Abstract:
The life of chromium phosphate coating baths is extended by at least fully restoring depleted Cr VI  ; bath efficiencies are significantly improved.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to H 3  PO 4  /CrO 3  coating baths for metal surfaces, and in particular to a method for extending the useful life of known H 3  PO 4  /CrO 3  coating baths and to a method of applying chromium phosphate coatings. 
     2. Statement of the Related Art 
     In order to deposit high-weight chromium phosphate coatings on metal surfaces (e.g., more than about 300 mg/ft 2  or about 3.24 g/m 2 ) active coating baths are employed to treat the substrate, causing high levels of displaced metal ions to build up rapidly in the bath. Since the presence of these ions in excess results in loose, powdery coatings, the baths must be discarded and renewed at frequent intervals, which is expensive and also creates waste disposal problems. A particular problem is presented by zinc-bonded aluminum surfaces of the type prepared by processes such as the ALFUSE process, (trademark of Modine Mfg. Corp., Racine, Wisc., U.S.A.) in which high zinc deposition ratios are employed. The use of an active H 3  PO 4  /CrO 3  coating bath on these substrates results in high levels of dissolved Zn and Al in the bath, which interfere with the coating process and rapidly decrease the useful life of the bath. Although replenishers for renewing H 3  PO 4  /CrO 3  baths are commercially available, such prior art replenishers characteristically have CrO 3  and H 3  PO 4  ratios comparable to fresh bath ratios; as a result, the useful life of baths replenished with these materials is not usually remarkably extended. 
     DESCRIPTION OF THE INVENTION 
     This invention relates to a method for replenishing used H 3  PO 4  CrO 3  coating baths employed in the production of chromium phosphate coatings on aluminum surfaces, especially zinc bonded aluminum surfaces and to a method of applying the chromium phosphate coatings. It has been found that increasing the relative CrO 3  (hexavalent chromium or Cr VI ) content of the used coating bath effectively counteracts the tendency of the chromium phosphate coatings to become loose and powdery as the dissolved aluminum content of the bath increases over time. The concept is particularly applicable to aluminum metal surfaces coated with zinc or similar metals, especially those produced by deposition of zinc from a zinc chloride flux onto an aluminum surface such as that produced by the above mentioned ALFUSE process. 
     According to the present invention, the metal substrate is treated with a conventional H 3  PO 4  /CrO 3  coating bath. Such baths typically contain a mole ratio of H 3  PO 4  to CrO 3  of about 2.5-3.0:1, preferably about 2.80-2.90:1, and have a usual hydrofluoric acid content of about 0.5 to about 2.0 grams per liter. Exemplary commercial replenisher formulations for these baths include ALODINE® 401, 405, 406 and 407, (proprietary compositions of Amchem Products, Inc., Ambler, Pa., U.S.A.), which contain representative mole ratios of H 3  PO 4  to CrO 3  of about 2.90:1.0 at concentrations of H 3  PO 4  and CrO 3  of about 650 g/l (grams/liter) and 225 g/l, respectively. Coating baths containing about 28 g/l H 3  PO 4  and about 10 g/l CrO 3  are typically prepared by appropriate dilution of these replenisher formulations, usually to about 4-5% by volume. HF is then added to activate the bath sufficiently to obtain coatings of the desired weight on the metal substrate. 
     As previously noted, coating weights in excess of about 300 mg/ft 2  require an active bath, wherein dissolved metal from the substrate rapidly builds up in the bath. Generally at a dissolved metal content above about 10 g/l, reaction products in these coating baths, especially dissolved aluminum and zinc, begin to promote loose and powdery coatings. At this point, conventional baths are considered to be exhausted, and are discarded. It has unexpectedly been discovered, however, that replenishment of these coating baths with a replenisher composition having an unusually high relative CrO 3  content markedly extends the useful life of the bath. While the present concept is particularly applicable to coating processes adapted to produce relatively heavy coatings of from about 300-450 mg/ft 2 , the concept is broadly applicable to processes for producing a chromium phosphate coating having a weight of from about 5 to 600 mg/ft 2 . (0.054 to 6.48 g/m 2 ). 
     In accordance with the present invention, the CrO 3  content of a used coating bath is increased at least about sufficiently to restore the bath to at least its original CrO 3  concentration usually of about 10 g/l and preferably up to about 150% of its original concentration usually of about 15 g/l, while maintaining the H 3  PO 4  content of the bath substantially constant. Surprisingly, the adverse effects of the high metal ion content of the bath are thus effectively counteracted, and a two-to threefold increase in bath life is usual. The addition can be repeated as required, until no longer effective. 
     The CrO 3  content of the coating bath can be gradually replenished or increased on a continuing basis or an appropriate amount of CrO 3  may be repeatedly added batchwise as the bath nears exhaustion. Exhausted baths are characterized by the production of loose and powdery coatings, attributable to an excessive dissolved metal content. Dissolved metal content can be conveniently monitored by determination of the Cr III  content by known methods. While particular systems will vary, a bath concentration of CR III  of about 1/3 of starting Cr VI  concentration generally signifies imminent bath exhaustion, and the bath should be renewed at or before this point. Exhaustion of the bath is also characterized by decreasing bath efficiency (wt. dissolved metal/wt. of coating produced). Generally, as the bath deteriorates, the weight of dissolved metal increases and, also, the coating weight decreases, with significant concomitant losses in coating efficiency. Increasing the hexavalent chromium concentration of a used bath according to the present invention not only yields tight coatings at relatively high dissolved metal concentrations (e.g., 20 or more g/l dissolved metal), but also significantly improves bath efficiency, as will be shown in the examples which follow. To restore the coating baths according to the invention, a sufficient amount of CrO 3  is added to the used bath to restore the Cr VI  content thereof to at least about the levels present in the fresh bath; a typical bath containing about 10 g/l of CrO 3  when fresh will require an increase in concentration of at least about 0.034 moles CrO 3  near the exhaustion point to restore bath efficiency, if the exhaustion point is taken as the point wherein about 1/3 of Cr VI  has been reduced. 
     To achieve this end, replenishers having a mole ratio of H 3  PO 4  to CrO 3  substantially lower than the comparable ratios in prior art make-up and replenishers are conveniently employed. Replenishers having a H 3  PO 4  to CrO 3  mole ratio of about 1.10 to 1.25:1 are suitable, and those having a mole ratio (H 3  PO 4  :CrO 3 ) of about 1.13 to 1.18:1 are particularly suitable. Such replenishers contrast sharply with prior art replenishers having characteristic H 3  PO 4  :CrO 3  ratios in excess of 2.80:1. 
    
