CN101067201A

CN101067201A - Method for promoting preprocessing of copper-clad zirconium tungstate composite powder

Info

Publication number: CN101067201A
Application number: CN 200710023649
Authority: CN
Inventors: 严学华; 程晓农; 王春生; 邱杰; 张成华
Original assignee: Jiangsu University
Current assignee: Jiangsu University
Priority date: 2007-06-12
Filing date: 2007-06-12
Publication date: 2007-11-07

Abstract

The present invention relates to powder coating technology, and is especially pre-treatment process for promoting cladding of zirconium tungstate (ZrW2O8) powder with copper. The micron level ZrW2O8 powder is surface roughened, sensitized and activated before it is clad chemically with copper powder under the irradiation of ultrasonic wave. The present invention makes it possible to clad ZrW2O8 powder easily with compact copper layer to prepare composite powder, and has simple technological process and high cladding effect, and the composite powder may be used in be used in producing substrate of SLSI and electronic device.

Description

Promote the pretreatment process of copper-clad zirconium tungstate composite powder

Technical field

Patent of the present invention relates to the pretreatment process that powder coats, and refers in particular to and adopts step sensitization activation wolframic acid zirconium powder surface, impels on difform wolframic acid zirconium powder surface the method that can Fast Packet be covered with copper particle.

Background technology

In recent years, the Sleight A.W of U.S. Oregon State University professor ^[1-4]Deng having found very strong " negative expansion " (Negative Thermal Expansion, be called for short NTE) effect in tungsten (molybdenum) hydrochlorate, phosphorus (vanadium) hydrochlorate, wherein most important material is a cube ZrW ₂O ₈, this material has very strong isotropy negative expansion effect, its negative expansion coefficient α～-8.7 * 10 in 0.3～1050K temperature range ^-6K ^-1[1-4].ZrW ₂O ₈The material of this good NTE performance has many potential Application Areass [5], pays close attention to widely so cause Chinese scholars.It both can be separately uses as structured material, also can be controlled with the compound preparation thermal expansivity of other materials or the matrix material of zero thermal expansion.Because copper has very high electroconductibility, thermal conductivity, solidity to corrosion and good processing performance, so adopt suitable preparation technology, utilizes high conduction, heat conductivility and the ZrW of Cu ₂O ₈The negative expansion performance compound, thereby the ZrW of synthetic high heat conduction, high conduction, low bulk ₂O ₈/ Cu matrix material becomes ZrW ₂O ₈A hot research direction in application facet.This matrix material all has important application in fields such as microelectronics, transmitter, aerospace, engine parts and precision optical machineries.

Metallographic phase and ceramic phase interfacial bonding property and dispersing uniformity are relatively poor, can solve by optimal preparation technology.Many Materials science investigators discover, the powder process stage is particularly important for the influence of the compactness of metal-base composites and phase dispersing uniformity.Adopt the method that coats to prepare composite ceramic material, can improve dispersing characteristic, improve the uniform mixing degree of metallographic phase/ceramic phase, improve sintering metal interfacial bonding property matter.

Adopt the synthetic ZrW of isostatic cool pressing method ₂O ₈/ Cu composite block material has had report [6-9] at present, but this class complex material also has problems to solve.In addition, the hole has equaled to propose in 2000 to adopt chemical plating technology to prepare fine and close ZrW on the sunny side ₂O ₈/ Cu composite granule [10].But do not relate to the detailed powder pretreatment process and the composition of chemical plating fluid in its patent, and adopt chemical plating method to prepare the copper-clad zirconium tungstate powder emphatically, after mixing up micro-superfine graphite C powder again, adopt cold isostatic compaction+microwave sintering process, thereby obtain ZrW ₂O ₈/ Cu matrix material.Here we develop a kind of ZrW that can promote different shape ₂O ₈Powder surface can both coat the pretreatment process of copper rapidly, and the acquisition of this kind method can more easily obtain copper-clad zirconium tungstate composite powder.

