CN103668419A - Device and method for reducing production of tin sludge in preparation process of tin plating solution - Google Patents
Device and method for reducing production of tin sludge in preparation process of tin plating solution Download PDFInfo
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- CN103668419A CN103668419A CN201210315873.2A CN201210315873A CN103668419A CN 103668419 A CN103668419 A CN 103668419A CN 201210315873 A CN201210315873 A CN 201210315873A CN 103668419 A CN103668419 A CN 103668419A
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Abstract
The invention relates to a device for reducing the production of tin sludge in preparation process of a tin plating solution and a method for reducing the production of the tin sludge in the preparation process of the tin plating solution by applying the device. Under the situation of not increasing additional equipment, a design scheme of a porous mesh plate is provided for ensuring that tin particles in a tin dissolving tank are in an ideal fluidized state, namely the tin particles are in a free flow state in the dissolving tank, and the tin particles are fully mixed with the tin plating solution containing dissolved oxygen to avoid the occurrence of local excess oxygen. In addition, the quantity of the tin particles in a mixing chamber is simultaneously increased, and the excess tin particles are used to ensure that oxygen can not be excess at the maximum tin dissolving rate; simultaneously, the production of the tin sludge is reduced to a relatively low level through the reasonable mixture ratio of components in the tin plating solution.
Description
Technical field
The present invention relates to a kind of device, particularly, relate to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process, simultaneously, the invention still further relates to a kind of method that described device reduces tin mud generation in tin plating electrolyte preparation process of applying, be applied to the plating solution preparation of insoluble anode.
Background technology
The mode of production of commodity electrolytic tinplate is divided into two kinds: a kind of is to use insoluble anode to carry out eleetrotinplate, and a kind of is to use solubility tin anode to carry out eleetrotinplate.Adopt insoluble anode, because anode electrode does not dissolve, can make the distance of anode and plated steel band remain unchanged, thereby the thickness of coating is more even.Simultaneously the life-span of insoluble anode, about 10 months, has so just been avoided the impact of the open severe operating environment in the heavy manual work that soluble anode must every class replacing and the scene of bearing.
Adopt the method for insoluble anode eleetrotinplate and the maximum of soluble anode not to be both that insoluble anode is zinc-plated must have one to carry out device prepared by tin plating electrolyte.This is the process of a chemical dissolution tin, accelerates tin be oxidized to Sn by oxygen blast
2+, but unavoidably will produce Sn
4+, i.e. tin mud.
Device prepared by tin plating electrolyte is that an inner filling has metallic tin particle, has plating solution flow at high speed and be blown into oxygen to make tin that the metallic tin dissolving vessel dissolving occur.When metallic tin particle runs into oxygen, its surface will generate tin protoxide, the H in tin protoxide and tin plating electrolyte
+reaction just generates the divalent tin ion that we need.Excessive dissolved oxygen can react with tin protoxide again and generate stannic oxide, and because stannic oxide is insoluble, so just become the mud in tin plating electrolyte, its existence not only can affect the quality of plating, is also a kind of manifestation of tin resource loss simultaneously.
Soluble anode eleetrotinplate is owing to not having this tin particle and the mandatory of oxygen to contact, and in the tin mud that it produces, the content of tin generally accounts for 0.5 ~ 1.5% (tin/dissolving tin that Xi Nizhong contains) of the usage quantity of total tin metal, and insoluble anode is 4 ~ 12%.Therefore, the tin mud loss of reduction insoluble anode eleetrotinplate just becomes a kind of pursuit of this technology.Also be the reason that current insoluble anode eleetrotinplate technology is not used widely.
In fact, the source of tin mud is caused by the reason of two aspects, and the one, in the exclusive tin process processed that insoluble anode technique faces, tin ion and the mandatory of purity oxygen contact; Be the eleetrotinplate process that these two kinds of techniques all will be faced on the other hand, the process of plating can produce oxygen, and simultaneously because tin plating electrolyte is to move in the groove tank of opening, in the process of electroplating, will certainly contact with air, and the process of therefore electroplating also can produce tin mud.The tin wastage rate that all its soluble anode eleetrotinplates of business-like zinc-plated production line produce are in the world that the per-cent that the content of tin in tin mud accounts for the usage quantity (consumption of the tin ÷ metallic tin that Xi Nizhong contains) of total tin metal is 0.5 ~ 1.5%, and insoluble anode eleetrotinplate is owing to also having a tin process processed, the per-cent of usage quantity that in all tin mud, the content of tin accounts for total tin metal is 4 ~ 12%.Therefore, the tin mud loss of reduction insoluble anode eleetrotinplate just becomes a kind of pursuit of this technology.Also be the reason that current insoluble anode eleetrotinplate technology is not used widely.
For the tin protoxide suppressing in tin dissolving vessel is further oxidized to stannic oxide precipitation and generates tin mud in plating solution, mainly there is at present following patent documentation:
Patent documentation 1: 3-No. 180493 communiques of Unexamined Patent have proposed metal ion to carry out mechanical stirring to accelerate the dissolution rate of tin, thereby reduce the generating capacity of tin mud.In fact, churned mechanically Main Function is that tin particles and the oxygen being blown into and mobile tin plating electrolyte are evenly mixed more fully.The method has increased facility investment, and meanwhile, in the situation that tin particles dissolving vessel has very large pressure, agitator turning axle just seems very important through the dynamic seal at dissolving vessel position, and under continuous duty, the reliability of normal work is difficult to guarantee.The agitator increasing has also increased the extra consumption of the energy.
Patent documentation 2: it is the electroplate liquid below 300ppm that Unexamined Patent-No. 131399 communique proposition is supplied with dissolved oxygen to the metallic tin particle in mixing section, reduces the generating capacity that reduces tin mud of excess of oxygen situation.Patent documentation 3:CN1993502A provides a kind of tin ion concentration has been controlled between target bound, thereby makes tin ion formation speed approach the average predetermined spending rate of tin ion, thereby can reduce the method for the generation of tin mud.The method is when adjusting the amount of being blown into of oxygen, according to the travelling speed of steel band, calculating the predetermined spending rate of tin ion measures over time, every the scheduled time, described tin ion formation speed is divided, by the interval in each division the tin ion formation speed of equalization be set as on average measuring over time, with this, adjust the amount of being blown into of oxygen, the average over time tin ion concentration that amount adapts is become and be no more than the tin ion formation speed of controlling target bound.Above-mentioned two patent documentations are all from how reducing the excessive oxygen amount of being blown into, to start with to reduce the generation of tin mud, but method is loaded down with trivial details and control method is complicated, and control accuracy is had relatively high expectations, and implement difficulty larger.