    
     The following Examples are illustrative of the practice of the invention. 
     EXAMPLES 
     A. 
     Methods 
     1. Cr III  Determination: RT-AT v. Total Aluminum Dissolved. 
     RT is &#34;Reaction Titration&#34; (total Cr +6  and Cr +3 ) and AT is &#34;Alodine® Titration&#34; (Cr +6  titration). To monitor dissolved aluminum, Cr +3  is oxidized and then titrated as Cr +6  by known methods. The difference (RT-AT) represents the amount of Cr +3  present in the used bath, which is a measure of the amount of dissolved (oxidized) metal present. The amount of Cr +3  in the bath is easily determined by this titration and provides a quick method for determination of dissolved metal, by calculation against a standard (RT-AT v. total metal dissolved). In an exemplary application: a fresh bath with no metal dissolved contains 10 g CrO 3  per liter (0.1 mole); for this bath, 15 mL 0.1N thiosulfate is required to starch endpoint on a iodimetric titration using a 5 mL aliquot. When the used bath attains an RT-AT value of 20RT-15AT=5.0, by calculation to standard approximately 11.5 g per liter of dissolved metal as aluminum and zinc is present in the bath, and loose coatings are almost certain in baths formulated for 300 to 400 mg per sq.ft. of coating weight. An RT-AT of 5.0 in this system calculates as 3.34 g/L of reduced CrO 3 , or 0.034 moles. A new bath adjustment is required by the time the reduced CrO 3  (Cr +3 ) reaches 1/3 of the concentration of the original hexavalent Cr content. 
     2. Bath Efficiency Determination 
     As coatings are formed, some metal dissolves from the surface of the substrate parts. The efficiency of the bath is determined by comparing the initial weight of a substrate part with the coated and stripped substrate part weights. The part is weighed and processed through the bath; the coated weight of the part is noted, the coating is then stripped, and the stripped weight of the part noted. For an example, in a 4&#34;×6&#34; aluminum panel: 
     (1) Initial Wt.=24.8755 g 
     (2) Coated Wt.=24.9719 g 
     (3) Stripped Wt.=24.8333 g 
     Bath efficiency is defined herein as the weight of metal dissolved per unit of coating weight produced, and calculated as follows: 
     
         Initial wt. less stripped wt.=metal dissolved 
    
     
         Coated wt. less stripped wt.=coating wt. 
    
