur (S) less than or equal to 0.01%,
Phosphorus (P) is less than or equal to 0.001%, balance of ferrum (Fe).
The mean temperature coefficient of resistance of 0 DEG C of the PTC thermistor B alloy wire of the present embodiment～150 DEG C is 4800 × 10-6/
℃；The precision of temperature-coefficient of electrical resistance is ± 50 × 10-6/℃；Resistivity of the B alloy wire at 20 DEG C is (0.19 ± 0.02) μ Ω
m.The tensile strength of the B alloy wire of soft state is more than 390Mpa.
Because emerging electrical equipment needs the control of more smart temperature and the resistive element for adjusting, it is necessary to improve resistance wire
The temperature-coefficient of electrical resistance upper limit is meeting requirement.And control by made by the PTC thermistor B alloy wire of above-mentioned high temperature coefficient of resistance
Warm instrument can more automatically, effectively, promptly control industry or the operating temperature in household electrical appliance, reach the purpose of temperature control；Avoid
General instrument be difficult to temperature control or can not be temperature automatically controlled defect.This is individual to the automaticity for further improving instrument and meter
Very big leap, had both saved the energy, and manpower is saved again.While the PTC thermistor B alloy wire system of high temperature coefficient of resistance
Into instrument due to preferably current limliting, constant current can be played a part of to whole circuit, greatly reduce the electrical equipment fully loaded time,
Thus improve the life-span of resistive element life-span or even whole equipment.
In addition, resistive element made by the PTC thermistor B alloy wire of high temperature coefficient of resistance also has more preferable power certainly
The dynamic function of adjusting；This aspect improves the precision of equipment, and another aspect also has the effect of energy-conservation.
Because the performance of B alloy wire is particularly what temperature-coefficient of electrical resistance was mainly determined by alloying component；PTC thermistor
In B alloy wire temperature-rise period when in use, affected by outside air or medium, Oxidation can be produced in alloy surface, from
And make the composition of alloy change, affect the performance of alloy.Add after metallic yttrium in nickel-base alloy, metallic yttrium exists during intensification
Alloy internal priority is oxidized, and forms fine and close diffusion trapping layer, prevents the severe oxidation of alloy key component, it is ensured that alloy
The stability and the long service life under Elevated Temperature Conditions of silk.
Due to unavoidably containing sulfur in the metals such as the nickel in alloy raw material, ferrum, sulfur can significantly speed up nickel-base alloy
Corrosion rate.Due to the formation of sulfide, metallic nickel is made in SO2And CO2Mixed gas in corrosion rate its than
The O of 0.1MPad2In oxidation rate be higher by the 4-6 order of magnitude, this just directly affects B alloy wire use in a heated condition
Life-span.And the addition of mischmetal can avoid metallic nickel by the sulfur corrosion in alloy raw material, B alloy wire is increased in heating
Under the conditions of service life.
The line footpath specification and tolerance such as table 1 below of the PTC thermistor B alloy wire of the present embodiment, and according to can using needs
To produce the B alloy wire of other line footpath specifications：
The line footpath specification of table 1 and tolerance
| Line footpath Φ (mm) | Φ≤0.05 | 0.05 ＜ Φ ＜ 0.17 | 0.17≤Φ ＜ 0.25 |
| Line footpath tolerance (mm) | ±0.005 | ±0.008 | ±0.01 |
The elongation percentage such as table 2 below of soft state PTC thermistor B alloy wire：
The B alloy wire of table 2 (soft state) elongation percentage
| Line footpath Φ (mm) | 0.05～0.06 | 0.06～0.10 | 0.10～0.15 | 0.15～0.25 |
| B alloy wire (soft state) elongation percentage | >=10% | >=12% | >=16% | >=20% |
PTC thermistor B alloy wire is per axle net quality such as table 3 below：
The analysis of the B alloy wire of the present embodiment and following examples is carried out as follows with measurement：
A, Chemical bath deposition are according to GB/T 223.25, and GB/T 223.62, GB/T 223.68, GB/T 223.69 is chemical
Analysis method is carried out.
B, line footpath specification and tolerance precision are not less than the micrometer of 0.001mm and measure.