Summary of the invention
For solving the problem of above-mentioned existence, the object of the present invention is to provide a kind of device for reducing tin mud generation in tin plating electrolyte preparation process, a kind of and method of applying tin mud generation in described device reduction tin plating electrolyte preparation process, in the situation that not increasing extras, provide the design of a porous web plate to guarantee that the tin particles in tin dissolving vessel can be in desirable fluidized state, be tin particles in dissolving vessel in a kind of free-pouring state, fully mix with the tin plating electrolyte that contains dissolved oxygen, avoid the generation of local excess of oxygen.Increase in addition the amount of tin particles in mixing section simultaneously, with excessive tin particles, guarantee that under maximum molten tin rate behavior, oxygen can be inexcessive yet, meanwhile, by the proportioning of rational tin plating electrolyte component, make tin mud generation be reduced to a lower level.
For achieving the above object, the present invention mainly adopts following technical scheme:
For reducing a device for tin mud generation in tin plating electrolyte preparation process, described device comprises that eleetrotinplate unit and tin dissolve unit,
Described eleetrotinplate unit comprises plating tank, and described plating tank one end is connected with the 3rd valve with the second recycle pump respectively by pipeline;
Described tin dissolves unit and comprises tin dissolving vessel, described tin dissolving vessel forms closed connection by pipeline and oxygen supply device, the first recycle pump, plating solution storage tanks and the first valve, and described tin dissolving vessel comprises separate chamber, mixing section and the distributing chamber setting gradually;
Described plating tank is connected with plating solution storage tanks by pipeline, and described the second recycle pump is connected with plating solution storage tanks by the 4th valve afterwards with the 3rd valve parallel connection, it is characterized in that:
Between described mixing section and distributing chamber, be provided with porous web plate, described porous web plate comprises the first web plate and the second web plate.
According to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, employing, is provided with the 3rd tensimeter between described distributing chamber and oxygen supply device.
According to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, what adopt is, described mixing section is connected with the first pressure warning unit, between described separate chamber and the first valve, be provided with the second pressure warning unit, between described separate chamber and the first valve, be also provided with under meter.
According to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, employing, is also provided with the second valve between described oxygen supply device and plating solution storage tanks, and described the second valve and the first recycle pump form and be connected in parallel.
According to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, what adopt is, described the second web plate is arranged at the first web plate top, described the first web plate thickness is 20 ~ 30mm, aperture is 6 ~ 8mm, percentage of open area is 28 ~ 32%, and described the second web plate thickness is 2 ~ 5mm, and aperture is greater than 0 and be less than 2.5mm.
According to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, employing, is bolted between described the first web plate and the second web plate.
Meanwhile, the present invention also provides a kind of device of applying tin mud generation in described reduction tin plating electrolyte preparation process to reduce the method for tin mud generation in tin plating electrolyte preparation process, it is characterized in that: described method comprises the steps:
(A), in mixing section (102), add tin particles, the add-on of described tin particles is determined by the following method:
The add-on > oxygen amount of the being blown into ÷ oxygen blast intensity of tin particles in mixing section
In above formula, the oxygen amount of being blown into is 300～1000Nl/min, and oxygen blast intensity is 65 ~ 120L/mint;
(B), plating solution is inputted to tin dissolving vessel (1), oxygen is blown in distributing chamber (103) and is mixed with plating solution according to the oxygen amount of being blown in step (A) and oxygen blast intensity, the plating solution that is mixed with oxygen enters mixing section (102) through porous web plate (11), dissolve the tin particles in mixing section (102), form tin plating electrolyte, finally, the tin plating electrolyte of generation from separate chamber (101) top exit discharge tin dissolving vessel (1);
(C), the numerical value P in observation the first pressure warning unit (5)
1, the numerical value P in the second pressure warning unit (6)
2and the flow velocity numerical value under meter (13), according to pressure reduction, i.e. P
1-P
2value, and flow velocity numerical value, determines that whether tin particles is in mixed uniformly state;
(D), keep the percentage of open area of the first web plate (1101) constant, then repeating step (A) ~ (C), by adjusting the percentage of open area of the second web plate (1102), make the percentage of open area of porous half tone 11 reach Critical Stability percentage of open area, finally make tin particles and plating solution reach even admixture.
According to a kind of method that reduces tin mud generation in tin plating electrolyte preparation process provided by the present invention, adopt, the diameter of described tin particles is 2.5 ~ 3mm, and described Critical Stability percentage of open area is 4 ~ 15%, the scope of described pressure reduction is 0.48 ~ 0.50MPa, and the scope of described flow velocity numerical value is 2.35 ~ 2.50m
3/ h.
According to a kind of method that reduces tin mud generation in tin plating electrolyte preparation process provided by the present invention, what adopt is, described plating solution is metilsulfate plating solution, described metilsulfate plating solution comprises following component: methylsulphonic acid salt concn 65 ~ 75ml/l, additive concentration 25 ~ 35ml/l, antioxidant concentration 15 ~ 25ml/l.
According to a kind of method that reduces tin mud generation in tin plating electrolyte preparation process provided by the present invention, employing, in described mixing section, tin particles add-on scope is 5 ~ 8 tons.
Beneficial effect of the present invention is:
1), between the distributing chamber of tin dissolving vessel and mixing section, a porous web plate is set, thereby guarantee that the tin particles in tin dissolving vessel can be in desirable good even admixture, thereby make tin particles in dissolving vessel in a kind of free-pouring state, fully mix with the plating solution that contains dissolved oxygen, avoid the oxygen excess of regional area, reduce tin mud generation;
2), the index of introducing " oxygen blast intensity " instructs the control to tin particles add-on in mixing section, thereby by using excessive tin particles, guarantees that under maximum molten tin rate behavior, oxygen can be inexcessive;
3), by the metilsulfate plating solution of specific proportioning and component, further effectively suppress the generation of tin mud.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that is related to of the total pressure drop of plating solution tin particles layer during by different percentage of open area web plate and apparent velocity.
