CN1185483C - Differential scanning calorimeter instrument and anticorrosive treating method thereof - Google Patents
Differential scanning calorimeter instrument and anticorrosive treating method thereof Download PDFInfo
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- CN1185483C CN1185483C CNB02133126XA CN02133126A CN1185483C CN 1185483 C CN1185483 C CN 1185483C CN B02133126X A CNB02133126X A CN B02133126XA CN 02133126 A CN02133126 A CN 02133126A CN 1185483 C CN1185483 C CN 1185483C
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Abstract
The present invention relates to a differential scanning calorimeter (DSC) and a corrosion-preventing treating method thereof, which can enhance the use range of the DSC and can particularly to cause the DSC to be used for the reaction of corrosive gas. In the corrosion-preventing treating method of the differential scanning calorimeter (DSC), the elements in a pool of the DSC or a high pressure differential scanning calorimeter (HPDSC) are put into Ni-P alloy or Ni-P-X alloy plating liquid, and a Ni-P or Ni-P-X non-crystalline state alloy plating layer with thickness within 20 mu m is formed the surface of each element in the pool. Compared with the prior art, the elements in the pool of the DSC obtained by the corrosion-preventing treating method of the differential scanning calorimeter (DSC) have strong corrosion resistance, the elements can be used for atmosphere with strong corrosiveness, such as hydrogen sulfide, etc., under high pressure at high temperature, and the use range of the DSC is widened. The corrosion-preventing treating method of the differential scanning calorimeter (DSC) has the advantages of simple operation, low cost, good plating-layer heat conductivity and no influence on the sensitivity of the meter.
Description
1, technical field
The present invention relates to a kind of differential scanning calorimeter (DSC) and method for anticorrosion treatment thereof, promptly can improve the disposal route of differential scanning calorimeter usable range, particularly make it can be used for containing the disposal route of corrosive gas reaction.
2, background technology
Differential scanning calorimeter (DSC) is a kind of of heat analysis method, and it is under program temperature controlled condition, and test sample changes with respect to the thermal capacity of inertia object of reference (as Alpha-alumina), its degree of detection height, consumption is few, therefore has been widely used in the glass transition of measuring samples, fusing, crystallization, response characteristic, stability, oxidation induction time and polycrystallinity, compatibility, character such as purity.Now, count tame instrument company in the world and producing DSC, the user reaches nearly ten thousand families.But, because the influence that a large amount of physical processes and chemical reaction are subjected to air pressure, DSC experiment usually must be carried out under pressure, so TA Instruments company developed first High Pressure Difference scanning calorimeter instrument (HPDSC) in the world in nineteen sixty-eight, can under high pressure carry out the DSC experiment.Manufacturer mainly contains TA Instruments company, Mettler-Toledo company and Netzsch company etc., the gesture of using the user also to become increasing.
Atmosphere when DSC and HPDSC experiment can be that static state also can be dynamically, but quite harsh to the requirement of atmosphere.This quasi-instrument of common model only limits can be at O
2, N
2, carry out in Ar, He and the air atmosphere, main cause be in DSC and HPDSC reaction tank in order to guarantee the sensitivity of heat conductance, used a large amount of metal materials, as silver, copper or its alloy etc.These materials are easy to by some corrosive gass, as erosions such as sulfuretted hydrogen, sulphuric dioxide, cause instrument damage and performance index to reduce, and especially under high-pressure situations, situation is even more serious.The DSC 204HP Phoenix that Netzsch company recent design is produced
Type HPDSC adopts method gold-plated in the DSC pond, preferably resolves the problems referred to above, makes the use atmosphere of instrument can expand to H
2, CO
2And CH
4, reaction pressure also rises to 15.0MPa from the 7.0MPa of common model simultaneously.
However, the usable range of DSC and HPDSC is subjected to very big restriction, and as under in High Temperature High Pressure during some corrosive atmosphere of contact, this quasi-instrument still can not carry out work.
Before using, hydrogenation catalyst must can reveal good activity and stable through sulfidation.During sulfuration, when carrying out vulcanization reaction, sulfuretted hydrogen that sulfuretted hydrogen or vulcanizing agent generate and catalyst surface metal produce a large amount of heats behind hydrogen reducing.Industrial, the generation of these heats will cause the catalyzer local overheating, has a strong impact on the performance of catalyzer.In order to control heat targetedly or detect to produce what of heat, it is quite necessary using instrumental analysis.The sulfuration of hydrogenation catalyst generally is to carry out under the elevated pressures of hydrogen and sulfuretted hydrogen, and therefore, HPDSC has significance in this work.
