CN104651667B - PTC thermistor B alloy wire of high temperature coefficient of resistance and preparation method thereof - Google Patents
PTC thermistor B alloy wire of high temperature coefficient of resistance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses PTC thermistor B alloy wire of a kind of high temperature coefficient of resistance and preparation method thereof, the chemical composition and its weight/mass percentage composition of the B alloy wire are：It is iron that nickel 78%~82%, silicon 0.28%~0.60%, manganese 0.30%~0.35%, yttrium 0.02%~0.04%, mischmetal 0.04%~0.06%, carbon, which are less than or equal to 0.05%, sulphur to be less than or equal to 0.01%, phosphorus to be less than or equal to 0.001%, surplus,；The mean temperature coefficient of resistance of 0 DEG C of B alloy wire~150 DEG C 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；The B alloy wire of the present invention is the higher B alloy wire of the temperature-coefficient of electrical resistance being badly in need of at present, and mean temperature coefficient of resistance highest can be to 5000 × 10‑6/ DEG C, the more smart temperature control for meeting emerging electrical equipment is required.
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) thermistor is a kind of with temperature
The semiconductor resistor of sensitiveness is spent, when more than certain temperature (Curie temperature), its resistance value is with the rise of temperature
Almost it is in increasing for phase step type.PTC thermistor can shield when in current surge, excessive, temperature is too high to circuit.
According to the difference of material, PTC thermistor include ceramic PTC thermistor, organic polymer PTC thermistor and
Metal PTC thermistor.
Ceramic PTC thermistor material is with BaTiO3Or SrTiO3Or PbTiO3For the sintered body of main component, wherein mixing
Enter the oxides such as micro Nb, Ta, Bi, Sb, Y, La to carry out valence control and be allowed to semiconducting, generally by this semiconducting
BaTiO3Semiconductor porcelain is referred to as Deng material；Also addition increases Mn, Fe, Cu, Cr of its positive temperature coefficient oxidation simultaneously
Thing and the additive for playing other, make barium titanate etc. and its solid solution half using the shaping of general ceramic process, high temperature sintering
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 general principle is
A kind of balance of energy.Heat is produced when electric current flows through element, a produced heat part is dispersed into environment, one
Divide the temperature for adding macromolecular material.Under operating current, the heat of generation and the heat distributed reach that balanced balanced current can be with
Normal through.When super-high-current by when, element produces substantial amounts of heat and can not timely distributed, and causes macromolecular material
Temperature rises, when temperature reaches material crystalline melt temperature, and 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.It is used as PTC thermistor alloy
It has medium resistivity, and big and positive temperature-coefficient of electrical resistance, its resistance value and temperature are linear, 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.In addition,
PTC thermistor B alloy wire can also be used to make resistance thermometer progress thermometric.
The production of China's PTC thermistor B alloy wire just has started in last century the eighties, but the kind produced 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 thermistor is in recent years
To replace ceramics and organic polymer thermistor extensively, using also having extended.According to the preliminary statistics, only metal PTC is warm at present
There is nearly more than 100 tons of demand in quick electric resistance alloy silk, the whole nation every year, but current domestic 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 do not have also.Due to emerging electric
Equipment needs the resistive element of the control of more smart temperature and regulation, it is necessary to improve the temperature-coefficient of electrical resistance upper limit of resistance wire.
The content of the invention
The technical problems to be solved by the invention be to provide a kind of high temperature coefficient of resistance PTC thermistor B alloy wire and
Its preparation method.
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 are less than or equal to less than or equal to 0.05%, sulphur less than or equal to 0.01%, phosphorus
0.001%, surplus is iron.
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 for 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, sulphur is less than or equal to 0.01%, phosphorus and is less than or equal to 0.001%, surplus when being iron, and 0 DEG C~150 DEG C of B alloy wire are averaged
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 for 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%, sulphur
When being less than or equal to 0.001%, surplus less than or equal to 0.01%, phosphorus for iron, 0 DEG C~150 DEG C of average resistance temperature of B alloy wire
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 aluminium；The chemical composition and its weight/mass percentage composition of above-mentioned B alloy wire are nickel
45%~49%, silicon 0.2%~0.3%, manganese 0.30%~0.35%, yttrium 0.02%~0.04%, mischmetal 0.04%~
0.06%th, aluminium 0.4%~0.5%, carbon be less than or equal to 0.05%, sulphur be less than or equal to 0.01%, phosphorus be less than or equal to 0.001%, it is remaining
When measuring as iron, 0 DEG C~150 DEG C of mean temperature coefficient of resistance of B alloy wire 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, above-mentioned PTC thermistor B alloy wire further can be divided into 6 according to mean temperature coefficient of resistance
Group, so as to obtain the PTC thermistor B alloy wire of 6 kinds, meets different use occasions respectively.