Fig. 2 is a kind of structural representation for reducing the device of tin mud generation in tin plating electrolyte preparation process provided by the present invention.
Fig. 3 is a kind of structural representation for reducing porous web plate in the device of tin mud generation in tin plating electrolyte preparation process provided by the present invention.
In Fig. 1, A, local fixedly tin particles layer, B, local fluidization tin particles layer, C, the part tin particles layer of gushing, α, real-time percentage of open area, α
cS, Critical Stability percentage of open area, U
mf, critical fluidized speed.
In Fig. 2,1, tin dissolving vessel, 101, separate chamber, 102, mixing section, 103, distributing chamber, the 2, first recycle pump, 3, oxygen supply device, the 4, the 3rd pressure warning unit, 5, the first pressure warning unit, the 6, second pressure warning unit, the 701, first valve, 702, the second valve, the 703, the 3rd valve, the 704, the 4th valve, 8, plating solution storage tanks, the 9, second recycle pump, 10, plating tank, 11, porous web plate, 12, pipeline, 13, under meter.
In Fig. 3, the 1101, first web plate, the 1102, second web plate.
Embodiment
Below in conjunction with accompanying drawing, a kind of devices and methods therefor for reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention is further explained.
A kind of structure for reducing the device of tin mud generation in tin plating electrolyte preparation process provided by the present invention is as follows:
As shown in Figure 2, described device comprises that eleetrotinplate unit and tin dissolve unit, described eleetrotinplate unit comprises plating tank 10, described plating tank 10 one end are connected with the 3rd valve 704 with the second recycle pump 9 respectively by pipeline 12, described tin dissolves unit and comprises tin dissolving vessel 1, described tin dissolving vessel 1 is by pipeline 12 and oxygen supply device 3, the first recycle pump 2, plating solution storage tanks 8 and the first valve 701 form closed connection, described tin dissolving vessel 1 comprises the separate chamber 101 setting gradually, mixing section 102He distributing chamber 103, between described distributing chamber 103 and oxygen supply device 3, be provided with the 3rd pressure warning unit 4, between described oxygen supply device 3 and plating solution storage tanks 8, be also provided with the second valve 702, described the second valve 702 and the first recycle pump 2 form and are connected in parallel, between described separate chamber 101 and the first valve 701, be also provided with under meter 13.
Described plating tank 10 is connected with plating solution storage tanks 8 by pipeline 12, after described the second recycle pump 9 is in parallel with the 3rd valve 703, by the 4th valve 704, be connected with plating solution storage tanks 8, described mixing section 102 is connected with the first pressure warning unit 5, between described separate chamber 101 and the first valve 701, be provided with the second pressure warning unit 6, between described mixing section 102He distributing chamber 103, be provided with porous web plate 11, described porous web plate 11 comprises the first web plate 1101 and the second web plate 1102, between described the first web plate 1101 and the second web plate 1102, be bolted, at the center of the first web plate 1101 and the second web plate 1102, establish a holding bolt, 6 holding bolts are on average established by 60 ° of angles in mid-way at web plate center to edge, so, guaranteed compound tight, convenient disassembly again.The installation at the second web plate 1102 edges can utilize the mounting means of original Stainless Steel Cloth.
Wherein, described the second web plate 1102 is arranged at the first web plate 1101 tops, and described the first web plate 1101 thickness are 20 ~ 30mm, and aperture is 6 ~ 8mm, and percentage of open area is 28 ~ 32%, and described the second web plate 1102 thickness are 2 ~ 5mm, and aperture is greater than 0 and be less than 2.5mm.
The first web plate 1101 used in the present invention and the second web plate 1102 are applied on industrial production device.
The invention provides most important parts in tin dissolving vessel 1---the design of porous web plate 11 guarantees that tin particles in tin dissolving vessel and the oxygen being blown into and mobile tin plating electrolyte evenly mix more fully, avoid local excess of oxygen, make tin mud generating capacity lower.Porous web plate 11 is wherein a kind of knockdown composite structures, it by two independently porous web plate form.
A web plate wherein, the first web plate 1101, is referred to as basic web plate, and its function is tin particles and the weight of plating solution and the high tank internal pressure in carrying dissolving vessel.Therefore this web plate must have certain thickness.Experience is told us, and its thickness is at 20 ~ 30mm, for easy to process hole can be opened more greatly, the diameter in hole is generally at 6 ~ 8mm, its percentage of open area is inevitable very large, generally 28 ~ 32%, is the porous web plate that belongs to low pressure drop.
Other one, the second web plate 1102, can be referred to as " stable and uniform mixing web plate ", owing to not needing load capacity, the thickness of plate can be thinner, and its function is that it and basic web plate (i.e. the first web plate 1101) percentage of open area of compound rear formation should reach the requirement of Critical Stability percentage of open area.Because the diameter of tin particles is generally in 3mm left and right, therefore the aperture of the second web plate 1102 must be less than 2.5mm, to prevent that tin particles from draining in distributing chamber 103.Because the hole of this web plate is smaller and intensive, add and can cause web plate distortion warpage man-hour, so this web plate again can not be too thin, thickness of slab is generally at 2 ~ 5mm, to machine rear indeformable being as the criterion.
Wherein above-mentioned two blocks of web plates must closely be combined with each other in tin dissolving vessel.If because there is space between the two, percentage of open area will change, the good even admixture of whole tank will change.Meanwhile, the space between two blocks of plates can be blocked by tin mud.The realization of the Critical Stability percentage of open area of the porous web plate 11 after compound is to guarantee tin particles unrestricted flow in tin dissolving vessel, with the well-mixed key of the plating solution that contains dissolved oxygen.The present invention is through verification experimental verification, and when tin particles diameter is 2.5 ~ 3mm, its Critical Stability percentage of open area is 4 ~ 15%.