Reference:

1.T.A.Mary，J.S.O.Evans，T.Vogt，A.W.Sleight，Negative?Thermal?Expansion?from?0.3?to?1050?Kelvin?inZrW ₂O ₈，Science，1996，Vol?272，90～92

2.J.S.O.Evans，Z.Hu，J.D.Jorgensen，D.N.Argyriou，S.Short，A.W.Sleight，Compressibility，Phase?Transition，and?Oxygen?Migration?in?Zirconium?Tungstate，ZrW ₂O ₈，Science，1997，Vol?275，61～65

3.C.A.Perottoni，J.A.H.da?Jornada，Pressure-Induced?Amorphization?and?Negative?Thermal?Expansion?inZrW ₂O ₈，Science，1998，Vol?280，886～889

4.G.Ernst，C.Broholm，G.R.Kowach，A.P.Ramirez，Phonon?density?of?states?and?negative?thermal?expansion?inZrW ₂O ₈，Nature，1998，Vol?396，147～149

5.J.S.O.Evans，W.I.F.David，A.W.Sleight，Structural?investigation?of?the?negative-thermal-expansionmaterial?ZrW ₂O ₈，Acta?Crystallographica?Section?B：Structural?Science，1999，55(3)，333-340

6.Dorian?K.Balch，David?C.Dunand，Copper-zirconium?tungstate?composites?exhibiting?low?and?negativethermal?expansion?influenced?by?reinforcement?phase?transformations，Metallurgical?and?materialstransactions?A，2004，35A(3)，1159-1162

7.Yilmaz?S.，Dunand?D.C.，Finite-element?analysis?of?thermal?expansion?and?thermal?mismatch?stresses?in?aCu-60Vol％?ZrW ₂O ₈?composite，Composites?science?and?technology，2004，64(12)，1895-1898

8.Yilmaz?S.，Thermal?mismatch?stress?development?in?Cu-ZrW ₂O ₈?composite?investigated?by?synchrotronX-ray?diffraction，Composites?science?and?technology，2002，62(14)，1835-1839

9.Hermann?H.，Davide?C.D.，Phase?transformation?and?thermal?expansion?of?Cu-ZrW ₂O ₈?metal?matrixcomposite，J.Mater.Res.，1999，14(3)，780-789

10. the hole faces south, Ceng Zhenpeng, Wu Jiansheng, high-thermal-conductivity low-expansibility compound material and preparation technology thereof, Shanghai Communications University, national inventing patent publication number CN1262336

Summary of the invention

The purpose of this invention is to provide a kind of promotion copper at different shapes ZrW ₂O ₈Powder surface coats the pretreatment process of Cu, with easily, synthesize ZrW fast ₂O ₈/ Cu composite granule.

The objective of the invention is to come pre-treatment ZrW with following flow process ₂O ₈Powder surface is realized:

(1) alligatoring: take by weighing ZrW ₂O ₈Powder heats about 30～60min, cleaning-drying simultaneously with the concentrated nitric acid magnetic agitation.

(2) one steps sensitization activation:, handle 10g ZrW by every 100ml sensitization activation solution to the powder pre-treatment after the alligatoring ₂O ₈Powder, sensitizing solution are reused three times at most, because the Pd ion in solution of every sensitization activation has reduced, and cleaning-drying behind sensitization activation 30～50min.Being formulated as follows of every liter of sensitization activation solution: 0.3g～0.4gPdCl ₂60ml HCl; 30～40g SnCl ₂140g～160g NaCl.

The preparation method of above-mentioned sensitization activation solution is: at first the PdCl that weighs up ₂Be dissolved in the hydrochloric acid, obtain solution I, NaCl is dissolved in obtains solution II in the distilled water again, mixed solution I, II obtain solution III, then SnCl ₂Be dissolved in the distilled water, obtain solution IV, the solution III for preparing is added in the solution IV adding distil water.

(3) preparation plating bath: by every liter, plating bath is composed as follows: main salt copper sulfate (CuSO ₄5H ₂O) 15～42g; Reductive agent formaldehyde (HCHO) 12～40ml; Complexing agent EDTA-2Na 44～66g; Stablizer yellow prussiate of potash 20mg; 2-2 ' dipyridyl 20mg; Short solvating agent methyl alcohol (CH ₃OH) 100ml; Adjusting to plating bath to pH value with sodium hydroxide (NaOH) is 12～13.