C, temperature-coefficient of electrical resistance are measured by the method that GB/T6148 specifies.
D, resistivity and rice resistance value are measured by the method that GB/T6146 specifies.
E, tensile strength and elongation percentage are carried out by the method that GB/T228 specifies.
F, surface quality are detected by an unaided eye, checked.
(embodiment 2 to embodiment 6, PTC thermistor B alloy wire)
The chemical composition of the PTC thermistor B alloy wire of embodiment 2 to embodiment 6 is shown in Table by weight percentage 3：
The embodiment 1 of table 3 is to embodiment 6
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Nickel (Ni) | 78.0% | 82% | 64.45% | 53% | 49% | 45% |
| Silicon (Si) | 0.6% | 0.28 | 0.1 | 0.1 | 0.25 | 0.25 |
| Manganese (Mn) | 0.3% | 0.35 | 0.22 | 0.22 | 0.35 | 0.35 |
| Yttrium (Y) | 0.03% | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
| Mischmetal | 0.05% | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| Aluminum (Al) | -- | -- | -- | -- | 0.45 | 0.45 |
| Carbon (C) | ≤ 0.05% | ≤ 0.05% | ≤ 0.05% | ≤ 0.05% | ≤ 0.05% | ≤ 0.05% |
| Sulfur (S) | ≤ 0.01% | ≤ 0.01% | ≤ 0.01% | ≤ 0.01% | ≤ 0.01% | ≤ 0.01% |
| Phosphorus (P) | ≤ 0.001% | ≤ 0.001% | ≤ 0.001% | ≤ 0.001% | ≤ 0.001% | ≤ 0.001% |
| Ferrum (Fe) | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
Embodiment 1 to the B alloy wire of embodiment 6 detects by an unaided eye：It is its any surface finish, smooth, smooth without joint, without hair
Thorn and interlayer, flawless and folding.Surface is in light light tone, often has more than the tiny cut of dimensional tolerance and affects the oxidation for using
Color.
The line footpath specification and tolerance of the PTC thermistor B alloy wire of embodiment 2 to embodiment 6 with described in table 1, likewise,
During actual production, can be producing the B alloy wire of other line footpath specifications according to specific use demand.
The elongation percentage of the soft state PTC thermistor B alloy wire of embodiment 2 to embodiment 6 is with described in table 2.
Mean temperature coefficient of resistance, the electricity of 0 DEG C of the PTC thermistor B alloy wire of embodiment 1 to embodiment 6～100 DEG C
Resistance rate, the tensile strength of soft state B alloy wire see the table below 4." TCR (average) " refers to 0 DEG C～150 DEG C of average resistance temperature system in table
Number, unit is 10-6/℃；The unit of resistivity is μ Ω m；The unit of the tensile strength of soft state B alloy wire is Mpa.
Table 4
The rice resistance such as table 5 below of the PTC thermistor B alloy wire (soft state) of embodiment 1 to 6：
Table 5, rice resistance
The mean temperature coefficient of resistance of PTC thermistor B alloy wire of the present invention, resistivity and rice resistance form series, full
Composite request of the sufficient electrical apparatus control system to temperature coefficient, resistivity and rice resistance.
It is contemplated that by the PTC thermistor B alloy wire of the present invention according to average resistance temperature system in producing and selling and use
Number is divided into 6 grades, obtains the PTC thermistor B alloy wire of 6 kinds, meets different such as instruments or circuit control system
Requirement.