Reach low tin mud amount, the porous web plate only having had is inadequate, good porous web plate can only be avoided the oxygen excess of regional area, it also needs not excessive cooperation the by overall oxygen, therefore, the invention provides the method that another prevents that oxygen is excessive, it does not need loaded down with trivial details control method, different from the method for patent documentation 2,3, the present invention is not with excessive the excessive of oxygen that guarantee of tin particles amount.The amount that the present invention introduces a kind of " oxygen blast intensity " instructs the control to tin particles weight, described " oxygen blast intensity ", 1 ton of metallic tin grain correspondence is blown into how many amount of oxygen (unit is mark Nl/min, be standard Liter Per Minute), in the situation that tin particles weight is greater than the tin particles weight that use " oxygen blast intensity " value calculates, the generating capacity of tin mud is minimum.Take MSA plating solution as example, at molten tin pressure 0.6 ~ 0.8MPa, bath flow rate 100 ~ 150mm/s in mixing section, the tin particles weight in mixing section should be controlled by being greater than the tin particles amount that 50 ~ 100Nl/min.t calculates.
The tin particles add-on > oxygen amount of being blown into ÷ oxygen blast intensity in mixing section
Meanwhile, the present invention is the control method of the low tin mud loss based on insoluble anode MSA plating solution, prepares in tin plating electrolyte process, and the proportioning of the various components of MSA plating solution (being metilsulfate plating solution) plays very large impact to the generation of tin mud.The solution additive that the present invention adopts is commodity TP-G7, must meet following component proportion condition and can obtain the loss of low tin mud in tin process processed.
| Control project | Span of control | Unit |
| Total acid (with MSA content meter) | 70±5 | ml/l |
| Additive TP-G7 | 30±5 | ml/l |
| Antioxidant | 20±5 | ml/l |
In upper table, total acid (with MSA content meter), actual is exactly the content of MSA, the saying of " with MSA content meter " is the expression method in electroplating industry, methylsulphonic acid in plating solution occurs with two kinds of forms, be the tin methane sulfonate combining with tin ion, a kind of is the methylsulphonic acid being free in plating solution, so what emphasize here to control is total acid.
A kind of step and principle that reduces the method for tin mud generation in tin plating electrolyte preparation process provided by the present invention is as follows:
(A), in mixing section 102, add tin particles, the add-on of described tin particles is determined by the following method:
The add-on > oxygen amount of the being blown into ÷ oxygen blast intensity of tin particles in mixing section
In above formula, the oxygen amount of being blown into is 300 ~ 1000Nl/min, and oxygen blast intensity is 65 ~ 120L/mint;
(B), plating solution is inputted to tin dissolving vessel 1, oxygen is blown in distributing chamber 103 and is mixed with plating solution according to the oxygen amount of being blown in step (A) and oxygen blast intensity, the plating solution that is mixed with oxygen enters mixing section 102 through porous web plate 11, dissolve the tin particles in mixing section 102, form tin plating electrolyte, finally, the tin plating electrolyte of generation from separate chamber 101 top exits discharge tin dissolving vessels 1;
(C), the numerical value P in observation the first pressure warning unit 5
1, the numerical value P in the second pressure warning unit 6
2and the flow velocity numerical value under meter 13, according to pressure reduction, i.e. P
1-P
2value, and flow velocity numerical value, determines that whether tin particles is in mixed uniformly state;
(D), keep the percentage of open area of the first web plate 1101 constant, then repeating step (A) ~ (C), by adjusting the percentage of open area of the second web plate 1102, make the percentage of open area of porous half tone 11 reach Critical Stability percentage of open area, finally make tin particles and plating solution reach even admixture.
The diameter of described tin particles is 2.5 ~ 3mm, and described Critical Stability percentage of open area is 4 ~ 15%, and the scope of described pressure reduction is 0.48 ~ 0.50MPa, and the scope of described flow velocity numerical value is 2.35 ~ 2.50m
3/ h.In described mixing section, tin particles add-on scope is 5 ~ 8 tons.The effect of described the 3rd valve 703 is the flows that regulate plating solution in electroplating process, and the effect of the second valve 702 is the flows that regulate plating solution in molten tin process.
Wherein, increase along with flow velocity, the corresponding increase of flow pressure drop in mixing section 102, when flow velocity reaches a certain value, now, actionless tin granulosa starts vibrations, then has small expansion, pressure drop in mixing section 102 slightly declines, and tin particles layer becomes the loose state mixing with plating solution by the state-transition compressing; Along with flow velocity increases gradually, the tin grain in tin particles can move freely, until do irregular random motion; Along with the further increase of flow velocity, whole tin particles layer demonstrates the feature of some liquid attribute; Along with tin grain pitch enlargement, tin particles layer further expands.The flow velocity when state of tin particles layer is converted into flow state by the state compressing is called critical even mixing velocity.Actual conversion process, due to the heterogeneity of tin grain granularity and the heterogeneity of filling operation, even the speed lower than stagnation point, the turbulence of local tin particles layer will occur, increase along with flow velocity, be further development of the inhomogeneous mixing in local hole, even can make tin particles layer under mixed uniformly flow velocity, still can there is not mixed uniformly particular in tin particles layer.Therefore, in real system, critical even mixing point is without meaning definitely clearly, and is the process of fuzzy gradual change, and different and different according to condition.
Effect and the principle of design of porous web plate 11 provided by the present invention are as follows:
A porous web plate 11 is set between distributing chamber 103, mixing section 102, its effect: the one, plating solution is uniformly distributed and is entered along the section of tin particles layer, with tin grain uniform contact, form uniform admixture; The 2nd, tin grain is play supporting role, eliminate the unstable of system; The 3rd, resist extraneous interference, limit unsettled malignant development.Porous web plate 11 is the uniform and stable mobile important guarantees of the tin particles in mixing section 102.Porous web plate 11 action principles make plating solution along tin particles layer section reallocation by " throttling " exactly, the degree of uniformity that plating solution distributes along tin particles layer section and the throttle degree of web plate and on the characteristic of tin particles layer relevant.Conventionally with plating solution, by the drooping characteristic of web plate and tin particles layer, assess, the real-time percentage of open area α of pressure drop Δ P and web plate, i.e. the percentage ratio %, plating solution that the web plate perforate total area accounts for the cross-sectional area of tin particles layer by the apparent velocity U of tin particles layer, the height H of the voidage ε of tin particles layer, tin particles layer, plating solution by the resistance coefficient ξ, Teeth granule density ρ in web plate aperture
s, fluid density ρ
frelevant.
