CN114783650B - 钛酸锶环形压敏电阻器用底层欧姆银浆及制备方法和应用 - Google Patents
钛酸锶环形压敏电阻器用底层欧姆银浆及制备方法和应用 Download PDFInfo
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- CN114783650B CN114783650B CN202210353067.8A CN202210353067A CN114783650B CN 114783650 B CN114783650 B CN 114783650B CN 202210353067 A CN202210353067 A CN 202210353067A CN 114783650 B CN114783650 B CN 114783650B
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- strontium titanate
- silver paste
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 122
- 239000004332 silver Substances 0.000 title claims abstract description 122
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000003466 welding Methods 0.000 claims abstract description 57
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 22
- 239000011521 glass Substances 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 239000000853 adhesive Substances 0.000 claims abstract description 14
- 230000001070 adhesive effect Effects 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 43
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- 238000000498 ball milling Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 16
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 9
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 9
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002344 surface layer Substances 0.000 claims description 9
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- 239000002893 slag Substances 0.000 claims description 6
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- BVCHZEOVPXACBQ-UHFFFAOYSA-N [Ca][Ba][Sr] Chemical compound [Ca][Ba][Sr] BVCHZEOVPXACBQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
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- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
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- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000001764 infiltration Methods 0.000 description 7
- 230000008595 infiltration Effects 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- 238000007792 addition Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000010892 electric spark Methods 0.000 description 2
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- 238000000227 grinding Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 229910000679 solder Inorganic materials 0.000 description 2
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- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 102220042297 rs587780883 Human genes 0.000 description 1
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
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- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
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- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
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- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
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- H01C17/283—Precursor compositions therefor, e.g. pastes, inks, glass frits
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- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
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Abstract
本发明公开了一种钛酸锶环形压敏电阻器用底层欧姆银浆,其特征在于:所述底层欧姆银浆包括:银粉、掺杂的二氧化锡SnO2微粉、玻璃粉、有机溶剂、有机粘接剂,其质量份数比为[65,85]∶[0.9,4.3]∶[0.5,5]∶[10,20]∶[10,15],还公开了其制备方法和应用,本发明欧姆银浆印刷在具备伏安特性的钛酸锶压敏电阻基片的表面高阻层上,[800,860]℃的空气中的烧结温度,形成了欧姆接触,且电极表面更光亮、致密、平整,满足耐焊、易焊、能承受激光焊接的要求,突破了电压E10值只形成于基片氧化烧结环节的固有模式。
Description
技术领域
本发明涉及半导体功能陶瓷领域,尤其涉及一种钛酸锶环形压敏电阻器用底层欧姆银浆及制备方法和应用。
背景技术