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 small less than or equal to 0.05%, sulphur
When 0.001%, surplus is less than or equal to equal to 0.01%, phosphorus for iron, 0 DEG C~150 DEG C of average resistance temperature system of B alloy wire
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 mentioned component and the PTC thermistor B alloy wire of 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 are 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 small less than or equal to 0.05%, sulphur
When 0.001%, surplus is less than or equal to equal to 0.01%, phosphorus for iron, 0 DEG C~150 DEG C of average resistance temperature system of B alloy wire
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 mentioned component and the PTC thermistor B alloy wire of content is higher, it is adaptable to need above-mentioned resistance temperature
Spend the occasion of coefficient range.And B alloy wire is easy to be processed into filament, the intensity and corrosion resistance of B alloy wire are 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 small less than or equal to 0.05%, sulphur
When 0.001%, surplus is less than or equal to equal to 0.01%, phosphorus for iron, 0 DEG C~150 DEG C of average resistance temperature system of B alloy wire
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
Mentioned component and the PTC thermistor B alloy wire of content are 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 are 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 small less than or equal to 0.05%, sulphur
When 0.001%, surplus is less than or equal to equal to 0.01%, phosphorus for iron, 0 DEG C~150 DEG C of average resistance temperature system of B alloy wire
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
Mentioned component and the PTC thermistor B alloy wire of content are 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 are 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%, aluminium 0.4%~0.5%, carbon are less than
Equal to 0.05%, sulphur be less than or equal to 0.01%, phosphorus to be less than or equal to 0.001%, surplus be iron 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 for (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 are 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%, aluminium 0.45%, carbon are less than or equal to less than or equal to 0.05%, sulphur less than or equal to 0.01%, phosphorus
0.001%th, when surplus is iron, 0 DEG C~150 DEG C of mean temperature coefficient of resistance of B alloy wire 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 are preferable.
The preparation method of above-mentioned PTC thermistor B alloy wire comprises the following steps：
1. the preparation of raw material.
2. vacuum melting：In nickel that 1. step is prepared, the crucible of iron input vacuum melting furnace, remaining micro- 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, iron fine melt；Charging
Refined after finishing；Calm after refining, then powered cast, pouring temperature is 1130 DEG C~1170 DEG C；It is cold with stove after being poured
But, come out of the stove after destruction vacuum.
3. hot forging is carried out to the spindle of gained after step 2. vacuum melting；Alloy heating-up temperature is 1010 DEG C~1050 DEG C,
Soaking time 30~40 minutes, hot stove total 90~120 minutes heat 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. being annealed to step carries out wire drawing and annealing successively, 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 micro- charging sequence in hopper be followed successively by silicon, manganese, mischmetal,
Yttrium.
Well formula tempering furnace is used when 6. above-mentioned steps anneal for the first time, greasy dirt is first rinsed dry by silk base with suds before annealing
It is net and dry；The furnace bottom of well formula tempering furnace places charcoal.
The present invention has positive effect：(1) what PTC thermistor B alloy wire of the invention was wherein constituted by changing matches somebody with somebody
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
Temperature-coefficient of electrical resistance including being badly in need of at present is higher than 3000 × 10-6/ 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 particularly resistance temperature system
What number was mainly determined by alloying component；In the temperature-rise period of PTC thermistor B alloy wire when in use, by outside air or Jie
The influence of matter, can produce oxidation in alloy surface, so that the composition of alloy changes, influence the performance of alloy.
Added in nickel-base alloy after metallic yttrium, metallic yttrium is oxidized in alloy internal priority during heating, 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 purifying alloy.
(3) present invention adds mischmetal in the process of PTC thermistor B alloy wire, it is to avoid metallic nickel is closed
Sulfur corrosion in golden raw material, adds the service life of B alloy wire in a heated condition.