The stagnation pressure of system is reduced to:
A mistake! Do not find Reference source.ε
mf) (mistake! Do not find Reference source.) (
a mistake! Do not find Reference source.m
Wherein, porous web plate have high pressure drop web plate and low pressure drop web plate minute, by the total pressure drop of different web plate tin particles layers and the relation of apparent velocity as shown in Figure 1, for high pressure drop web plate, real-time percentage of open area α is less than Critical Stability percentage of open area α to plating solution
csweb plate, its stagnation pressure is reduced to the single-valued function of bath flow rate, tin particles lamination falls only relevant with tin particles layer thickness, for given pressure drop, tin particles layer is corresponding a definite flow velocity only, tin particles layer everywhere flow velocity equate, reached the admixture of stable and uniform.Yet for low pressure drop web plate, percentage of open area α is greater than Critical Stability percentage of open area α in real time
csweb plate, in tin particles layer, have three states, with the crossing A point of fixed pressure drop line, local tin particles layer shows as the fixedly tin particles of low gas velocity; Intersection points B, local tin particles layer shows as good even mixing; Intersection point C, local tin particles layer is at a high speed lower jet flow, i.e. local fountain tin particles.This flow state has unstable, and it can collapse into local fixedly tin particles layer and local channel, and tin particles layer loses good even mixing completely, and this is completely undesirable.
In the step of method provided by the present invention (C), according to pressure reduction, i.e. P
1-P
2value, and flow velocity numerical value, whether tin particles in mixed uniformly state, according to Fig. 1 in curve contrast, thereby confirm that whether tin particles is in mixed uniformly state by after porous web plate 11 percentage of open area of Set For Current.
In the step of method provided by the present invention (D), if tin particles is not in even admixture, repeating step (A) ~ (C), by keeping the percentage of open area of the first porous web plate 1101 constant, adjust the percentage of open area of the second porous web plate 1102, and then the percentage of open area of adjustment porous web plate 11, make the percentage of open area of porous web plate 11 reach Critical Stability percentage of open area, i.e. α shown in Fig. 1
cS(Critical Stability percentage of open area).Thereby effectively reduce the growing amount of tin mud.
The advantage of high pressure drop web plate is to guarantee good even admixture, but causes moving consumable increase, and uneconomical; Although the consumption of low pressure drop web plate kinetic energy is lower, it can cause tin particles layer normally not mix.Can know by inference, certainly exist one and can guarantee that tin particles layer stable and uniform flows,, there is the percentage of open area of a suitable web plate in the rational web plate of kinetic energy consumption simultaneously.We are referred to as Critical Stability percentage of open area.Its condition is
A mistake! Do not find Reference source.=0
Under this condition, when the flow velocity of plating solution is increased gradually by little, plating solution is by the corresponding increase gradually of pressure drop of tin particles layer, when reaching a certain flow velocity, tin particles layer starts to expand, tin particles starts to flow, now, the weight of tin particles by plating solution to the drag force of tin particles and buoyancy institute balance, when further increase flow velocity, the corresponding increase of drag force that tin particles is subject to, the movement of the tin grain in tin particles layer is further expanded tin particles layer, tin particles stressor layer gradient reduces, but the total pressure drop of tin particles layer remains unchanged.The curve that tin particles layer pressure drop bath flow rate increases will change level into by rising, and the corresponding bath flow rate of its flex point is minimum good even mixing velocity, and this is also the economic velocity that we pursue.
The percentage of open area of theoretical accurate calculation web plate is more difficult, a lot of metallic tin dissolving vessels in use can not form good even admixture because web plate percentage of open area calculates the incorrect tin particles layer that causes, patent documentation 1,3-No. 180493 communiques of Unexamined Patent propose, and metallic tin particle is carried out to mechanical stirring is exactly in the situation that the web plate in metallic tin dissolving vessel cannot provide a solution of a suitable good even admixture.Its objective is by mechanical stirring, make that tin particles and plating solution are full and uniform to be mixed, to accelerate the dissolution rate of tin, solve the local situation that has excess of oxygen, thereby reduce the generating capacity of tin mud.The method has increased facility investment, and meanwhile, in the situation that tin particles dissolving vessel has very large pressure, agitator turning axle just seems very important through the dynamic seal at dissolving vessel position, and under continuous duty, the reliability of normal work is difficult to guarantee.The agitator increasing has also increased the extra consumption of the energy.
Therefore, method of the present invention is in the situation that not increasing extras and energy consumption, provide the design of a porous web plate to guarantee that the tin particles in tin dissolving vessel can be in desirable good even admixture, thereby make tin particles in dissolving vessel in a kind of free-pouring state, fully mix with the plating solution that contains dissolved oxygen, avoid local excess of oxygen, make tin mud generating capacity lower.
The percentage of open area of porous web plate 11 provided by the present invention, is Critical Stability percentage of open area.
The realization of Critical Stability percentage of open area is to guarantee tin particles unrestricted flow in dissolving vessel, with the well-mixed key of the plating solution that contains dissolved oxygen.Because the present invention is a set of assembly reticular lamina, " the stable and uniform mixing web plate " on it (i.e. the second web plate 1102) can be dismantled very easily, as long as change the percentage of open area of " stable and uniform mixing web plate ", just can obtain the percentage of open area of new assembly reticular lamina.We know, high pressure drop web plate can guarantee good even admixture, and shortcoming is consumable increase.Therefore we can just install the combination porous web plate of thinking oneself as high pressure drop for the first time, in actual moving process, by being arranged on the upper and lower pressure warning unit of mixing section (as the first pressure warning unit 5, the second pressure warning unit 6), under meter 13 observed and recorded data, mapping obtains the curve of similar Fig. 1, thereby can accurately determine that whether tin particles that this web plate causes is in mixed uniformly state.So that constantly improve the percentage of open area of " stable and uniform mixing web plate ", reach the best good even admixture of Critical Stability.The present invention is through verification experimental verification, and when tin particles diameter is 2.5 ~ 3mm, its combined type porous web plate 11 Critical Stability percentage of open area are 4 ~ 15%.Be less than 4%, although can guarantee good even admixture, cause moving consumable increase, and uneconomical; Be greater than 15%, although kinetic energy consumption is lower, it can cause tin particles layer can not with oxygen and tin plating electrolyte is full and uniform to mix.
Yet, the porous web plate 11 with Critical Stability percentage of open area is only provided, can only make tin particles layer in the tin dissolving vessel state in suspending, thereby guarantee tin particles and the plating solution that contains dissolved oxygen being in contact with one another cmpletely, can not form local oxygen excess.Make tin mud generating capacity lower, also must accomplish that oxygen is inexcessive in whole tin process processed.