钛酸锶压敏电阻是以钛酸锶为主要原料,模压成型、排胶后,先通过施主掺杂和还原气氛烧结的共同作用,实现晶粒和坯片半导化,再通过受主掺杂和高温氧化的共同作用实现晶界和坯片外层高阻绝缘化,从而制得一种表面层型半导体基片,再丝印、烧渗电极,最后制得同时具备非线性压敏特性和电容特性的双重功能的半导体陶瓷敏感器件。
高温氧化处理后的钛酸锶陶瓷表面存在氧吸附层,是高阻绝缘层,银是稳定贵金属,纯银浆料烧渗形成的电极与钛酸锶半导体陶瓷基片的表面高阻层之间无法实现欧姆接触,为了能够实现欧姆接触,钛酸锶环形压敏电阻的银电极的制备分为底层欧姆浆料的印刷和面层银浆的印刷两部分,欧姆浆料为在银浆中添加还原性强的金属,如金属锌、铝和镍等金属粉,其中还原性金属粉添加量约15~40%;面层银浆为银含量约70%~80%的纯银浆料。
虽然银浆中添加还原性强的金属粉可以使电极与基片之间达到良好的欧姆接触,但是,微米级金属锌、铝和镍在高温空气中极易氧化,因此,钛酸锶环形压敏电阻电极的烧渗温度只能控制在550℃~620℃范围内,烧渗温度再高会使欧姆银浆中的还原性金属氧化而失去欧姆特性,进而钛酸锶环形压敏电阻器的非线性压敏特性无法在与之并联的直流微电机中起作用,所以,表层银电极由于烧结温度无法提高而不能形成致密的银层,因而钛酸锶环形压敏电阻器的电极焊接性能并不十分理想,在微电机焊接装配过程中压敏电阻的电极易出现“烧银层”和“不上锡”的问题。随着高周波焊接和激光焊接等现代化的、高效的、严苛的焊接工艺快速发展,压敏电阻的电极焊接性的耐高温需求越来越强烈,许多钛酸锶环形压敏电阻生厂商采用增加银层厚度的方法,通过印刷多层面银浆来解决压敏电阻银电极焊接不良的问题,这种方法虽然能够暂缓上述问题,却增加了压敏电阻的生产和材料成本。
授权公告号:CN102855960B,一种SrTiO3压敏电阻器用欧姆银浆及其制备方法,将银粉、铝粉或锌粉、玻璃粉、有机粘结剂混合研磨,再加入稀释剂,搅拌均匀,得到SrTiO3压敏电阻器用欧姆银浆。该发明克服了目前国内浆料的欧姆接触差,烧结性能不好等问题,综合性能与国外同类产品相当。但没能满足高温焊接的要求。
授权公告号:CN1629986B,铜电极钛酸锶环形压敏电阻器,产品克服了银电极环形压敏电阻器的“挥银”现象,具有更好的耐焊接性能,但是依然承受不了激光焊接。
在保证良好的欧姆接触性和银电极本身电阻率必须尽量小的条件下,如何改善现有钛酸锶环形压敏电阻的电极的耐高温焊接,解决钛酸锶压敏电阻焊接时烧银、不上锡的现象,是本技术方案将要解决的问题。
用掺杂的二氧化锡SnO2微粉替代强还原性的锌等金属在钛酸锶银浆里的添加,以克服单纯银的稳定性无法在具备伏安特性的环形压敏电阻表面的高阻层上形成欧姆接触的做法,我们还没有看到先例或公开技术。
本技术方案中相关描述的补充定义和说明:
所述焊接是指环形压敏电阻在装机时直流电机电枢绕组上的导线在环形钛酸锶压敏电阻表面电极上的焊接。
所述耐焊易焊是指比现有技术在更短的时间内、更高的温度下完成焊接,能多次承受比常规焊接温度350-380℃要高的380-420℃温度,满足高周波焊接或激光焊接等现代化的、高效的、严苛的焊接要求。
所述丝印为丝网印刷的简称,所述还原气氛为氢气或氮氢混合气氛。
电极与钛酸锶环形压敏电阻器的欧姆接触是指两接触面之间的电阻是个纯电阻常数,其阻值大小不随位置、电流方向、焊接因素的影响,阻值越小越好,该阻值的存在不影响钛酸锶环形压敏电阻器本身的非线性伏安特性。
所述钛酸锶环形压敏电阻器基片的非线性伏安特性可近似地由下公式表示:
I=(U/C)α
式中,I为流过环形压敏电阻器的的电流,U为环形压敏电阻器的两端的电压,C为材料有常数,α为非线性系数且大于1,可由下述公式表示:
α=1/lg(E10/E1)
式中E1、E10值为流经钛酸锶环形压敏电阻器的电流为1mA、10mA时环形压敏电阻器的电压。
所述[65, 85]表示包括端值65、85区间的实数集合,其它同比类推。
发明内容
有鉴于此,本发明的主要目的是在保证电极与钛酸锶压敏电阻基片良好欧姆接触、烧成电极的电阻尽量小的恒定常数的前提下,提出一种钛酸锶环形压敏电阻器用底层欧姆银浆及制备方法和应用,以满足日益苛刻的如激光、高频等焊接,同时有助于提高微电机常规焊接的工作效率。