     In this case No. 1-No. 3 is the metal dissolved, or 42.2 mg. The coating weight is calculated from No. 2-No. 3 as 138.6 mg of coating produced on this panel. Then, ##EQU1## 
     An increase in the calculated efficiency value reflects a decrease in the efficiency of the bath. 
     For example, the same bath which has reached exhaustion may have the following exemplary efficiency: 
     (1) Initial Wt. of aluminum part: 24.5290 g 
     (2) Coated Wt. of aluminum part: 24.5990 g 
     (3) Stripped Wt. of aluminum part: 24.4690 g 
     (Employing comparable 4&#34;×6&#34; aluminum panels). The bath efficiency is ##EQU2## Thus, for each gram of coating produced, 0.461 grams of aluminum is being dissolved into the bath with equivalent reduction of Cr VI  to Cr III . Note that both the dissolved metal value has increased and coating weight values have decreased over the comparable values in the preceding calculation, indicating that both increased metal content and decreased coating weight may result from bath exhaustion, and that either or usually both these phenomena may contribute to decreased bath efficiency. (It is noted that coating weights are usually expressed in weight per sq. ft. of surface; since the surface area is constant in these determinations, this parameter is omitted. As the test panels have a surface area of 1/3 sq. ft., coating weights in mg/ft 2  are here obtained by multiplying coating weight in mg. by 3.) 
     EX. I 
     Replenisher Formulation 
     A replenisher is prepared as follows: 
     350 g CrO 3  and 330 ml 75% H 3  PO 4  are combined with water to a total volume of 1 liter. 
     The H 3  PO 4  :CrO 3  mole ratio is 3.987:3.5=1.139:1 (350 g CrO 3/1  and 390.72 g H 3  PO 4/1 ). 
     EX. II 
     Replenisher Formulation 
     A replenisher is prepared as follows: 
     327 g CrO 3  is admixed with 325 mL 75% H 3  PO 4 , and H 2  O to a total volume of 1 liter. 
     The H 3  PO 4  :CrO 3  mol ratio is 1.20:1 (327 g CrO 3/  l and 386.9 g H 3  PO 4/  l). 
     EX. III 
     Coating Process According to Invention 
     A field trial was conducted on a prior art bath close to exhaustion. The CrO 3  content of this bath was increased by 3.34 g per liter or 0.034 moles to a Cr O   3  concentration of 13.34 g/l from the original concentration by addition of CrO 3 . Table 1 below shows the results of this increase in hexavalent chromium while holding H 3  PO 4  and HF constant. 
     
                       TABLE 1______________________________________Value       Before Adjustment                     1/2 hr After Adjustment______________________________________AT (sodium  14.3          19.4thiosulphate)(ml)RT (ml)     21.1          26.4RT-AT (ml)  6.8           7.0Zinc (g/l)  7.25          7.20Aluminum (g/l)       7.55          7.40Initial Wt. (g)       25.6434       24.5290Coated Wt. (g)       25.7210       24.6230Stripped Wt. (g)       25.5791       24.4738Efficiency  0.453         0.368Coating Wt. 425.7         448.8(mg/ft.sup.2)______________________________________ 
    
     Note the improvement in bath efficiency and increase in coating weight. After the first adjustment, this bath was replenished with replenisher according to Example I for two more days with continued success until one 55 gallon drum was used. Subsequent efficiencies over the course of this one 55 gallon drum of replenishment were 0.347, 0.357, 0.365, 0.371 and 0.380. At termination, the bath contained 9.85 g zinc and 11.5 g aluminum per liter or a total of 21.4 g of metal. Prior baths could only tolerate about 12 or 13 g/l of dissolved metal before producing loose coatings. (cf. Ex. V). 
     The following table shows the laboratory titrations, including free acid (F.A.) and total acid (T.A.). The free acid values indicate that the reduced phosphoric acid in the replenisher employed was at a high enough concentration to keep the free acid at a constant level. 
     