Patent documentation 2: it is the method for the electroplate liquid below 300ppm that Unexamined Patent-No. 131399 communique proposition is supplied with dissolved oxygen to the metallic tin particle in mixing section, its essence is exactly for certain tin particles amount, guarantees that the aggregate level of oxygen is inexcessive with low oxygen-supply quantity.Its shortcoming is when needs are produced high tin coating, and the molten tin ability of the method is unable to catch up with the spending rate of tin ion in plating solution, makes to produce normally to carry out.And patent documentation 3:CN 1993502A provides, tin ion concentration is controlled between target bound, thereby makes tin ion formation speed approach the average predetermined spending rate of tin ion, thereby can reduce the method for the generation of tin mud.The method of patent documentation 3 can not change for certain tin particles amount, when the dissolved oxygen of supplying with is electroplate liquid more than 300ppm, may occur the phenomenon that tin mud amount increases.When needs are produced high tin coating, although the molten tin ability of the method can be caught up with the spending rate of tin ion in plating solution, now will inevitably there is the phenomenon that tin mud amount increases, only the method can be accomplished accurate control, thereby reduces tin mud generating capacity.The starting point of above-mentioned two patent documentations is all to avoid the generation of excess of oxygen in molten tin process, and so-called excess of oxygen is exactly that the add-on of oxygen has surpassed tin particles total amount in dissolving vessel and may be dissolved as the needed amount of oxygen of tin ion.Above-mentioned patent is all from how controlling the oxygen amount adding to find one's way out.
The present invention proposes from other angle the method solving.Method of the present invention is:
The add-on of tin particles in mixing section is increased, with excessive tin particles, guarantee that under maximum molten tin rate behavior, oxygen can be inexcessive yet.
Take MSA plating solution as example, and the principal reaction process that tin particles dissolves in dissolving vessel is as follows:
1.2Sn+O
2+4H
+→2Sn
2++2H
2O
2.Sn+O
2+4H
+→Sn
4++2H
2O
3.2Sn
2++O
2+4H
+→2Sn
4++2H
2O
4.Sn
2++2MSA→Sn(MSA)
2
5.Sn+Sn
4+→2Sn
2
From 5 formulas, can find out, tin or a kind of good reductive agent, therefore excessive tin not only can guarantee that oxygen is inexcessive, meanwhile, can reduce tetravalent tin ion.In the presence of excess amounts of tin, can accomplish that the tin mud producing is lower.
Thus, the amount that the present invention introduces a kind of " oxygen blast intensity " instructs the control to tin particles weight.Its 1 ton of metallic tin grain correspondence is blown into how many amount of oxygen (unit is standard liter/min), in the situation that tin particles weight is greater than the tin particles weight that use " oxygen blast intensity " value calculates, the generating capacity of tin mud is minimum.Take MSA tin plating electrolyte as example, at molten tin pressure 0.6 ~ 0.8MPa, bath flow rate 100 ~ 150mm/s in mixing section, the tin particles weight adding should be controlled by being greater than the tin particles amount that 50 ~ 100Nl/min.t calculates.
The tin particles add-on > oxygen amount of being blown into ÷ oxygen blast intensity in tin ion dissolving vessel
Actually operating in large production is as controlling benchmark by the needed oxygen of the corresponding tin ion spending rate of the zinc-plated amount of the maximum amount of being blown in covering 80% product, calculate tin particles weight, that is to say that tin process processed has 80% to be in stable process, only have when the zinc-plated amount of product is greater than above-mentioned value and just need to increase the tonnage of tin particles in tin ion dissolving vessel, thereby keep constantly the excessive of tin particles.In described mixing section, tin particles add-on scope is 5 ~ 8 tons.
The present invention is the control method of the low tin mud loss based on insoluble anode MSA plating solution.The proportioning of the various components in tin process processed plays very large effect to the generation of tin mud.The solution additive that the present invention adopts is commodity TP-G7, and also having in addition a kind of additive that can be used for insoluble anode MSA plating solution is commodity TP-H.In tin process processed, must meet following component proportion condition and can obtain low tin mud loss.
| Control project | Aimed concn and span of control | Unit |
| Total acid (with MSA content meter) | 70±5 | ml/l |
| Additive TP-G7 | 30±5 | ml/l |
| Antioxidant | 20±5 | ml/l |
For tin plating electrolyte of the present invention, the target of tin process processed is to make the divalent tin ion concentration in work tin plating electrolyte remain on 15 ± 3g/l.Divalent tin ion in MSA tin plating electrolyte is that the form with tin methane sulfonate exists.In the process of tin processed, when metallic tin particle runs into oxygen, its surface will generate tin protoxide, from above-mentioned reaction formula, can find out, tin protoxide can generate the tin methane sulfonate that we need with the reaction of MSA plating solution.Also can generate stannic oxide with excessive dissolved oxygen reaction, therefore, it is to reduce the important means that tin mud produces that the total acidity of tin process processed is remained on to a higher level.Therefore, we control with total acid in tin process processed.
Organic additive TP-G7 compares with the additive of other trades mark, and itself just has the feature of low tin mud loss, in system of the present invention, as long as just can obtain the actual result of low tin mud loss in above-mentioned span of control.
Antioxidant just can play oxidation resistant effect while only reaching the amount of above-mentioned span of control.Be greater than above-mentioned controlling valu, can not increase effect.