一种钛酸锶环形压敏电阻器用底层欧姆银浆,其特征在于:所述底层欧姆银浆包括:银粉、掺杂的二氧化锡SnO2微粉、玻璃粉、有机溶剂、有机粘接剂,其质量份数比为[65,85]∶[0.9, 4.3]∶[0.5, 5]∶[10, 20]∶[10, 15]。
进一步,所述掺杂的二氧化锡SnO2微粉为掺杂元素如锑、氟、磷、钨离子的一种或其中两种掺杂的二氧化锡SnO2微粉。
进一步,所述掺杂的二氧化锡SnO2微粉的掺杂为Sb2O3。
进一步,所述掺杂的二氧化锡SnO2微粉中SnO2∶掺杂质量比为[89,99]∶[1,11],两者质量比之和为100。
进一步,所述掺杂的二氧化锡SnO2微粉为球状,中位粒度D50为0.5~3μm。
进一步,所述掺杂的二氧化锡SnO2微粉比表面积为2~50 m2/g,常温下电阻率为0.1~1Ω•cm。
进一步,所述玻璃粉的制备方法为:H3BO3、SiO2、BaCO3、ZnO、Al2O3、Na2CO3、K2CO3 按质量比[20, 60]∶[15, 25]∶[10, 20]∶[15, 20]∶[1, 10]∶[5, 20]∶[1, 10] 混合球磨,在1250℃熔炼2~3h,熔炼后经过水淬得到玻璃渣,将玻璃渣放入球磨罐中,球磨4~24h,过筛,烘干后得到软化点为 635~ 700℃、中位粒度 D50≤ 3μm的玻璃粉。
进一步,所述银粉包括粒径为 [1.0, 2.5]μm球状银微粉A、粒径为 [0.8, 1.0]μm球状银微粉B、粒径为 [0.2,0.8]μm 球状银微粉C,A∶B∶C的质量比为[30, 60]∶[20, 30]∶[5, 10]。
进一步,所述有机粘接剂的制备方法为:准确称量[80, 90]质量份数松油醇、丁基卡必醇中的至少一种加入到制胶机中加热至80℃,加入[10, 20] 质量份数乙基纤维素,控制温度在[90, 95]℃,充分搅拌使混合物形成透明胶状混合液,放入塑料桶或不锈钢桶内自然冷却至室温,所述的有机粘结剂的粘度为400~600dPa.S。
进一步,所述的有机溶剂为松油醇、丁基卡必醇、邻苯二甲酸二丁酯中的一种或两种混合。
进一步,所述底层欧姆银浆的制备方法为:银粉、掺杂的氧化锡SnO2微粉、玻璃粉、有机溶剂、有机粘接剂按质量份数[65, 85]∶[0.9, 4.3]∶[0.5, 5]∶[10, 20]∶[10, 15]配料、球磨、辊压制得。
进一步,所述底层欧姆银浆印刷在具备非线性伏安特性的钛酸锶基片的高阻层表面,空气中烧结,烧结温度为[800, 860]℃。
一种提高钛酸锶环形压敏电阻器耐焊易焊性能的方法,在具备伏安特性的钛酸锶环形压敏电阻器基片上丝印底层欧姆银浆,烘干,在相同位置上再丝印面层银浆,烘干后在空气中烧结成银电极,其特征在于:所述底层欧姆银浆为上所述的任一种钛酸锶环形压敏电阻器用底层欧姆银浆。
进一步,所述钛酸锶环形压敏电阻器基片制备方式包括以下步骤:SrCO3、BaCO3、CaCO3与TiO2按比例配料、球磨混料、干燥、固相合成钛酸锶钡钙粉体;掺杂Nb2O5、La2O3、Ta2O5中的一种或几种与SiO2、MnCO3;球磨、造粒、成型制得钛酸锶钡钙环形压敏电阻器的瓷坯;经排胶、还原烧结、氧化烧结制成具备非线性伏安特性的钛酸锶环形压敏电阻器基片。
进一步,所述面层银浆为银含量百分比[70,80]的银导电浆料。
一种耐焊易焊的环形压敏电阻器,由上述一种提高钛酸锶环形压敏电阻器耐焊易焊性能的方法制得。
有益效果
1. 本技术方案具体实施例800~860℃空气中烧结,添加了掺杂Sb2O3的二氧化锡SnO2微粉的底层欧姆银浆,在银极烧渗过程虽然Sb离子下也存在变价,从Sb2O3到Sb2O4、Sb2O5其一或者共存,无从确认,但从本实施例制成的钛酸锶环形压敏电阻器的各项电气特性都能满足压敏变阻器的各项技术要求的事实可以得知,在直流微电机的外加电压下,足够的载流子浓度迁移克服了单凭银电极导体本身无法逾越的钛酸锶基片表面的高阻层,形成了欧姆接触:电压稳定性好、三极差小;正反方向电压变化小;焊接前后电压变化率小;不同个体间的电压一致性好,详见表2、3。