Because the existence of sulfuretted hydrogen, the DSC and the HPDSC of common model ban use of.Even DSC is 204 HP Phoenix
Type HPDSC, though adopted gold-plated processing in its sample cell, can get rid of the corrosion of sulfuretted hydrogen fully at normal temperatures and pressures, but under high temperature (maximum temperature of vulcanization reaction is 420 ℃), high pressure (top pressure of sulfuration is 8.5MPa), reaction tank will be corroded to the DSC pond.Simultaneously, thin Gold plated Layer porous, more than 300 ℃, parent metals such as silver or copper can be diffused in the Gold plated Layer, make the afunction of Gold plated Layer.Thick Gold plated Layer then causes instrument cost to raise, the waste resource.In addition, Thiourea organic compound (the normal a kind of vulcanizing agent that adopts of the outer sulfuration of device) is also quite strong to the corrosion of gold at normal temperatures and pressures, therefore adopts gold plating method also to have many defectives with the anticorrosion problem that solves DSC and HPDSC.
Certainly, in order to guarantee the sensitivity of DSC and HPDSC, the existence of higher relatively silver, copper and the alloy thereof of heat conductance is that inevitably key issue is how it suitably to be handled, to reach the reaction that can contain corrosive gas in the pond.
Adding one deck coating to prevent the erosion of corrosive gas, is reasonable selection.The use of electro-plating method is comparatively easy, but every performance index of its coating are then not ideal, or has other problem.For example, we think that corrosion-resistant chromium coating preferably is a kind of more satisfactory functional coating.But, because the uneven coating that may exist in electroplating process is even and the plating leakage situation still will have influence on serviceable life of DSC.Simultaneously since sexavalent chrome to the serious harm of human body and to the severe contamination of environment, the environmental administration of countries in the world has carried out strict restriction to the discharging of chromium mist and chromate waste water.Prove that now the propagation of hexavalent chromium in air and water is the main cause that causes rhinocarcinoma and lung cancer.U.S. authority plating technical magazine " product finish " editor Gray lies prostrate this (Bev Graves) and points out: the U.S. so that if global auto manufacturing thinks little of nickel-base alloy coating from now on, will cause closing down even being removed name from the rolls in this industry.
In order to seek the corrosion resistance that chrome plating has, remedy the weak point of chromium plating simultaneously again, people have carried out a large amount of development test work, make great efforts the various nickel-base alloy coatings of research and development.In recent years at home and abroad, the electroless plating technology application of new development is extensive gradually.Compare with plating, electroless plating is little to the pollution of environment, and coating performance is good.After treatment, the resistance to corrosion of workpiece is greatly improved, and coating is evenly distributed on whole work-piece, as long as plating bath arrives part, can both plate coating, and thickness of coating is even, does not exist to electroplate distinctive corner effect problem.This is for complex-shaped and foraminate part, and electro-plating method is difficult to solve, and electroless plating can address this problem easily.In addition, compare with electrodeposited coating, the porosity of chemical deposit is low, density is high, corrosion resistance is strong, and has perfect performance price ratio.Therefore, this method has than electroplating even more ideal effect.
3, summary of the invention
At the deficiencies in the prior art, the invention provides a kind of differential scanning calorimeter and anti-corrosive treatment method that can effectively prevent corrosive gas that in DSC or HPDSC experimentation, use or generation to DSC and the corrosion of HPDSC pond.
Differential scanning calorimeter of the present invention comprises element in the calorimeter pond, and element surface has a layer thickness 20 μ m with interior Ni-P alloy or Ni-P-X amorphous alloy coating in the pond, thickness of coating is preferably 5～10 μ m, and element comprises reference and example platform, fixed underpan, pond and silver lid etc. in the described pond.
The anti-corrosion treatment process of differential scanning calorimeter of the present invention is:
In DSC (HPDSC) instrument pond in the preparation process of element, with element in the pond, especially with the experiment atmosphere position that can contact, place the Ni-P-X alloy electroplating bath that has prepared, make its surface form layer of Ni-P alloy or Ni-P-X amorphous alloy chemical deposit.Coating be one deck densification, can be at the chemical plating Mi-P alloy or the Ni-P-X alloy layer of corrosive gases corrosion under the High Temperature High Pressure, thickness is no more than 20 μ m, is preferably 5～10 μ m, is not corroded in the instrument pond in DSC (HPDSC) experimentation guaranteeing.
Element adopts Ni-P alloy or Ni-P-X amorphous alloy coating in DSC of the present invention (HPDSC) the instrument pond, and the coating corrosion resistance is strong, can be suitable for the strong atmosphere of corrosivity such as sulfuretted hydrogen under high temperature, high pressure, has widened the usable range of DSC instrument.The inventive method is simple to operate, and cost is low, and the coating thermal conductivity is good, does not influence the sensitivity of instrument.