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) be less than or equal to 0.05%, sulphur (S) be less than or equal to 0.01%,
Phosphorus (P) is less than or equal to 0.001%, and surplus is iron (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 resistive element of the control of more smart temperature and regulation, it is necessary to improve resistance wire
The temperature-coefficient of electrical resistance upper limit is to meet requirement.And the control being made up of the PTC thermistor B alloy wire of above-mentioned high temperature coefficient of resistance
Warm instrument can more automatic, effectively, promptly control the operating temperature in industry or 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, has both saved the energy, manpower has been saved again.While the PTC thermistor B alloy wire system of high temperature coefficient of resistance
Into instrument due to current limliting, constant current preferably can be played a part of to whole circuit, greatly reduce the time of electrical equipment at full capacity,
Thus improve resistive element life-span or even the life-span of whole equipment.
In addition, the resistive element that the PTC thermistor B alloy wire of high temperature coefficient of resistance is made also has more preferable power certainly
The function of dynamic regulation；This aspect improves the precision of equipment, and another aspect also has the effect of energy-conservation.
Because the performance particularly temperature-coefficient of electrical resistance of B alloy wire is mainly what is determined by alloying component；PTC thermistor
In the temperature-rise period of B alloy wire when in use, influenceed by outside air or medium, oxidation can be produced in alloy surface, from
And the composition of alloy is changed, influence the performance of alloy.Added in nickel-base alloy after metallic yttrium, metallic yttrium exists during heating
Alloy internal priority is oxidized, and is formed fine and close diffusion trapping layer, is prevented 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 sulphur in the metals such as the nickel in alloy raw material, iron, sulphur can significantly speed up nickel-base alloy
Corrosion rate.Due to the formation of sulfide, make metallic nickel in SO2And CO2Mixed gas in corrosion rate its than
0.1MPad O2In oxidation rate be higher by the 4-6 order of magnitude, this just directly affects the use of B alloy wire 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 added 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 can according to use 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 2-in-1 spun gold of table (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 the net quality of axle such as table 3 below：
The analysis of the present embodiment and the B alloy wire of following examples is carried out as follows with measurement：
A, Chemical bath deposition are according to GB/T 223.25, GB/T 223.62, GB/T 223.68, the chemistry of GB/T 223.69
Analysis method is carried out.
The micrometer that B, line footpath specification and tolerance are not less than 0.001mm with precision is measured.
C, the temperature-coefficient of electrical resistance method as defined in GB/T6148 are measured.
D, resistivity and rice the resistance value method as defined in GB/T6146 are measured.
E, tensile strength and the elongation percentage method as defined in GB/T228 are carried out.
F, surface quality are detected by an unaided eye, examined.
(embodiment 2 to embodiment 6, PTC thermistor B alloy wire)
Embodiment 2 to the chemical composition of the PTC thermistor B alloy wire of embodiment 6 is shown in Table 3 by weight percentage：
The embodiment 1 of table 3 is to embodiment 6
The B alloy wire of embodiment 1 to embodiment 6 detects by an unaided eye：There is no joint, it is its any surface finish, smooth, smooth, it is hairless
Thorn and interlayer, flawless and folding.Surface is in bright color, the oxidation that the tiny cut and influence for often having more than dimensional tolerance are used
Color.
Embodiment 2 to the PTC thermistor B alloy wire of embodiment 6 line footpath specification and tolerance with described in table 1, similarly,
During actual production, the B alloy wire of other line footpath specifications can also be produced according to specific use demand.
Embodiment 2 to the soft state PTC thermistor B alloy wire of embodiment 6 elongation percentage with described in table 2.
0 DEG C~100 DEG C of mean temperature coefficient of resistance of the embodiment 1 to the PTC thermistor B alloy wire of embodiment 6, electricity
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
Mean temperature coefficient of resistance, resistivity and the rice resistance of the PTC thermistor B alloy wire of the present invention 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 is 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 being advocated 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；Iron is the pure iron as raw material DT3 that standard is GB/T9971；.
2. vacuum melting：
Equipment used in vacuum melting is the EG-25 vaccum sensitive stove intermediate frequency machine equipments that Shanghai Electric Furnace Factory produces, 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 inductor 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 iron input vacuum melting furnace, remaining micro- material is each
It is placed in hopper and waits to put into；Component ratio of the ratio fed 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 is begun to warm up after reaching.