2. 源于电极烧结温度的差异,现有技术对比例1的银电极表面,无论光泽、致密、平整性都远不如本技术方案,因为其电极烧渗温度只能控制在550℃~620℃范围内,原因在于虽然有机粘接浆料和玻璃浆料的包裹浸润,但是随着烧渗温度的升高,浆料中有机成分的挥发,玻璃浆料在基片上的结合,微米级金属锌、铜、铝和镍在空气中高温极易氧化,若超过750℃后,欧姆接触效果将会变劣;本技术方案具体实施例因掺杂为氧化物、高达800~860℃空气中烧结而成的银电极,银极表面更为细腻、致密,避免了常规550℃~620℃烧成电极中的细微空洞导致焊接牢固性的减弱,可以节约常规电极焊接时间、减小电极厚度,同时与基片的附着效果更好,满足电极剥离强度的要求;在分选、测试、焊接工艺流转过程中不易被摩擦变黑,以上,都为电极的耐焊、易焊、承受激光焊接提供了保障。
本技术方案银极烧渗过程也不需像铜电极烧渗时的充氮气氛保护,节约了生产成本。
3. 实施例1至10添加掺杂Sb2O3的二氧化锡SnO2的做法,量产操作容易,也不增加制作成本。
4. 现有技术钛酸锶压敏电阻的压敏电压来自钛酸锶基片的氧化烧结环节,本技术方案具体实施例相同的目标电压E10值范围的基片氧化时间较对比例都要短,显然银极烧渗工艺环节也贡献了E10目标值一部分的电压值,这是对现有技术工艺预想不到的突破,不仅节约制造工艺能耗,还有助于钛酸锶环形压敏电阻的E10电压的提高,突破现有的E10值规格。详见表4。
为了更好的阐明本发明的技术方案,以下通过具体实施例,结合附图进行详细说明,本技术方案实施例所有具体参数和描述都是为了更好地说明,而不是对本技术方案的技术特征的限制,任何对本技术方案没有超出预期效果的等效替换、重新组合、删减、添加都将落入本技术方案的保护范围。
附图说明
]图1,现有技术和本技术方案工艺流程比较图,流程分支A为本技术方案特有的工艺步骤,底层欧姆银浆添加了掺杂的二氧化锡SnO2微粉,银层烧渗温度为[800, 860]℃、时长为[0.5, 1]小时,流程分支B为现有技术底层欧姆银浆为常规添加强还原性金属Zn、Ni、Al之一,银层烧渗温度为[550, 620]℃,时长[0.5, 1]小时。
图2,Masafumi的导电结构模型,该模型很好解释了钛酸锶环形压敏电阻器的导电机理,一个壳层结构,从外往里依次为,烧渗在钛酸锶表面上的电极1,表面高阻层2,晶界层3,半导化层4。
半导体陶瓷生产工艺的共同特点是必须经过半导化过程,钛酸锶压敏电阻的半导化过程是通过同时掺杂施主:与Ti4+,Sr2+半径相近的异价离子如Nb5+、Ta5+,五价或5价以上离子,如Y3+、La3+、Bi3+,正三价离子取代部分主晶相离子,使晶格产生缺陷,先在还原气氛中烧结造成氧不足,还原气氛和施主态共同作用形成氧空位,氧空位电离产生自由电子,化合物的组成偏离化学计量而达到陶瓷半导化;然后氧化烧结,由于同时掺杂受主如Mn2+、Cu2+,由于氧过剩,氧向钛酸锶表面扩散,从表面向晶界扩散,从表面、晶界向晶粒内部扩散,氧和受主态共同作用捕获自由电子,自由电子被耗,在晶界处形成高阻绝缘层,产生了势垒及电容的双重功能,其发生的几率由表往里越来越小,钛酸锶压敏电阻的高阻层仅仅存在于数十微米的表面层,Masafumi的导电结构模型很好描述了钛酸锶压敏电阻的半导体机理,由外往里依次为耗尽层、晶界层和传导层的导电机理,其电阻值依次为十千欧姆数量级、十欧姆数量级、欧姆数量级。可以看出,压敏电阻E10值电压的控制来源于钛酸锶压敏电阻的基片的氧化过程。相关描述可以详见刘浩杰的硕士学位论文《钛酸锶压敏环形压敏电阻器》。
图3,一种常用规格的钛酸锶环形压敏环形压敏电阻器平放时的俯视图和侧视图,3个银电极A、B、C,烧渗在具备非线性伏安特性的钛酸锶环形压敏电阻基片平面上,基片尺寸规格:φ9.5±0.20×φ5.7±0.20×1.05max,单位mm,其技术要求为E10=17-29V;α值≥2.5;C≤50nF;K≤0.3%/℃;抗折强度≥9.8N;银层剥离强度≥9.8N;表面光滑平整;涂银均匀。
直流微型电机的一个电枢绕组上的导线将分别焊接在压敏电阻相邻的电极上,电机运转时,环形压敏电阻器将依次与直流电机的一个绕组并联,吸收电机因换向产生的高频瞬时反电动势、消灭电火花、降噪、减少电磁干扰。