Mean temperature coefficient of resistance (× 10-6/ DEG C) stepping is as follows：It is first grade 4800～5000, corresponding to have the He of embodiment 1
The PTC thermistor B alloy wire of embodiment 2, the resistivity of this grade is (0.17 ± 0.02) μ Ω m～(0.19 ± 0.02) μ
Ω·m；Second gear 4300～4800, the corresponding PTC thermistor B alloy wire for having embodiment 1 and an embodiment 3, the resistance of this grade
Rate is (0.19 ± 0.02) μ Ω m～(0.27 ± 0.02) μ Ω m；Third gear 4000～4300, it is corresponding to have the He of embodiment 3
The PTC thermistor B alloy wire of embodiment 4, the resistivity of this grade is (0.27 ± 0.02) μ Ω m～(0.36 ± 0.02) μ
Ω·m；Fourth speed 3000～4000, the corresponding PTC thermistor B alloy wire for having embodiment 4 and an embodiment 5, the resistance of this grade
Rate is (0.36 ± 0.02) μ Ω m～(0.40 ± 0.02) μ Ω m；Fifth speed 2500～3000, it is corresponding to have the He of embodiment 5
The PTC thermistor B alloy wire of embodiment 6, the resistivity of this grade is (0.40 ± 0.02) μ Ω m～(0.43 ± 0.02) μ
Ω·m；Sixth speed 2500, the PTC thermistor B alloy wire of correspondence embodiment 6, the resistivity of this grade is (0.43 ± 0.02) μ
Ω·m。
PTC thermistor B alloy wire as heating element heater, with the excellent of its high temperature coefficient of resistance in instrument and meter
Characteristic, makes many-sided functions such as the temperature automatically controlled of instrument, Power auto-adjustment, constant current, current limliting, raising component life more be entered
The lifting of one step.These functions are always the pursuits that instrument and meter industry produces control instrument, it can be said that advocating currently
Under the overall situation of " energy-saving and emission-reduction ", the importance that PTC thermistor B alloy wire is produced to instrument and meter industry control instrument is aobvious
And be clear to.
(embodiment 7, the preparation method of PTC thermistor B alloy wire)
The preparation method of the PTC thermistor B alloy wire of the present embodiment specifically includes following steps：
1. the preparation of raw material：Nickel is No. 1 electrolytic nickel Ni-1 that standard is GB6516；Silicon is the one-level that standard is GB2881
Silicon metal Si-1；Manganese is the electrolytic manganese DJMn99.5 that standard is GB3418；Yttrium is the rare earth metal yttrium Y- that standard is Q/HUAC23
3；Mischmetal is the mixed rare earth Ce-45 that standard is GB/T4153；Ferrum is the pure iron as raw material DT3 that standard is GB/T9971；.
2. vacuum melting：
The equipment that vacuum melting is used is the EG-25 vaccum sensitive stove intermediate frequency machine equipments of Shanghai Electric Furnace Factory's production, wherein:
A. 60 kilowatts of the motor power (output) of frequency converter sets, motor three-phase, 375/750 volt of generator voltage, electronic electromechanics
380/220 volt of source, 50 kilowatts of generator power, 2500 hertz of generator power supply frequency.
B. 350 volts of the induction apparatuss voltage of vacuum melting furnace, 4 liters of crucible volume (magnesia), 1700 DEG C of operating temperature, crucible holds
25 kilograms of amount (magnesia), working chamber's final vacuum 5 × 10-4Millimetres of mercury.
C. liter/second of the booster pump speed of exhaust 1500 of vacuum pump set, liter/second of the mechanical pump speed of exhaust 30, are pressurized pump limit
Vacuum 5 × 10-4Millimetres of mercury, mechanical pump final vacuum 5 × 10-2Millimetres of mercury.
Vacuum Melting is as follows：
A. feed：In nickel that 1. step is prepared, the crucible of ferrum input vacuum melting furnace, remaining trace element material is each
It is placed in hopper and waits to put into；Component ratio of the ratio for feeding intake as required by finished product simultaneously considers the volatilization of its smelting process, loss
Amount.
B. vacuum drying oven is verified before melting, reaches 10-2Millimetres of mercury vacuum begins to warm up after reaching.
C. when material starts fusing in stove, note adjusting power and grate operation to prevent from being splashed when " bridging " and blanking.
D. the trace element in loading hopper is started in stove after nickel, iron charge fine melt, charging sequence is followed successively by Si, Mn, mixes dilute
Soil, Y.Charging finishes rear refine ten minutes, and refining temperature is 1250 ± 20 DEG C.
E. powered cast after calm 7～8 minutes after refine, pouring temperature is 1150 ± 20 DEG C, and the duration of pouring is 3～4 points
Clock, and according to actually carrying out feeding operation.