C. when material starts fusing in stove, notes that adjustment power and grate operate to prevent from " putting up a bridge " and splash during 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 is refined ten minutes after finishing, and refining temperature is 1250 ± 20 DEG C.
E. powered cast after calm 7~8 minutes after refining, pouring temperature is 1150 ± 20 DEG C, and the duration of pouring is 3~4 points
Clock, and carry out feeding operation according to actual.
F. come out of the stove after being poured shutdown, furnace cooling more than 10 minutes, destruction vacuum.
G. spindle puts on product designation and heat (batch) number, and removes analysis sample in cap mouthful.
3) standard is examined in founding is：A. composition acceptability limit is met；B. spindle must not surge；C. cap mouthful must not it is askew go out ingot
Body；D. spindle must not have overlap to be transferred to lower process.
3. hot forging, hot forging is carried out to the spindle of gained after step 2. vacuum melting, is required such as using equipment and technological parameter
Under：
A. firing equipment uses fuel oil reflection heating furnace, and hot forging equipment is forged using 750Kg air.
B. hot forging parameter：Alloy heating-up temperature is 1030 ± 20 DEG C, soaking time 30~40 minutes, hot stove total heat 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 allow to be wiped off with scraper；Shrinkage cavity should thoroughly be cut off totally, and forging stock is most
High flexibility<5mm, forging stock must be checked end to end, and the shrinkage cavity for going hot forging to leave and defect are sawed with a chainsaw.
4. hot rolling, is rolled into diameter 7mm~8.8mm wire rods by the square forging stock of step 3. gained, uses equipment and technique to join
Number requires as follows：
A. heating uses fuel oil reflection heating furnace, and hot rolling uses 230 Hot Rolling Mills.
B. Hot Rolling Parameters：Alloy heating-up temperature is 970 ± 30 DEG C, soaking time >=30 minute.
C. technological requirement：7~8.8mm of diameter wire rod 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 be sheared 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, require as follows using equipment and technological parameter：
A. annealing device uses 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, soaking time 80 minutes；Protective atmosphere is argon gas, and protection is just
Pressure, more than 0.1Mpa, it is desirable to rear applying argon gas are first vacuumized after charging, heating process will often 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 proper extension insulation is wanted in cooling charging
Between (30 minutes or so), soaking time, which terminates to hang out, will keep the pressure of furnace gas until furnace shell is cooled to room temperature after body of heater
When, the opening that can just deflate bell is come out of the stove.
6. the wire rod after 5. being annealed to step carries out wire drawing and annealing, reciprocal three times successively：
Ith, first time wire drawing, diameter 1.37mm is pulled to from 7~8.8mm of diameter.
Device therefor is as follows successively 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 once daily, 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 uses 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, soaking time 80 minutes；Protective atmosphere is argon gas, protection
Malleation, more than 0.1Mpa, it is desirable to first vacuumize rear applying argon gas after charging, heating process will often 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, about 3 kilograms of industrial charcoal is put into furnace bottom.Work loading height no more than flat-temperature zone, it is cold enter stove it is appropriate
Extension time of 30 minutes or so, soaking time is hung out after terminating will keep the pressure of furnace gas until furnace shell is cooled down after body of heater
It during to room temperature, can just deflate, open bell discharging.
IIIth, second of wire drawing, diameter 0.52mm is pulled to from diameter 1.37mm.
Second of 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 of wire drawing is with lubricator suds, exchanges newly match somebody with somebody daily；Mould is dimond synneusis mould.
Second of drawing process parameter：
IVth, second of annealing, the annealing of the B alloy wire of diameter 0.52：
A. annealing device uses 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 is used, flow keeps malleation.
C. technological requirement：Furnace temperature constant homogeneous is controlled, tensioner is adjusted in time to optimum state, hydrogen keeps malleation,
Keep a close eye on silk material surface-brightening degree not aoxidize, black furnace leads to hydrogen and after 15-20 minute again switched on power heating in advance, notes 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 is 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：
, it is necessary to note in first to three drawing process：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, makes it ensure soft state rice resistance requirement, so as to determine that finished product accounts for mould
Size is finished product line footpath size.Allow to adjust in the range of≤± 0.02.