4, embodiment
The parts that can contact with atmosphere in common DSC and the HPDSC pond comprise reference and example platform, fixed underpan, Chi Gai (Cover) (being copper or aldary material), pool wall (for stainless steel) and silver lid (SilverLid, silver-colored material).In the present invention, add chemical plating Mi-P alloy or Ni-P-X alloy layer with being primarily aimed at above-mentioned parts.
In the present invention, the chemical plating Mi-P alloy plating bath principal ingredient of selection comprises 15-25 grams per liter nickelous sulfate, 10-40 grams per liter inferior sodium phosphate, 20-30 grams per liter Sodium acetate trihydrate etc.Also comprise X in the Ni-P-X alloy electroplating bath.By regulator solution pH value is 4.8-5.3, and 90 ± 1 ℃ of heated solutions are immersed in metal material in this solution after 20-60 minute, form Ni-P alloy or Ni-P-X alloy layer at metal material surface.
In the present invention, the X in the coating is SiC, adamas, α-Al
2O
3Etc. inertia insoluble matter particulate, granularity is 0.5～5 μ m, and the concentration in alloy electroplating bath is 10～15 grams per liters.
In the present invention, the thickness of Ni-P alloy or Ni-P-X alloy layer is generally at 2.5～100 μ m, in order to take into account antiseptic effect simultaneously and to try one's best the influence of reduction to instrumental sensitivity, the thickness of selecting coating is in 20 μ m, be preferably 5～10 μ m, in the present invention, do not contact with the position that will add the inorganics coating in order to guarantee the corrosive gas molecule, coating should guarantee compactness.
Because amorphous phosphorus-nickel alloy is the homogeneous homogeneous structure, there are not tissue defects and chemical constitution segregations such as grain boundary dislocation, by the coating that chemical plating bath obtained, have the hardness height, wearing quality is good, corrosion-resistant characteristics such as strong.After measured, the corrosion of alkaline matter such as acidic materials such as coating ability sulfuretted hydrogen, sulfuric acid, hydrochloric acid and caustic soda.And coating itself is high temperature resistant, does not come off, and can replace Gold plated Layer fully, save gold.Chinese patent 89104018,99127028 etc. has been reported the compound method of Ni-P alloy electroplating bath; And Chinese patent 91106947,93116923 and the then important use that biases toward Ni-P alloy electroplating method such as USP 5,863,609,5,705,234 grades.The present invention in the pond of DSC and HPDSC all with element that corrosive gas contacts on add one deck chemical plating Mi-P alloy or Ni-P-X alloy layer, solved the etching problem that exists during DSC (HPDSC) uses well.
Be described in further detail method of the present invention below by embodiment.
Example 1
Principal ingredient comprises 25 grams per liter nickelous sulfates, 25 grams per liter inferior sodium phosphate and 20 grams per liter Sodium acetate trihydrates in the chemical plating Mi-P alloy plating bath.By regulator solution pH value 5.0, heated solution is immersed in the reference in the common DSC pond and example platform, fixed underpan, pond, Yin Gai in this solution after 50 minutes about 90 ℃, forms 7.4-8.6 μ mNi-P alloy layer at metal material surface.
Pass through under sulfuretted hydrogen/nitrogen atmosphere that above-mentioned processing DSC pond later is 0.1MPa, sulfide hydrogen 15% at pressure and be raised to 550 ℃ of constant temperature 4h also 5 times repeatedly with 15 ℃/min, do not see that the Ni-P alloy layer of light corrodes from room temperature.
Example 2
Principal ingredient comprises 25 grams per liter nickelous sulfates, 25 grams per liter inferior sodium phosphate and 20 grams per liter Sodium acetate trihydrates in the chemical plating Mi-P alloy plating bath.By regulator solution pH value 5.0, heated solution is immersed in the reference in the HPDSC pond and example platform, fixed underpan, Chi Gai, pool wall, Yin Gai in this solution after 50 minutes about 90 ℃, forms 7.5-8.8 μ mNi-P alloy layer at metal material surface.
Pass through under sulfuretted hydrogen/nitrogen atmosphere that above-mentioned processing HPDSC pond later is 5.5MPa, sulfide hydrogen 15% at pressure and be raised to 550 ℃ of constant temperature 4h also 5 times repeatedly with 15 ℃/min, do not see that the Ni-P alloy layer of light corrodes from room temperature.