The unstable easily generation of preparation plating bath is decomposed needs matching while using.Take by weighing complexing agent EDTA-2Na limit heating edge magnetic agitation and make it to be dissolved in distilled water, turn off heater switch, obtain solution V.Take by weighing main salt CuSO ₄5H ₂O dissolves distilled water, obtains solution VI, VI is added among the V continues to stir, and obtains solution VII, takes by weighing yellow prussiate of potash and 2-2 ' dipyridyl (bistable agent) respectively and is added to and obtains solution VIII among the solution VII.Take by weighing NaOH and be dissolved in distilled water, wait the interpolation methyl alcohol that cools down, add formaldehyde then, obtain solution I X, then solution I X is added among the solution VIII to obtaining plating bath.

(4) take by weighing the ZrW that the sensitization of 2.5～10g/L activated ₂O ₈Powder adds in the plating bath, through supersound process 30～45min, ZrW ₂O ₈Powder surface will the plating layer of copper.

By the enforcement of present method, make Cu coat ZrW ₂O ₈Have following several characteristics in the preparation process of composite granule: (1) can disposable as required a large amount of processing ZrW ₂O ₈Powder; (2) can handle the ZrW of different shape, particle diameter ₂O ₈Powder; (3) whole electroless plating treating processes is short, and covered effect is good.

Description of drawings

Fig. 1 process flow diagram of the present invention

Fig. 2 Cu coats ZrW ₂O ₈The XRD figure spectrum (a) of composite granule does not add stablizer, (b) bistable agent

Fig. 3 Cu coats ZrW ₂O ₈The SEM figure of composite granule

Fig. 4 composite granule EDS collection of illustrative plates

Embodiment

Further specify effect of the present invention below by specific embodiment.

Its sensitization activation solution of embodiment 1:(is got 200ml; Plating bath is got 200ml)

(1) alligatoring: take by weighing prepared ZrW ₂O ₈Powder heats about 30min, cleaning-drying simultaneously with the concentrated nitric acid magnetic agitation.

(2) one steps sensitization activation: the 0.06gPdCl that weighs up ₂Be dissolved in the 15ml hydrochloric acid, obtain solution I, 28gNaCl is dissolved in the 100ml distilled water obtains solution II again, mixed solution I, II obtain solution III, then 6.5gSnCl ₂Be dissolved in the 70ml distilled water, obtain solution IV, the solution III for preparing is added in the solution IV, adding distil water is to 200ml.Handle the 10g inorganic powder by every 100ml sensitization activation solution, sensitizing solution is reused three times at most, because the Pd ion in solution of every sensitization activation has reduced.Cleaning-drying behind the sensitization activation 30min.

(3) plating bath: take by weighing 9g complexing agent EDTA-2Na heating magnetic agitation and be dissolved in distilled water, turn off heater switch, obtain 100ml solution V.Take by weighing 5g master's salt CuSO ₄5H ₂O is dissolved in distilled water, obtain 40ml solution VI, VI is added to continues among the V to stir, obtain solution VII, taking by weighing the yellow prussiate of potash of 2～3mg and 2-2 ' dipyridyl respectively is added to and obtains solution VIII among the solution VII, take by weighing 5gNaOH dissolving 30ml distilled water, waiting cools down adds 20ml methyl alcohol, adds the formaldehyde of 3.5ml then, obtain solution I X, then solution XI is added among the solution VIII to obtaining plating bath, adding distil water is to 200ml, and the pH value of plating bath is 12.

(4) take by weighing the pretreated ZrW of 0.9g ₂O ₈Powder adds in the plating bath, and this beaker is put into the ultrasonic cleaning machine, under action of ultrasonic waves, and through 30min, ZrW ₂O ₈Powder surface will the plating layer of copper.

Its sensitization activation solution of embodiment 2:(is got 500ml; Plating bath is got 500ml)

(1) alligatoring: take by weighing prepared ZrW ₂O ₈Powder heats about about 60min cleaning-drying simultaneously with the concentrated nitric acid magnetic agitation.

(2) one steps sensitization activation: at first the 0.2gPdCl that weighs up ₂Be dissolved in the hydrochloric acid, obtain solution I, 80gNaCl is dissolved in the 250ml distilled water obtains solution II again, mixed solution I, II obtain solution III, then 20gSnCl ₂Be dissolved in the 200ml distilled water, obtain solution IV, the solution III for preparing is added in the solution IV, adding distil water is to 500ml.Handle the 10g inorganic powder by every 100ml sensitization activation solution, sensitizing solution is reused three times at most, because the Pd ion in solution of every sensitization activation has reduced.Cleaning-drying behind the sensitization activation 50min.