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 should typically be cleaned, light, without severe contamination, must not have
Longitudinal crack and mechanical damage etc., only allow have a small amount of burr and little local cut, its depth allows inclined no more than diameter
Difference.
D. the parcels of Φ 0.52 must be arranged respectively end to end ties up, and must not disarray.Cylinder silk should be arranged substantially on Φ 0.20mm
Straight uniform, one of wire drawing of finished product is with new polycrystalline diamond mould.
E. finished product should in time shift 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 uses 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
To use reducibility gas hydrogen, flow keeps malleation.
C. technological requirement：Furnace temperature constant homogeneous is controlled, tensioner is adjusted in time to optimum state, hydrogen keeps malleation,
Keep a close eye on silk material surface-brightening degree not aoxidize, black furnace leads to hydrogen and after 15-20 minute again switched on power heating in advance, notes often
Axle row's silk is uniform, with the ABS new plastic axles of the special cleaning of finished product, and finished product circulates censorship in time, in order to avoid oxidation.
First is expressed as follows table to the mechanical performance of third time annealing process and its finished product in the present embodiment：
7. finished product detection packaging is dispatched from the factory:
A. examine：
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 method as defined in GB/T6148 is measured.The measurement per axle.
C. finished product packing dispatches from the factory：Packed after the confirmation item by item for project of being tested to the finished product for sending warehouse for finished product, it is qualified
Product are encapsulated with thermoplastic film, in order to avoid making moist, the finished product external packing sent is firm, suitable for 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 the original powdered lubricant of change, and
With vegetable oil, this not only ensure that surface is difficult injury, it also avoid work in-process because surface is overheated and is aoxidized.
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 charcoal.Charcoal is strong reducing agent, the carbon produced in combustion process, can be alloy silk table
Face is restored in the nonmetallic inclusion that drawing process is produced, and plays surface cleaning, the effect of light.
It is right in order to improve the uniformity and uniformity of silk material after annealing in filament continuous annealing in above-mentioned preparation method
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 is 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 of high temperature coefficient of resistance, it is characterised in that the chemical composition of the B alloy wire and
Its weight/mass percentage composition is：Nickel 78%~82%, silicon 0.28%~0.60%, manganese 0.30%~0.35%, yttrium 0.02%~0.04%, mixing
It is iron that rare earth 0.04%~0.06%, carbon, which are less than or equal to 0.05%, sulphur to be less than or equal to 0.01%, phosphorus to be less than or equal to 0.001%, surplus,；
The mean temperature coefficient of resistance of 0 DEG C of B alloy wire~150 DEG C is 4800 × 10-6/ DEG C~5000 × 10-6/ DEG C, the electricity of B alloy wire
Resistance rate is（0.17~0.19）± 0.02 μ Ω m.
2. a kind of preparation method of the PTC thermistor B alloy wire of high temperature coefficient of resistance as claimed in claim 1, its feature
It is to comprise the following steps：
1. the preparation of raw material；
2. vacuum melting：In nickel that 1. step is prepared, the crucible of iron input vacuum melting furnace, remaining micro- 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, iron fine melt；Charging is finished
After refine；Calm after refining, 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. hot forging 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 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. being annealed to step carries out wire drawing and annealing successively, 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 uses 800 type well formula tempering furnaces, and alloy heating-up temperature is 850 ± 20 DEG C, 80 points of soaking time during annealing
Clock, protective atmosphere is argon gas；Second of 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；Second of annealing
Using continuous identical tension bright annealing furnace, alloy heating-up temperature is 980~1000 DEG C during annealing, and take-up linear velocity is 15 ms/min,
Protective atmosphere is to use reducibility gas hydrogen；Third time wire drawing device therefor is horizontal multi-die wire drawing water tank drawbench, draw line
Specification 0.3~1.8mm of Φ, draw linear velocity≤70 m/min, are with lubricator suds, and mould is dimond synneusis mould；The
Three times annealing use continuous identical tension bright annealing furnaces, alloy annealing heating temperature be 980 ± 10 DEG C, take-up linear velocity be 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 micro- charging sequence 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 6. for the first time
Well formula tempering furnace is used during annealing, silk base first rinses greasy dirt and dry well with suds before annealing；The stove of well formula tempering furnace
Place charcoal in bottom.
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| 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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| 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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