本技术方案覆盖钛酸锶环形压敏电阻器所有系列规格,例如电极数量包括3极、5极、6极、10极、12极等等,位置可以是上下端面、内外侧面以及上述的不同的组合,电压E10值从1.5~3.5V到60V~100V的系列,尺寸从φ2.5±0.10×φ1.75±0.05×0.45max到φ23.00±0.50×φ15.10±0.50×1.90max的系列,图3只是其中一例。
图4,本技术方案具体实施例1-10产品中任选其一的电极表面扫描电镜图。
图5,现有技术对比例1产品中任选其一产品的电极表面扫描电镜图。
图6,本技术方案具体实施例1-10产品中任选其三的电极激光焊接后结果照片。
图7,对比例1产品中任选其三银电极激光焊接结果照片。
图8,对比例2产品中任选其三铜电极激光焊接结果照片。
具体实施例方式
具体实施例
一种钛酸锶环形压敏电阻器用底层欧姆银浆,包括:银粉、掺杂的二氧化锡SnO2微粉、玻璃粉、有机溶剂、有机粘接剂,其质量份数比为75∶1.125∶5∶10∶10。
所述玻璃粉的制备方法为:H3BO3、SiO2、BaCO3、ZnO、Al2O3、Na2CO3、K2CO3 按质量比20∶20∶14∶19∶2.88∶19∶4.8混合;放入球磨罐中球磨混合4h~24h;再放入氧化铝坩埚中,在高温马弗炉中 1250℃熔炼2~3h;熔炼后经过水淬得到玻璃渣,将玻璃渣放入球磨罐中用滚筒球磨机,去离子水为球磨介质,球磨12~24h,过筛,烘干后得到软化点为 650℃、中位粒度D50≤3μm的玻璃粉。
其中,银粉粒度搭配,包括粒径为 1.0~2.5μm球状银微粉 A、粒径为 0.8~1.0μm球状银微粉 B、粒径为 0.2 ~0.8μm 球状银微粉C,A∶B∶C质量比为60 ∶20 ∶10。
其中,有机溶剂为松油醇、丁基卡必醇按7:3重量比混合。
其中,有机粘接剂的制备,称取40 wt.%的松油醇,40 wt.%丁基卡必醇加入到制胶机中加热至80℃,称取20 wt.%乙基纤维素,控制温度在90℃,充分搅拌2h,形成透明胶状混合液,放入不锈钢桶内自然冷却至室温,制得粘度为450dPa.S的有机粘结剂。
其中掺杂的二氧化锡SnO2微粉为球形、中位粒度D50为0.5~3μm;比表面积为2~50m2/g、电阻率为0.1~1Ω·cm;所述掺杂为Sb2O3,SnO2∶Sb2O3质量比为下表1所示。
如图1工艺流程图A分支所示,本技术方案一种钛酸锶环形压敏电阻器的制备方法,其中底层银浆的制备方法:
制备底层欧姆银浆:上述方法所得的银粉、掺杂的二氧化锡SnO2微粉、玻璃粉、有机溶剂、有机粘接剂按质量比75∶1.125∶5∶10∶10配料,倒入球磨罐中,球磨15~16小时,浆料经三辊机辊轧3~4次得到底层欧姆银浆。
上述方法制得的底层欧姆银浆,经180目丝网印刷在如图3所示规格具备非线性伏安特性的钛酸锶环形压敏电阻器基片上,150~200℃下烘干,在相同位置上再次经250目丝网印刷面层银浆,180~220℃烘干,丝印了银浆的钛酸锶基片放入网带炉中,800~860℃空气中烧结,时长为 0.5~1小时。
所述钛酸锶环形压敏电阻器基片制备方式包括以下步骤:SrCO3、BaCO3、CaCO3与TiO2按比例配料、球磨混料、干燥、固相合成钛酸锶钡钙粉体;掺杂Nb2O5、La2O3、Ta2O5中的一种或几种与SiO2、MnCO3;球磨、造粒、成型制得钛酸锶钡钙环形压敏电阻器的瓷坯;经排胶、还原烧结、氧化烧结制成具备非线性伏安特性的钛酸锶环形压敏电阻器基片。
所述面层银浆为银含量75%的银导电浆料。
如图3所示规格的一种耐焊易焊的环形压敏电阻器,由上述一种提高钛酸锶环形压敏电阻器耐焊易焊性能的方法制得。
对以上钛酸锶环形压敏电阻的相关性能的检测和相关工艺参数的比较,记录于表2、3、4。
按照SnO2∶Sb2O3为95∶5的比例,分别按表5添加掺杂的二氧化锡SnO2微粉占银粉质量比,如上述具体实施例制备一种钛酸锶环形压敏电阻器用底层欧姆银浆,所得银浆印刷在图3规格的具备非线性压敏电阻基片的高阻层表面,烘干、再印刷面层银浆,烘干,烧结,进行与上述条件相同的操作后,检测欧姆接触性能相关参数,结果是三极差E1值不超过1.0V、E10值不超过1.5V;正反方向电压变化E1和E10值不超过0.3V;焊接前后E1值和E10值电压变化率不超过6.5%,依然在图3规格要求的电压范围内,满足欧姆接触要求。