(3) plating bath: take by weighing 20g complexing agent EDTA-2Na heating magnetic agitation and be dissolved in distilled water, turn off heater switch, obtain 250ml solution V.Take by weighing 13g master's salt CuSO ₄5H ₂O is dissolved in distilled water, obtain 100ml solution VI, VI is added to continues among the V to stir, obtain solution VII, taking by weighing the yellow prussiate of potash of 6～8mg and 2-2 ' dipyridyl respectively is added to and obtains solution VIII among the solution VII, take by weighing 12gNaOH and be dissolved in 90ml, waiting cools down adds 50ml methyl alcohol, adds the formaldehyde of 9ml then, obtain solution I X, then solution I X is added among the solution VIII to obtaining plating bath, adding distil water is to 500ml, and the pH value of plating bath is 13.

(4) take by weighing the pretreated ZrW of 2.5g ₂O ₈Powder adds in the plating bath, and this beaker is put into the ultrasonic cleaning machine, under action of ultrasonic waves, and through 45min, ZrW ₂O ₈Powder surface will the plating layer of copper.

With the phase structure (Fig. 2) of x-ray powder diffraction instrument working sample, pattern of sem observation sample (Fig. 3) and energy spectrum analysis (Fig. 4) institute synthetic composite granule.The result shows: its composite granule is at ZrW ₂O ₈Powder can coat the copper of last layer successive, densification, and covered effect is good.

Claims

1, promote the pretreatment process of copper-clad zirconium tungstate composite powder, it is characterized in that, carry out according to following steps:

(1) alligatoring: take by weighing ZrW ₂O ₈Powder heats about 30～60min, cleaning-drying simultaneously with the concentrated nitric acid magnetic agitation;

(2) one steps sensitization activation:, handle 10g ZrW by every 100ml sensitization activation solution to the powder pre-treatment after the alligatoring ₂O ₈Powder, cleaning-drying behind sensitization activation 30～50min, being formulated as follows of every liter of sensitization activation solution: 0.3g～0.4gPdCl ₂60ml HCl; 30～40g SnCl ₂140g～160g NaCl;

(3) preparation plating bath: by every liter, plating bath is composed as follows: main salt copper sulfate (CuSO ₄5H ₂O) 15～42g; Reductive agent formaldehyde (HCHO) 12～40ml; Complexing agent EDTA-2Na 44～66g; Stablizer yellow prussiate of potash 20mg; 2-2 ' dipyridyl 20mg; Short solvating agent methyl alcohol (CH ₃OH) 100ml; Adjusting to plating bath to pH value with sodium hydroxide (NaOH) is 12～13;

2, the pretreatment process of the described promotion copper-clad zirconium tungstate composite powder of claim 1 is characterized in that: the preparation method of the sensitization activation solution in the step (2) is: at first the PdCl that weighs up ₂Be dissolved in the hydrochloric acid, obtain solution I, NaCl is dissolved in obtains solution II in the distilled water again, mixed solution I, II obtain solution III, then SnCl ₂Be dissolved in the distilled water, obtain solution IV, the solution III for preparing is added in the solution IV adding distil water.

3, the pretreatment process of the described promotion copper-clad zirconium tungstate composite powder of claim 1, it is characterized in that: the preparation method of plating bath is in the step (3): take by weighing complexing agent EDTA-2Na limit heating edge magnetic agitation and make it to be dissolved in distilled water, turn off heater switch, obtain solution V, take by weighing main salt CuSO ₄5H ₂O dissolves distilled water, obtain solution VI, VI is added to continuation stirring among the V, obtain solution VII, take by weighing yellow prussiate of potash and 2-2 ' dipyridyl (bistable agent) respectively and be added to and obtain solution VIII among the solution VII, take by weighing NaOH and be dissolved in distilled water, Deng the interpolation methyl alcohol that cools down, add formaldehyde then, obtain solution I X, then solution I X is added among the solution VIII to obtaining plating bath.

4, the pretreatment process of the described promotion copper-clad zirconium tungstate composite powder of claim 2 is characterized in that: sensitizing solution is reused at most three times.