F. shutdown is poured, furnace cooling more than 10 minutes is come out of the stove after destruction vacuum.
G. spindle puts on product designation and heat (batch) number, and removes analysis sample in cap mouth.
3) standard is examined in founding is：A. composition acceptability limit is met；B. spindle must not surge；C. cap mouth must not it is askew go out ingot
Body；D. spindle must not have overlap to proceed to lower operation.
3. forge hot, to the spindle of gained after step 2. vacuum melting forge hot is carried out, and is required such as using equipment and technological parameter
Under：
A. firing equipment adopts fuel oil reflection heating furnace, hot forging equipment to forge using 750Kg air.
B. forge hot parameter：Alloy heating-up temperature is 1030 ± 20 DEG C, temperature retention time 30～40 minutes, hot stove total heat time heating time
90～120 minutes, after-swage dimension 45 × 45+2 -3Mm, 400～2000mm of length.
C. technological requirement：Open first that furnace temperature is constant in the range of technological requirement before forging；45mm side's forging stock occur crackle or
Other defects, it is general on corner, and at≤5m/m, then permission is wiped off with scraper；Shrinkage cavity should thoroughly cut off totally, and forging stock is most
High flexibility<5mm, forging stock must check end to end, and with a chainsaw saw goes the shrinkage cavity and defect that forge hot stays.
4. hot rolling, by the square forging stock of step 3. gained diameter 7mm～8.8mm wire rods are rolled into, and are joined using equipment and technique
Number requires as follows：
A. heating adopts fuel oil reflection heating furnace, hot rolling to adopt 230 Hot Rolling Mills.
B. Hot Rolling Parameters：Alloy heating-up temperature is 970 ± 30 DEG C, temperature retention time >=30 minute.
C. technological requirement：The wire rod of 7～8.8mm of diameter is rolled into, bar base surface is not allow for the bilateral ears or side handles of a utensil and misalignment ear
Son, bar base two ends must shear totally, be visible by naked eyes hollow and cracking, and bar base surface is not allow for seriously sticking up skin, folding and can
See crackle, bar base substance >=5Kg.
5. anneal, the wire rod obtained by step 4. hot rolling is annealed, required using equipment and technological parameter as follows：
A. annealing device adopts 800 type well formula tempering furnaces, power 60KW, 1000 DEG C of maximum temperature, interior chamber size： Maximum charge weight：500Kg.
B. annealing parameter：Alloy heating-up temperature is 790 DEG C, temperature retention time 80 minutes；Protective atmosphere is argon, and protection is just
Pressure, more than 0.1Mpa, it is desirable to which applying argon gas after first evacuation after charging, heating process wants Jing often to observe the change of furnace pressure and temperature
Change, to remain the malleation (0.1Mpa) in stove.
C. technological requirement：Note charge weight, work loading height can not exceed flat-temperature zone, when cooling charging wants proper extension to be incubated
Between (30 minutes or so), temperature retention time terminates to hang out the pressure that furnace gas is kept after body of heater until furnace shell is cooled to room temperature
When, the opening that just can deflate bell is come out of the stove.
6. the wire rod after 5. annealing to step carries out successively wire drawing and annealing, reciprocal three times：
Ith, first time wire drawing, from 7～8.8mm of diameter diameter 1.37mm is pulled to.
Successively device therefor is as follows for first time wire drawing：
| Device name | Roller diameter | Power of motor | Control linear velocity |
| 450 vertical single die wire drawing machines | Φ450mm | 22KW | 40 ms/min |
| 400 vertical single die wire drawing machines | Φ400mm | 18.5KW | 120 ms/min |
| 300 vertical single die wire drawing machines | Φ300mm | 5.5KW | 80～140 ms/min |
First time wire drawing mould therefor is wolfram steel wire drawing die, and lubricant is vegetable oil, and lubricant is at least changed daily once, with
Ensure cleaning and lubricity.
First time drawing process parameter list：
IIth, anneal for the first time, the alloy of diameter 1.37mm after first time wire drawing is annealed：
A. annealing device adopts 800 type well formula tempering furnaces, power 60KW, 1000 DEG C of maximum temperature, interior chamber size： Maximum charge weight：500Kg.