备注:其中1.5的比例相当上具体实施例步骤2中75∶1.125
对比例1
如图1工艺流程图B分支所示,现有技术一种常规钛酸锶环形压敏电阻器制备方法,其中,底层欧姆银浆为市面在售的银含量为55%的欧姆银浆,在银浆中添加还原性强的金属如金属锌、铝、镍之一的金属粉,还原性金属粉添加量约15~40%。
如图3所示规格,在具备伏安特性的钛酸锶环形压敏电阻器基片上经180目丝网印刷现有技术常规的底层欧姆银浆,在150~200℃下烘干,在相同位置上经250目再次印刷面层银浆,180~220℃烘干,丝印了银浆的钛酸锶基片放入网带炉中,600℃烧结,时长为 0.5~1小时。
所述面层银浆为市面上银含量75%的银导电浆料。
对比例2
市面在售铜电极环形压敏电阻,尺寸和电压规格与图3所示一致。
对比例3
与对比例1不同之处是没有印刷现有技术常规的底层欧姆银浆。
具体实施例和3个对比例作如下检测和记录:
1.表2、表3为欧姆特性的检测对比,表中记录数据为各基数500pcs中任选20pcs进行检测所得的平均值。
2.表4为相关制备工艺参数的记录对比。
检测结果分析1
从表2、表3结果可知,本技术方案具体实施例中,电极与钛酸锶环形压敏电阻基片之间都实现了欧姆接触,表现在焊接前后的三极电压变化率、三极差、正反方向电流的极差、α值、都能满足电机使用时对压敏电阻电性能的要求,钛酸锶环形压敏电阻的非线性伏安特性都能正常发挥,和对比例1的在银浆中添加还原性强的金属作为底层欧姆银浆的现有技术做法欧姆接触特性相当,对比例3出现的非欧姆接触的典型缺陷都得以克服,具体实施例都能实现直流微电机运转时高频瞬间的超压保护、吸收换向器产生的电火花、使马达静音,减少电磁干扰的功能,银层剥离强度也符合要求。也可以明显得出结论89∶11以后的比例将使相关参数变恶劣。
备注:表中“无”表示没有检测该数据,因为A-B间的电压已经足以说明问题。
备注:表中三极差为A-B、B-C、C-A三电极电压中最大值减最小值。
检测结果分析2
银极表面电镜图4、5对比后可以清晰发现,较现有技术银电极,本技术方案实施例图4电极烧渗后银极表面晶粒颗粒更大,空洞较少,表面更为平滑、平整,富有更多的光泽,相同的焊接条件下,本技术方案电极在焊接时焊锡将达到更好的流平附着效果,易焊、耐焊,且可以在400℃焊接2s,可重复4次;可以经受激光焊接,且能降低工艺流转过程中银电极表面的磨黑几率。
检测结果分析3
经过对比分析发现,本实施例图6激光焊接后焊锡在电极上的浸润、流平正常,电极光泽依然能保持;图7对比例1现有技术电极中“烧银”“不上锡”现象,无法承受激光焊接,电极和焊锡都有炸裂的现象发生,露出钛酸锶基片;图8,铜电极也是无法承受激光焊接,焊锡和电极都缺失了。
检测结果和分析4
分析表4数据,为实现相同规格的E10值17-29V,实施例1-10基片的氧化时间只需要4.5h,相较对比例现有技术基片的氧化时间节约了超过50%,节约了氧化工艺加工成本;相同的氧化温度和时间9.5h,本技术方案的实施例的成品电压要高,E10值达到了25-34V,显然实施例的烧渗银极工序贡献了一部分E10值,突破了现有技术钛酸锶压敏电阻的E10值只形成于基片的氧化工序的固有模式。
备注:对比例2电极烧渗工艺需在保护气氛中进行。
Claims (14)
1.一种钛酸锶环形压敏电阻器用底层欧姆银浆,其特征在于:所述底层欧姆银浆包括:银粉、掺杂的二氧化锡SnO2微粉、玻璃粉、有机溶剂、有机粘接剂,其质量份数比为[65, 85]∶[0.9, 4.3]∶[0.5, 5]∶[10, 20]∶[10, 15]; 所述掺杂的二氧化锡SnO2微粉的掺杂为Sb2O3;所述掺杂的二氧化锡SnO2微粉中SnO2∶掺杂质量比为[89,99]∶[1,11],两者质量比之和为100。
2.如权利要求1所述的一种钛酸锶环形压敏电阻器用底层欧姆银浆,其特征在于:所述掺杂的二氧化锡SnO2微粉为掺杂元素如锑、氟、磷、钨离子的一种或其中两种掺杂的二氧化锡SnO2微粉。