Example 3
Principal ingredient comprises 25 grams per liter nickelous sulfates, 25 grams per liter inferior sodium phosphate and 20 grams per liter Sodium acetate trihydrates and 12 grams per liter SiC (diameter is 1-3 μ m, and density is 3150 grams per liters, and microhardness is 2900-3250HV) in chemical Ni-P plating-SiC alloy electroplating bath.By regulator solution pH value 5.0, heated solution is about 90 ℃, reference in the common DSC of the metal material pond and example platform, fixed underpan, Chi Gai, pool wall, Yin Gai were immersed in this solution after 50 minutes, form 6.4-7.6 μ mNi-P-SiC alloy layer at metal material surface.
Pass through under sulfuretted hydrogen/nitrogen atmosphere that above-mentioned processing DSC pond later is 0.1MPa, sulfide hydrogen 15% at pressure and be raised to 550 ℃ of constant temperature 4h also 5 times repeatedly with 15 ℃/min, do not see that the Ni-P-SiC alloy layer of light corrodes from room temperature.
Example 4
Principal ingredient comprises 25 grams per liter nickelous sulfates, 25 grams per liter inferior sodium phosphate and 20 grams per liter Sodium acetate trihydrates and 12 grams per liter SiC (diameter is 1-3 μ m, and density is 3150 grams per liters, and microhardness is 2900-3250HV) in chemical Ni-P plating-SiC alloy electroplating bath.By regulator solution pH value 5.0, heated solution is immersed in the reference in the common DSC pond and example platform, fixed underpan, pond, Yin Gai in this solution after 50 minutes about 90 ℃, forms 6.1-7.5 μ mNi-P-SiC alloy layer at metal material surface.
Pass through under sulfuretted hydrogen/nitrogen atmosphere that above-mentioned processing DSC pond later is 5.6MPa, sulfide hydrogen 15% at pressure and be raised to 550 ℃ of constant temperature 4h also 5 times repeatedly with 15 ℃/min, do not see that the Ni-P-SiC alloy layer of light corrodes from room temperature.
Above-mentioned four kinds of embodiment compare as table one with the DSC sensitivity that Ni-P alloy or Ni-P-X alloy layer front and back are not arranged.
The variation of DSC sensitivity before and after table one electroless plating
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Sensitivity before the plating, μ w | 18 | 30 | 20 | 30 |
| Plating back sensitivity, μ w | 20 | 31 | 21 | 32 |
As can be seen from Table I, by DSC (HPDSC) pond and other and the electroless plating of reaction atmosphere contact element are handled, great changes will take place in the sensitivity of instrument, can satisfy the needs of operating fully.
Claims (10)
1, a kind of differential scanning calorimeter comprises element in the calorimeter pond, it is characterized in that element surface in the pond has Ni-P or the Ni-P-X amorphous alloy coating of a layer thickness 2.5 μ m～20 μ m, and wherein X is SiC, adamas or α-Al
2O
3
2,, it is characterized in that described thickness of coating is 5-10 μ m according to the described differential scanning calorimeter of claim 1.
3,, it is characterized in that element comprises reference and example platform, fixed underpan, Chi Gai, pool wall and Yin Gai in the described pond according to the described differential scanning calorimeter of claim 1.
4, a kind of method for anticorrosion treatment of differential scanning calorimeter, it is characterized in that element in the pond of differential scanning calorimeter is placed Ni-P or Ni-P-X alloy electroplating bath, form one deck chemistry Ni-P or Ni-P-X amorphous alloy coating on its surface, thickness of coating 2.5 μ m～20 μ m, wherein X is SiC, adamas or α-Al
2O
3
5,, it is characterized in that element comprises reference and example platform, fixed underpan, Chi Gai, pool wall and Yin Gai in the described differential scanning calorimeter pond according to the described method for anticorrosion treatment of claim 4.
6,, it is characterized in that described Ni-P alloy electroplating bath comprises 15-25 grams per liter nickelous sulfate, 10-40 grams per liter inferior sodium phosphate, 20-30 grams per liter Sodium acetate trihydrate according to the described method for anticorrosion treatment of claim 4.
7,, it is characterized in that described Ni-P alloy electroplating bath pH value is 4.8-5.3 according to the described method for anticorrosion treatment of claim 6.
8, according to the described method for anticorrosion treatment of claim 4, it is characterized in that the coating operating conditions is: heated solution is immersed in Ni-P or the Ni-P-X alloy electroplating bath 20-60 minute with element in the pond.
9, according to the described method for anticorrosion treatment of claim 4, it is characterized in that described SiC, adamas or α-Al
2O
3Be that granularity is the particulate of 0.5～5 μ m.
10, according to the described method for anticorrosion treatment of claim 9, it is characterized in that described SiC, adamas or α-Al
2O
3Content in alloy electroplating bath is 10～15 grams per liters.
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