B. annealing parameter：Alloy heating-up temperature is 850 ± 20 DEG C, temperature retention time 80 minutes；Protective atmosphere is argon, protection
Malleation, more than 0.1Mpa, it is desirable to applying argon gas after first evacuation after charging, heating process wants Jing often to observe furnace pressure and temperature
Change, will remain the malleation (0.1Mpa) in stove.
C. technological requirement：Silk base first rinses greasy dirt and dry well with suds before annealing, charge weight is noted, in order to increase
Strong annealing effect, in furnace bottom about 3 kilograms of industrial Linesless charcoal is put into.Work loading height no more than flat-temperature zone, it is cold enter stove it is appropriate
Extend time of 30 minutes or so, temperature retention time hangs out after terminating will keep the pressure of furnace gas until furnace shell is cooled down after body of heater
During to room temperature, can just deflate, open bell discharging.
IIIth, second wire drawing, from diameter 1.37mm diameter 0.52mm is pulled to.
Second wire drawing device therefor is horizontal multi-die wire drawing water tank drawbench, power of motor 5.5KW, draw line specification Φ
1.8～0.3mm, draws linear velocity≤70 m/min.
Second wire drawing is with lubricator suds, exchanges newly match somebody with somebody daily；Mould is dimond synneusis mould.
Second drawing process parameter：
IVth, anneal for second, the annealing of the B alloy wire of diameter 0.52：
A. annealing device adopts the continuous identical tension bright annealing furnaces of 1#, the use of maximum temperature is 1080 DEG C, warm area length 1.3
Rice, constant speed wheel diameter 110mm, protective atmosphere is hydrogen.
B. annealing parameter：Alloy heating-up temperature is 980～1000 DEG C, and take-up line linear velocity is 15 ms/min；Protective atmosphere is
Reducibility gas hydrogen, flow is used to keep malleation.
C. technological requirement：Control furnace temperature constant homogeneous, adjust in time tensioner to optimum state, and hydrogen keeps malleation,
Keep a close eye on silk material surface-brightening degree not aoxidize, black furnace switches on power again intensifications after leading to hydrogen 15-20 minutes in advance, note often
Axle row's silk is uniform.
Vth, third time wire drawing, the B alloy wire after second is annealed is pulled to 0.20mm from diameter 0.52mm again.
Third time wire drawing device therefor be horizontal multi-die wire drawing water tank drawbench, power of motor 5.5KW, draw line specification Φ
0.3～1.8mm, draws linear velocity≤70 m/min.
Third time wire drawing is with lubricator suds, exchanges newly match somebody with somebody daily；Mould is dimond synneusis mould.
Third time drawing process parameter：
In the first to three drawing process, should be noted：A. in pulling finished goods, to try to draw and measure hard state rice electricity per axle
Resistance, according to the rice resistance corresponding relation of hard state and soft state so as to ensure soft state rice resistance requirement, so as to determining that finished product accounts for mould
Size is finished product line footpath size.Allow≤± 0.02 in the range of adjust.
B. semi-finished product silk table face is not allow for crackle and severe spur, but allows a small amount of slight scuffing, its burr and sticks up
The defects such as skin.
C. finished silk line footpath is in the range of tolerance a line, silk table face typically should be cleaned, light, without severe contamination, must not have
Longitudinal crack and mechanical damage etc., only allow a small amount of burr and little local cut, its depth to allow less than diameter inclined
Difference.
D. the parcels of Φ 0.52 must respectively arrange tie up end to end, must not disarray.Φ 0.20mm top cylinders silks should be arranged substantially
Straight uniform, one wire drawing of finished product is with new polycrystalline diamond mould.
E. finished product should in time be shifted and send annealing, in order to avoid oxidation.
VIth, third time is annealed, the annealing of the B alloy wire of diameter 0.20：
A. annealing device adopts the continuous identical tension bright annealing furnaces of 1#, and maximum operation (service) temperature is 1080 DEG C, warm area length 1.3
Rice, constant speed wheel diameter 110mm, protective atmosphere is hydrogen.