Provide a kind of embodiment that reduces the method for tin mud generation in tin plating electrolyte preparation process provided by the present invention below:
Embodiment 1
In being 45l at a plating solution capacity for reducing tin plating electrolyte preparation process, on the device of tin mud generation, test.Observe the numerical value P in the first pressure warning unit
1, the numerical value P in the second pressure warning unit
2and the flow velocity numerical value under meter, according to pressure reduction, i.e. P
1-P
2value, and flow velocity numerical value, determine the percentage of open area of described porous web plate, keep the percentage of open area of the first web plate 1101 constant, by regulating the percentage of open area of the second web plate 1102, obtain the percentage of open area of required porous web plate 11, on this device, carry out different percentage of open area, different MS A bath system and be the comparative example of the test of the tin metal particle that additive selects two kinds of different trade mark TP-G7 or TP-H and different add-ons, each test period is 1 hour, the oxygen amount of being blown into is 0.6l/min, and oxygen pressure is 0.6MPa.The additive trade mark that sequence number 1,2 adopts is TP-H, and concentration is respectively 27ml/l and 33ml/l, and the additive trade mark that sequence number 3 ~ 5 adopts is TP-G7, and concentration is respectively 15ml/l, 29ml/l and 35ml/l.Sequence number the 1, the 4th, is covered with one deck Stainless Steel Cloth above the porous web plate that percentage of open area is 27.5%, and that sequence number 2,3,5 is respectively is provided by the invention, percentage of open area is 4%, 6.2% and 14% combined type porous web plate.In sequence number 1 ~ 5, the concentration of total acid is followed successively by 65ml/l, 58ml/l, 71ml/l, 73ml/l and 75ml/l.In sequence number 1 ~ 5, add the concentration of antioxidant to be followed successively by 15ml/l, 16ml/l, 18ml/l, 22ml/l and 25ml/l.Concrete outcome sees the following form:
As seen from the above table, when adopting the MSA electroplate liquid formulation of TP-G7 trade mark additive, add low combined type porous web plate percentage of open area, i.e. percentage of open area in 4% ~ 15% scope, and high tin particles add-on just can obtain low tin wastage rate.Here effect is set is the most obvious to the percentage of open area of porous web plate.
Embodiment 2
Producing per year on the big scale production equipment of 200,000 tons of tin plates, need 80m
3tin plating electrolyte carry out cycle operation.It has the tin dissolving vessel of an about 1m of internal diameter, on a porous web plate, is covered with one deck Stainless Steel Cloth, to play, stops that tin particles drops to the effect in distributing chamber.Improved method is that porous web plate is made to combined type web plate, retains original porous web plate constant, and the percentage of open area of porous web plate is originally 27.5%.Reprocess in addition a thin web plate (i.e. the second web plate 1102), make the percentage of open area after compound reach the Critical Stability percentage of open area having measured in laboratory.Percentage of open area after compound is 6.1%, has been significantly less than original value.In order to reach closely compound effect, can use bolted method, at the center of web plate, establish a holding bolt, in the mid-way at web plate center to edge, by 60 ° of angles, on average establish 6 holding bolts, so guaranteed compound tight, convenient disassembly again.The installation at newly-increased web plate edge can utilize the mounting means of original Stainless Steel Cloth.Improvement is in addition the tin particles amount adding, and can attempt being increased to 8 tons from original 4 tons always, if the height of mixing section does not increase, the tin particles of 8 tons may be gone in separate chamber in tin process processed, can make tin grain discharge tin dissolving vessel.Need to determine whether newly to do tin dissolving vessel by practical operation situation.
On this equipment, move MSA bath system, using the trade mark of additive is TP-G7, the component proportion according to the form below operation that need to control during molten tin
| Control project | Aimed concn and span of control | Unit |
| Total acid (with MSA content meter) | 70±5 | ml/l |
| Additive TP-G7 | 30±5 | ml/l |
| Antioxidant | 20±5 | ml/l |
Solution presasure is controlled at 6kg/cm
2, the tin particles amount in dissolving vessel is that blowing oxygen quantity regulates according to producing required tin ion meltage, the zinc-plated amount maximum that the product of this unit 80% covers be 5.6g/m
2.The corresponding maximum needed oxygen of the tin ion spending rate amount of being blown into is 300Nl/min, oxygen blast intensity is calculated with 65 liters/min of tons, tin particles add-on is controlled at 5 tons of left and right, according to formula: the tin particles add-on > oxygen amount of being blown into ÷ oxygen blast intensity in tin ion dissolving vessel, determine tin particles add-on.Be unit when producing lower zinc-plated amount coating, as long as turn down blowing oxygen quantity, the tin particles weight in molten tin can keep 6 tons constant.If desired produce 5.6g/m
2during tin plate, the oxygen that need to pass into will be increased to 400Nl/min just can catch up with tin ion spending rate, at this moment needs in advance tin particles weight to be increased to more than 6 tons.Under this pattern, move, tin waste is that the per-cent of the content of tin in the tin mud usage quantity that accounts for total tin metal remains on 1% left and right all the year round.
Embodiment 3
On device after above-mentioned improvement, with MSA, open cylinder operation, make open cylinder liquid requirement be within the shortest time, to generate the tin plating electrolyte that meets production requirement tin ion content, open tin ion in cylinder liquid since 0.Using the trade mark of additive is TP-G7, the component proportion according to the form below operation that need to control during molten tin
| Control project | Aimed concn and span of control | Unit |
| Total acid (with MSA content meter) | 70±5 | ml/l |
| Additive TP-G7 | 30±5 | ml/l |
| Antioxidant | 20±5 | ml/l |
Solution presasure is controlled at 8kg/cm
2, the tin particles amount in dissolving vessel is 8 tons, and in order to meet the requirement of tin processed fast, the oxygen amount of being blown into is 1000Nl/min, and oxygen blast intensity reaches 120 liters/min of tons, the degree in excess of oxygen, tin mud generating capacity will inevitably increase to some extent.Under this pattern, move 2 hours, just make 80m
3the tin ion of opening in cylinder liquid reaches 12.5g/l from 0.Tin mud after opening cylinder and completing in plating solution is 0.3582g/l only.The per-cent that the content that is converted to tin waste and is tin in tin mud accounts for the usage quantity of total tin metal is 1.72%.Still be significantly less than the waste of same type units.
Claims (10)
1. for reducing a device for tin mud generation in tin plating electrolyte preparation process, described device comprises that eleetrotinplate unit and tin dissolve unit,
Described eleetrotinplate unit comprises plating tank (10), and described plating tank (10) one end is connected with the 3rd valve (704) with the second recycle pump (9) respectively by pipeline (12);
Described tin dissolves unit and comprises tin dissolving vessel (1), described tin dissolving vessel (1) forms closed connection by pipeline (12) and oxygen supply device (3), the first recycle pump (2), plating solution storage tanks (8) and the first valve (701), and described tin dissolving vessel (1) comprises separate chamber (101), mixing section (102) and the distributing chamber (103) setting gradually;
Described plating tank (10) is connected with plating solution storage tanks (8) by pipeline (12), after described the second recycle pump (9) is in parallel with the 3rd valve (703), by the 4th valve (704), is connected with plating solution storage tanks (8), it is characterized in that:
Between described mixing section (102) and distributing chamber (103), be provided with porous web plate (11), described porous web plate (11) comprises the first web plate (1101) and the second web plate (1102).