3.如权利要求1所述的一种钛酸锶环形压敏电阻器用底层欧姆银浆的制备方法,其特征在于:所述掺杂的二氧化锡SnO2微粉为球状,中位粒度D50为0.5~3μm。
4.如权利要求1所述的一种钛酸锶环形压敏电阻器用底层欧姆银浆,其特征在于:所述掺杂的二氧化锡SnO2微粉比表面积为2~50 m2/g,常温电阻率为0.1~1 Ω·cm。
5.如权利要求1所述的一种钛酸锶环形压敏电阻器用底层欧姆银浆,其特征在于:所述玻璃粉的制备方法为:H3BO3、SiO2、BaCO3、ZnO、Al2O3、Na2CO3、K2CO3 按质量比[20, 60]∶[15,25]∶[10, 20]∶[15, 20]∶[1, 10]∶[5, 20]∶[1, 10]混合球磨,在 1250℃熔炼2~3h,熔炼后经过水淬得到玻璃渣,将玻璃渣放入球磨罐中,球磨4~24h,过筛,烘干后得到软化点为635~ 700℃、中位粒度 D50≤ 3μm的玻璃粉。
6.如权利要求1所述的一种钛酸锶环形压敏电阻器用底层欧姆银浆,其特征在于:所述银粉包括粒径为 [1.0, 2.5] μm球状银微粉 A、粒径为 [0.8, 1.0]μm球状银微粉 B、粒径为 [0.2,0.8] μm 球状银微粉C,A∶B∶C的质量比为[30, 60]∶[20, 30]∶[5, 10]。
7.如权利要求1所述的一种钛酸锶环形压敏电阻器用底层欧姆银,其特征在于:所述有机粘接剂的制备方法为:准确称量[80, 90]质量份数松油醇、丁基卡必醇中的至少一种加入到制胶机中加热至80℃,加入[10, 20] 质量份数乙基纤维素,控制温度在[90, 95]℃,充分搅拌使混合物形成透明胶状混合液,放入塑料桶或不锈钢桶内自然冷却至室温,所述的有机粘接剂的粘度为400~600dPa.S。
8.如权利要求1所述的一种钛酸锶环形压敏电阻器用底层欧姆银浆,其特征在于:所述的有机溶剂为松油醇、丁基卡必醇、邻苯二甲酸二丁酯中的一种或两种混合。
9.如权利要求1所述的一种钛酸锶环形压敏电阻器用底层欧姆银浆,其特征在于:所述底层欧姆银浆的制备方法由银粉、掺杂的二氧化锡SnO2微粉、玻璃粉、有机溶剂、有机粘接剂按质量份数比为[65, 85]∶[0.9, 4.3]∶[0.5, 5]∶[10, 20]∶[10, 15]配料、球磨、辊压制得。
10.如权利要求1所述的一种钛酸锶环形压敏电阻器用底层欧姆银浆,其特征在于:所述底层欧姆银浆印刷在具备非线性伏安特性的钛酸锶基片的高阻层表面上,空气中烧结,烧结温度为[800, 860]℃。
11.一种提高钛酸锶环形压敏电阻器耐焊易焊性能的方法,在具备伏安特性的钛酸锶环形压敏电阻器基片上丝印底层欧姆银浆,烘干,在相同位置上再丝印面层银浆,烘干后在空气中烧结成银电极,其特征在于:所述底层欧姆银浆为权利要求1至权利要求10所述的任一种钛酸锶环形压敏电阻器用底层欧姆银浆。
12.如权利要求11所述的一种提高钛酸锶环形压敏电阻器耐焊易焊性能的方法,其特征在于:所述钛酸锶环形压敏电阻器基片制备方式包括以下步骤:SrCO3、BaCO3、CaCO3与TiO2按比例配料、球磨混料、干燥、固相合成钛酸锶钡钙粉体;掺杂Nb2O5、La2O3、Ta2O5中的一种或几种与SiO2、MnCO3;球磨、造粒、成型制得钛酸锶钡钙环形压敏电阻器的瓷坯;经排胶、还原烧结、氧化烧结制成具备非线性伏安特性的钛酸锶环形压敏电阻器基片。
13.如权利要求11所述的一种提高钛酸锶环形压敏电阻器耐焊易焊性能的方法,其特征在于:所述面层银浆为银含量百分比[70,80]的银导电浆料。
14.一种耐焊易焊的环形压敏电阻器,其特征为,由权利要求11所述的一种提高钛酸锶环形压敏电阻器耐焊易焊性能的方法制得。
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CN113345622A (zh) * | 2021-06-28 | 2021-09-03 | 河源市飞利华电子有限公司 | 一种陶瓷基材rfid专用高温烧结银浆及其制备方法 |
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