B. annealing parameter：Alloy annealing heating temperature is 980 ± 10 DEG C, and line linear velocity is 15～16 ms/min；Protective atmosphere
It is to use reducibility gas hydrogen, flow keeps malleation.
C. technological requirement：Control furnace temperature constant homogeneous, adjust in time tensioner to optimum state, and hydrogen keeps malleation,
Keep a close eye on silk material surface-brightening degree not aoxidize, black furnace switches on power again intensifications after leading to hydrogen 15-20 minutes in advance, note often
Axle row's silk is uniform, and with the ABS new plastic axles of the special cleaning of finished product, finished product circulates in time censorship, in order to avoid oxidation.
The mechanical performance of the first to third time annealing process and its finished product is expressed as follows table in the present embodiment：
7. finished product detection packaging is dispatched from the factory:
A. check：
1) line footpath and its tolerance, ovality is with reference to GB/T4990 GBs.
2) surface quality, with reference to GB/T4990 GBs.
3) tension test, surveys elongation percentage, with reference to GB228 " metal tensile test method ".
4) resistivity and every meter of resistance value, with reference to GB6146 " precision electrical resistance alloy resistivity measurement method ".
B. temperature-coefficient of electrical resistance test resistance temperature coefficient is measured by the method that GB/T6148 specifies.The measurement per axle.
C. finished product packing dispatches from the factory：Finished product to sending warehouse for finished product test project confirmation item by item after pack, it is qualified
Product are encapsulated with thermoplastic film, in order to avoid making moist, the finished product outer package for sending is firm, are suitable to transport, per single-piece freight weight limit at 25 kilograms
Left and right.
In above-mentioned drawing process, in order to improve the surface quality of silk material, the processing to alloy is optimized.Due to alloy
Plasticity preferably, alloy wire surface quality is easily produced defect by external influence, so change original powdered lubricant, and
With vegetable oil, this not only ensure that surface is difficult injury, it also avoid work in-process and aoxidize because surface is overheated.
For enhanced annealing effect in above-mentioned preparation method, before 800 type well formula tempering furnaces are annealed to crin, in stove
Bottom is put into about 3 kilograms of industrial Linesless charcoal.Linesless charcoal is strong reducing agent, in the carbon that combustion process is produced, can be alloy silk table
Face restores in the nonmetallic inclusion that drawing process is produced, and plays surface cleaning, the effect of light.
In filament continuous annealing in above-mentioned preparation method, in order to improve annealing after silk material uniformity and concordance, it is right
Bright continuous annealing equipment has carried out the transformation of identical tension, and each Wire winding shaft of each annealing furnace has independent equipment to control
Tension force in system and regulation annealing process, so each axial filament is all keeping constant linear speed from empty axle to the overall process of full axle
Degree, it is ensured that the uniformity of silk material.And traditional continuous annealing apparatus are that constant speed is realized with constant speed wheel, but it is just like can not
Many defects such as independent control so that each side's surface uniformity of alloy wire can not be solved very well always.
Claims (4)
1. a kind of PTC thermistor B alloy wire, it is characterised in that the chemical composition and its weight/mass percentage composition of the B alloy wire be：
Nickel 64%～78%, silicon 0.1%～0.60%, manganese 0.22%～0.30%, yttrium 0.02%～0.04%, mischmetal 0.04%～0.06%,
Carbon is less than or equal to 0.05%, sulfur less than or equal to 0.01%, phosphorus less than or equal to 0.001%, balance of ferrum；0 DEG C of B alloy wire～150 DEG C
Mean temperature coefficient of resistance be 4300 × 10-6/ DEG C～4800 × 10-6/ DEG C, the resistivity of B alloy wire is（0.19～0.27）
± 0.02 μ Ω m.