                                           TABLE 2__________________________________________________________________________Sample                              g/lNo. Time   Comment          AT RT RT - AT                      FA TA pH Zn Al Metal                                         Efficiency__________________________________________________________________________1   Wed.   Table/bath          14.3             21.1                6.8   2.3                         8.4                            1.54                               7.25                                  7.55                                     14.80                                         0.453    0700   before   adjustment2   Wed.   Add 3.34          19.4             26.4                7.0   2.4                         8.7                            1.54                               7.20                                  7.40                                     14.60                                         0.368    0730   g CrO.sub.3 /L3   Wed.   Adding 21.8             30.0                8.2   2.5                         9.3                            1.40                               8.15                                  9.55                                     17.70                                         0.357    1500   Ex. I   Replenisher4   Thurs.   End of addn.          24.1             35.8                11.7  2.5                         10.5                            1.52                               9.30                                  10.95                                     20.25                                         0.365    1000   of Ex. I   Replenisher5   Thurs.   No     22.3             34.5                12.2  2.5                         10.5                            1.58                               9.85                                  11.55                                     21.40                                         0.371    1330   Additions6   Thurs.   Discard          21.7             34.5                13.0  2.5                         10.6                            1.63                               10.30                                  12.10                                     22.40                                         0.368    1500__________________________________________________________________________ 
    
     The run ended at Thurs. 1500, at which time the bath was discarded. Note the F.A. remained constant, which indicates sufficient H 3  PO 4 . No. 2 had 0.368 efficiency after CrO 3  addition; thereafter efficiency slightly decreased from 0.357 to 0.368 at discard time. 
     No partial bath stabilization was done. In typical prior art systems, 20% of the bath is discarded at noon and 30% at 3 p.m. of each day of operation to stabilize the bath and prolong useful life. The present invention thus saves on make-up chemical, and expense of disposing of discarded bath. 
     EX. IV 
     Coating Process According to Invention 
     A comparable field test was run with the replenisher of Ex. II, a diluted version of the replenisher employed in Ex. III. As a comparison with the bath composition used in Example V below, the bath ran for a week without stabilization. The metal content of the bath rose to 16 g/l zinc and 16 g/l aluminum with a RT-AT value of 15 mL without producing powdery coatings and while maintaining a bath efficiency below 0.45. In this same amount of time, twice the volume of a conventional bath would have been dumped via bath stabilization (i.e., discard of bath and replenishment with equal volume of prior art replenisher). 
     EX. V 
     Comparison Example--Prior Art Coating Process 
     The following data represents a prior art field run. A commercial bath (28 g/l H 3  PO 4 , 10 g/l CrO 3 ) was monitored from start to finish. The typical buildup of aluminum and zinc is shown in the following chart. Analysis via atomic absorption on the samples taken at 8 a.m., noon, and 3 p.m. are presented. At 3 p.m., a portion of the bath was discarded, and water and an additional quantity of the above commercial bath (mole ratio of CrO 3  :H 3  PO 4  of 1.0:2.89; 227 g/l CrO 3 , 645 g/l H 3  PO 4 ) were added to reduce the dissolved metal (Al+Zn) content for the next day&#39;s run. 
     
                       TABLE 3______________________________________Concentration in ppmDAY     TIME    ZINC      ALUMINUM  METAL______________________________________1       8 a.m.    1         0         1   Noon    1097       591      1688   3 p.m.  2050      1131      31812       8 a.m.  1750       981      2731   Noon    1825      1016   3 p.m.  1902      1151      30533       8 a.m.  1618       909   Noon    2267      1371   3 p.m.  2534      1576      41104       8 a.m.  2257      1470   Noon    2680      2040   3 p.m.  3738      2576      63145       8 a.m.  3012      1996   Noon    4012      2782   3 p.m.  4655      3359      80146       8 a.m.  3881      2660   Noon    4741      3255   3 p.m.  5283      3583      88667       8 a.m.  4351      2974   Noon    5189      3491   3 p.m.  5771      3827      95988       8 a.m.  4586      3064   Noon    5243      3563   3 p.m.  5786      3892      96789       8 a.m.  4619      3117   Noon    5333      3493   3 p.m.  5991      3875      986610      8 a.m.  4881      3249   Noon    5643      3768   3 p.m.  6571      4032      10,603______________________________________ 
    
     As is apparent, even with daily bath stabilization, the total dissolved metal content reached 10.6 g/l. At this time loose coatings were persistent and the total bath as discharged to treatment and disposal.