2. a kind of device for reducing tin mud generation in tin plating electrolyte preparation process according to claim 1, is characterized in that being provided with between described distributing chamber (103) and oxygen supply device (3) the 3rd pressure warning unit (4).
3. a kind of device for reducing tin mud generation in tin plating electrolyte preparation process according to claim 1, it is characterized in that described mixing section (102) is connected with the first pressure warning unit (5), between described separate chamber (101) and the first valve (701), be provided with the second pressure warning unit (6), between described separate chamber (101) and the first valve (701), be also provided with under meter (13).
4. a kind of device for reducing tin mud generation in tin plating electrolyte preparation process according to claim 1, it is characterized in that being also provided with the second valve (702) between described oxygen supply device (3) and plating solution storage tanks (8), described the second valve (702) forms and is connected in parallel with the first recycle pump (2).
5. a kind of device for reducing tin mud generation in tin plating electrolyte preparation process according to claim 1, it is characterized in that described the second web plate (1102) is arranged at the first web plate (1101) top, described the first web plate (1101) thickness is 20 ~ 30mm, aperture is 6 ~ 8mm, percentage of open area is 28 ~ 32%, described the second web plate (1102) thickness is 2 ~ 5mm, and aperture is greater than 0 and be less than 2.5mm.
6. a kind of device for reducing tin mud generation in tin plating electrolyte preparation process according to claim 1 or 5, is characterized in that being bolted between described the first web plate (1101) and the second web plate (1102).
7. application rights requires a method for tin mud generation in the device reduction tin plating electrolyte preparation process described in 1, it is characterized in that: described method comprises the steps:
(A), in mixing section (102), add tin particles, the add-on of described tin particles is determined by the following method:
The add-on > oxygen amount of the being blown into ÷ oxygen blast intensity of tin particles in mixing section
In above formula, the oxygen amount of being blown into is 300 ~ 1000Nl/min, and oxygen blast intensity is 65 ~ 120L/mint;
(B), plating solution is inputted to tin dissolving vessel (1), oxygen is blown in distributing chamber (103) and is mixed with plating solution according to the oxygen amount of being blown in step (A) and oxygen blast intensity, the plating solution that is mixed with oxygen enters mixing section (102) through porous web plate (11), dissolve the tin particles in mixing section (102), form tin plating electrolyte, finally, the tin plating electrolyte of generation from separate chamber (101) top exit discharge tin dissolving vessel (1);
(C), the numerical value P in observation the first pressure warning unit (5)
1, the numerical value P in the second pressure warning unit (6)
2and under meter
(13) the flow velocity numerical value in, according to pressure reduction, i.e. P
1-P
2value, and flow velocity numerical value, determines that whether tin particles is in mixed uniformly state;
(D), keep the percentage of open area of the first web plate (1101) constant, then repeating step (A) ~ (C), by adjusting the percentage of open area of the second web plate (1102), make the percentage of open area of porous half tone 11 reach Critical Stability percentage of open area, finally make tin particles and plating solution reach even admixture.
8. a kind of method that reduces tin mud generation in tin plating electrolyte preparation process according to claim 7, it is characterized in that: the diameter of described tin particles is 2.5 ~ 3mm, described Critical Stability percentage of open area is 4 ~ 15%, the scope of described pressure reduction is 0.48 ~ 0.50MPa, and the scope of described flow velocity numerical value is 2.35 ~ 2.50m
3/ h.
9. a kind of method that reduces tin mud generation in tin plating electrolyte preparation process according to claim 7, it is characterized in that: described plating solution is metilsulfate plating solution, described metilsulfate plating solution comprises following component: methylsulphonic acid salt concn 65 ~ 75ml/l, additive concentration 25 ~ 35ml/l, antioxidant concentration 15 ~ 25ml/l.
10. a kind of method that reduces tin mud generation in tin plating electrolyte preparation process according to claim 7, is characterized in that: in described mixing section, tin particles add-on scope is 5 ~ 8 tons.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132998A (en) * | 2015-09-16 | 2015-12-09 | 中冶南方工程技术有限公司 | Automatic tin adding device and method and application of device |
| CN106149017A (en) * | 2016-08-29 | 2016-11-23 | 首钢京唐钢铁联合有限责任公司 | A kind of pre-galvanized system of pyrovinic acid electrotinning |
| WO2022221498A1 (en) * | 2021-04-15 | 2022-10-20 | Lam Research Corporation | Control of dissolved gas concentration in electroplating baths |
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| CN1993502A (en) * | 2004-08-05 | 2007-07-04 | 新日本制铁株式会社 | Method of electric tinning |
| CN102586851A (en) * | 2011-01-06 | 2012-07-18 | 宝山钢铁股份有限公司 | Electrolytic method for relieving and reducing tin sludge generated in tin plating solution |
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| CN1107524A (en) * | 1993-11-27 | 1995-08-30 | Sms舒路曼-斯玛公司 | Apparatus for solving zinc by using of electrolyte of acid containing liquid |
| JPH0931699A (en) * | 1995-07-21 | 1997-02-04 | Kawasaki Steel Corp | Electro tin plating method using insoluble anode |
| KR20010063655A (en) * | 1999-12-23 | 2001-07-09 | 신현준 | Tin electroplating process using insoluble anode for the metal strip |
| CN1993502A (en) * | 2004-08-05 | 2007-07-04 | 新日本制铁株式会社 | Method of electric tinning |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132998A (en) * | 2015-09-16 | 2015-12-09 | 中冶南方工程技术有限公司 | Automatic tin adding device and method and application of device |
| CN105132998B (en) * | 2015-09-16 | 2017-10-17 | 中冶南方工程技术有限公司 | A kind of automatic tin feeding device and its plus tin methods and applications |
| CN106149017A (en) * | 2016-08-29 | 2016-11-23 | 首钢京唐钢铁联合有限责任公司 | A kind of pre-galvanized system of pyrovinic acid electrotinning |
| WO2022221498A1 (en) * | 2021-04-15 | 2022-10-20 | Lam Research Corporation | Control of dissolved gas concentration in electroplating baths |
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|---|---|
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