2. a kind of preparation method of PTC thermistor B alloy wire as claimed in claim 1, it is characterised in that including following step
Suddenly：
1. the preparation of raw material；
2. vacuum melting：In nickel that 1. step is prepared, the crucible of ferrum input vacuum melting furnace, remaining trace element material is each
It is placed in hopper and waits to put into；Verifying vacuum drying oven and heating makes to start the trace element in loading hopper after nickel, ferrum fine melt；Charging is finished
Refine afterwards；Calm after refine, then powered cast, pouring temperature is 1130 DEG C～1170 DEG C；Rear furnace cooling is poured, is broken
Come out of the stove after bad vacuum；
3. forge hot is carried out to the spindle of gained after step 2. vacuum melting；Alloy heating-up temperature is 1010 DEG C～1050 DEG C, insulation
30～40 minutes time, hot stove total 90～120 minutes heat time heating times；
4. hot rolling, by step 3. gained square forging stock be rolled into 7 mm of diameter～8.8mm wire rods；
5. anneal, the wire rod obtained by step 4. hot rolling is annealed；
6. the wire rod after 5. annealing to step carries out successively wire drawing and annealing, reciprocal three times, divides 3 times by 7 mm～8.8mm wire rods
Wire drawing is to required B alloy wire diameter；Wherein first time wire drawing mould therefor is wolfram steel wire drawing die, and lubricant is vegetable oil；
First time annealing device adopts 800 type well formula tempering furnaces, and alloy heating-up temperature is 850 ± 20 DEG C during annealing, 80 points of temperature retention time
Clock, protective atmosphere is argon；Second wire drawing device therefor is horizontal multi-die wire drawing water tank drawbench, draw line specification Φ 1.8
～0.3mm, draws linear velocity≤70 m/min, is with lubricator suds, and mould is dimond synneusis mould；Anneal for second
Using continuous identical tension bright annealing furnace, during annealing alloy heating-up temperature be 980～1000 DEG C, take-up linear velocity be 15 meters/
Point, protective atmosphere is to use reducibility gas hydrogen；Third time wire drawing device therefor is horizontal multi-die wire drawing water tank drawbench, is drawn
Line gauge lattice 0.3～1.8mm of Φ, draw linear velocity≤70 m/min, are with lubricator suds, and mould is dimond synneusis mould；
Third time annealing adopts continuous identical tension bright annealing furnace, and alloy annealing heating temperature is 980 ± 10 DEG C, and take-up linear velocity is 15
～16 ms/min；Protective atmosphere is to use reducibility gas hydrogen；
7. finished product detection packaging is dispatched from the factory.
3. the preparation method of PTC thermistor B alloy wire according to claim 2, it is characterised in that：2. vacuum melts step
During refining, the charging sequence of the trace element in hopper is followed successively by silicon, manganese, mischmetal, yttrium.
4. the preparation method of PTC thermistor B alloy wire according to claim 2, it is characterised in that：Step is 6. for the first time
Well formula tempering furnace is adopted during annealing, silk base first rinses greasy dirt and dry well with suds before annealing；The stove of well formula tempering furnace
Place Linesless charcoal in bottom.
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| CN105695795A (en) * | 2016-03-09 | 2016-06-22 | 江阴市诚信合金材料有限公司 | High-strength and low-resistance alloy wire and preparation method thereof |
| CN111041276A (en) * | 2019-12-26 | 2020-04-21 | 江阴市诚信合金材料有限公司 | Easy-to-machine corrosion-resistant constantan alloy wire and production process thereof |
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| CN115261676A (en) * | 2022-07-26 | 2022-11-01 | 北京航玻新材料技术有限公司 | Thermistor alloy, thermistor, manufacturing method of thermistor and glass |
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| CN102352453A (en) * | 2011-10-29 | 2012-02-15 | 重庆川仪自动化股份有限公司 | Resistance material capable of preventing overheat generation caused by excessive current |
| CN102735361A (en) * | 2012-06-13 | 2012-10-17 | 江苏华鑫合金有限公司 | High-precision nickel-chromium/copper-nickel thermocouple alloy wires |
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| CN102352453A (en) * | 2011-10-29 | 2012-02-15 | 重庆川仪自动化股份有限公司 | Resistance material capable of preventing overheat generation caused by excessive current |
| CN102735361A (en) * | 2012-06-13 | 2012-10-17 | 江苏华鑫合金有限公司 | High-precision nickel-chromium/copper-nickel thermocouple alloy wires |
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